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WO2024126267A1 - Biodegradable graft polymers - Google Patents

Biodegradable graft polymers Download PDF

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Publication number
WO2024126267A1
WO2024126267A1 PCT/EP2023/084824 EP2023084824W WO2024126267A1 WO 2024126267 A1 WO2024126267 A1 WO 2024126267A1 EP 2023084824 W EP2023084824 W EP 2023084824W WO 2024126267 A1 WO2024126267 A1 WO 2024126267A1
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WO
WIPO (PCT)
Prior art keywords
sub
unit
block
vinyl
monomer
Prior art date
Application number
PCT/EP2023/084824
Other languages
French (fr)
Inventor
Jan Ole MUELLER
Ouidad Benlahmar
Sophia Ebert
Florian Schoen
Kian Molawi
Adam BLANAZS
Rosa Corberan Roc
Frank Huelskoetter
Pieter Jan Maria Saveyn
Renae Dianna Fossum
Gang SI
Katarzyna GORCZYNSKA COSTELLO
Natalia STERGIOPOULOU
Original Assignee
Basf Se
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Publication of WO2024126267A1 publication Critical patent/WO2024126267A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers

Definitions

  • the present invention relates to novel graft polymers comprising a polymer backbone (A) as a graft base having polymeric sidechains (B) grafted thereon.
  • the polymeric sidechains (B) are obtainable by (co-)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), and optionally further monomer(s) (B3), and optionally further monomers.
  • the polymer backbone (A) is made from at least two sub-units (a1) and (a2), wherein (a1) is derived from at least one alkylene oxide monomer, and (a2) is a unit derived from at least one lactone and/or at least one hydroxy acid.
  • the present invention further relates to a process for obtaining such a graft polymer, the process is preferably carried out by polycondensation. Furthermore, the present invention relates to the use of such a graft polymerwithin, for example, fabric and home care products.
  • Another subject-matter of the present invention are compositions comprising at least one graft polymer, such as fabric and home care products.
  • Polyalkylene oxides are important polymers with a wide range of applications. They have been extensively used as basis to produce graft polymers which are widely employed in consumer formulations, including cleaning compositions for household and other uses.
  • graft polymers of a vinylester being grafted onto polyalkylene oxide-polymers such as vinylacetate-graft-polyethylene glycol are known polymers. Their application in the detergent area as well as many other application areas are known as well.
  • biodegradability is one of the upcoming very important features not only in the area of detergents, as a biodegradable polymer can avoid the issue of building up in the environment.
  • the functionalities imparted by such polymers is of utmost importance as well, as they allow for high cleaning efficiencies and thus among other advantages also for a low use of cleaning additives for a single cleaning run, and thus allow for saving material used and hence avoid also the pollution of the environment.
  • those specialty polymers also allow for cleaning at lower temperatures, in shorter times and with lower amounts of water, they are needed for an environment-friendly cleaning process.
  • bio-degradable polymers for the area of detergents is of utmost importance to solve the problem of pollution of the environment without compromising cleaning efficiency, as such lower cleaning efficiency would also pollute the environment more than unavoidable.
  • One such widely known polymer is a graft polymer of vinyl acetate on PEG6000 with a wt. ratio 60% (VAc) to 40% (PEG) known and employed widely for its cleaning and whiteness benefits in liquid laundry formulations (liquid and gel-like detergents).
  • polyalkylene oxides decreases in the range from a few hundred g/mol molecular weight up to a few thousand g/mol molecular weight. Even more so, graft polymers based on such polyalkylene oxides are usually even poorer in their biodegradation likely due to the grafting.
  • US 2019/0390142 relates to fabric care compositions that include a graft copolymer, which may be composed of (a) a polyalkylene oxide, such as polyethylene oxide (PEG); (b) N- vinylpyrrolidone(VP); and (c) a vinyl ester, such as vinyl acetate.
  • a graft copolymer which may be composed of (a) a polyalkylene oxide, such as polyethylene oxide (PEG); (b) N- vinylpyrrolidone(VP); and (c) a vinyl ester, such as vinyl acetate.
  • PEG polyethylene oxide
  • VP N- vinylpyrrolidone
  • a vinyl ester such as vinyl acetate
  • W02020/005476 discloses a fabric care composition
  • a fabric care composition comprising a graft copolymer and a so- called treatment adjunct, the graft copolymer comprising a polyalkylene oxide as backbone based on ethylene oxide, propylene oxide, or butylene oxide, preferably poly ethylene oxide, and N-vinylpyrrolidone and vinyl ester as grafted side chains on the backbone and with backbone and both monomers in a certain ratio.
  • W02020/264077 discloses cleaning compositions containing a combination of enzymes with a polymer such composition being suitable for removal of stains from soiled material.
  • This publication discloses a so-called “suspension graft copolymer” which is selected from the group consisting of poly (vinylacetate)-g-poly (ethylene glycol), poly(vinylpyrrolidone)- poly(vinyl acetate)-g-poly(ethylene glycol), and combinations thereof.
  • the graft polymer as defined in this invention however is not disclosed.
  • US31816566 discloses graft polymers of so-called “lactone polyesters” and blends thereof with PVC.
  • the lactone polyesters are either homo-polymers of epsilon-caprolactone or copolesters thereof with epsilon-alkyl-epsilon-caprolactones. No polymers are disclosed being made from lactones and alkyleneoxides as in the present invention used as graft bases.
  • the lactone polyesters of US31816566 were grafted with ethylenically unsaturated monomers, among a long list also “vinyl esters of aliphatic acids” are mentioned, with vinyl formate, vinyl acetate and vinyl propionate being exemplified in this list.
  • the 22 examples show graft polymerization using acrylic acid, butylacrylate, dimethylaminomethacrylate, styrene, acrylonitrile, and methylmethacrylate as the only monomers actually being employed, all only as single monomer and no monomer mixtures being employed.
  • Only one example uses vinyl acetate as monomer and poly-epsilon-caprolactone as graft base (i.e. a graft base not comprising any alkylene oxide), employing 200 gram of backbone and 30 gram of vinyl acetate, i.e.
  • WO2022/136409 of BASF discloses amphiphilic alkoxylated polyalkylene imines or amines; no graft polymers are discloses comprising a polymer as graft backbone made from lactones and alkylene oxides being grafted in a radical polymerization with olefinically unsaturated monomers comprising at least a vinyl ester.
  • his publication is completely unrelated to the present invention except to the fact that it also targets polymeric structures for use in areas similar to those of the present invention, and in that those products comprise lactone and alkylene oxides.
  • lactones and alkylene oxides are polymerized to produce lactonealkylene oxide-copolymers which are attached to the amine groups of the starting compound polyethylene imine or polyamine. No graft polymerization is performed after the formation of those side chains. Thus, the structures and their preparation are completely different as well as the properties and thus the function in the application of such compounds. Graft polymers of the types shown in this invention are not disclosed nor pointed at.
  • US2022/0056380 discloses cleaning compositions focusing on specific enzymes, thus there is no focus on a specific polymer as such, its structure or preparation or properties.
  • graft polymers are mentioned as an ingredient.
  • the graft polymers however are the typically, known graft polymers (such as the preferred mentioned “Sokalan® HP22 of BASF” - all of which do not contain a lactone in the backbone of the polymer, thus such backbone being made only of alkylene oxides.
  • alkylene oxides - and especially the preferred polymers of molecular weight of the backbones of around 6000 g/mol are not very much biodegradable at all, with the graft polymers being made with the use of such polyalkylene oxide-backbones having an even poorer biodegradation as shown in this present invention.
  • Graft polymers of the types shown in this invention are not disclosed nor pointed at. All the prior art graft polymers use no polymers made from lactones and alkylene oxides as backbone; thus, the biodegradation of those polyalkylene oxides is low or neglectable, whereas the polyesters might show good biodegradation but a poor performance in the intended application areas, and also are typically not well suited for graft polymerization.
  • the polymers in this disclosure suffer from the two-step-synthesis for the backbone: the oxidation as first reaction step is expensive and lengthy, and the composition obtained from the oxidation is difficult to control, as - depending on the time taken for the reaction - the content of the mixture changes.
  • the mixture obtained contains non-oxidized starting material, polyalkylene oxides with one hydroxy-group being oxidized to carboxyl-function and polyalkylene oxides with both ends being oxidized.
  • the flexibility of designing the backbone is highly limited.
  • This present invention discloses the uses of three main types of polymeric backbones comprising (oligo-Zpoly-)alkylene oxide-moieties and (oligo-/poly-)lactone/hydroxy acid- derived moieties.
  • W02002046268 discloses biodegradable polymers as surfactants, emulsifier etc., obtained by reacting an organic initiator with 1. alkylene oxides, 2. mixture of alkylene oxides and lactones.
  • Organic initiator is defined on page 4 as mono- or polyfunctional alcohol or amine.
  • Alcohols with 2 hydroxy groups are used as starters.
  • diols are: ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1 ,3-propylene diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, and the like.
  • Used alkylene oxides in combination with caprolactone are: ethylene oxide, 1 ,2-propylene oxide or 1 ,2-butylene oxide, 2,3-butylene oxide, 1 ,2-pentylene oxide, preferred ethylene oxide and propylene oxide.
  • the copolymerization of alkylene oxides and caprolactone is carried out under typical conditions for alkoxylation reactions.
  • Basic catalysts are used like potassium hydroxide, sodium hydroxide, sodium methoxide, potassium methoxide.
  • (A2)-backbone-type polymers can be obtained in principle by alkoxylation of polylactones.
  • Polylactones are for example accessible by polymerization of lactones such as caprolactone onto starters having 2 hydroxy-groups such as diols like ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1 ,3-propylene diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, and the like.
  • the alkoxylation of such polycaprolactones is done under typical alkoxylation conditions. Due to basic reaction conditions for the alkoxylation, transesterification reaction at ester bonds from polycaprolactone can occur.
  • US4281172 describes acrylic acid esters from polyester-polyether copolymers. To obtain these structures, a polylactone ester from mono-, di-, tri-, or tetraols, is reacted with alkylene oxides.
  • the polylactone esters are synthesized according to US3169945 from a hydroxy group - containing component with various catalysts, including Ti or Sn catalysts or alkali metal hydroxides.
  • the alkoxylation reaction is catalyzed with BF3-etherate or potassium hydroxide etc.
  • JP07149883 describes the process to obtain polyester-polyols from a compound with at least two active hydrogen, reacted with a lactone, followed by reaction with alkylene oxide. Both reactions are carried out with the same catalyst.
  • Catalysts are alkali metal hydroxides or alkali metal alcoholates.
  • WO9636656 claims biodegradable alkylene oxide-lactone copolymers.
  • the polymers are synthesized from a di- or polyfunctional starter, that are reacted with alkylene oxide and lactones in a copolymerization reaction, followed by an end-cap with an alkylene oxide block.
  • Catalysts are alkali metal hydroxide or earth alkali metal hydroxide or Lewis acid.
  • the patent application describes improved biodegradability of claimed polymers over polyalkylene oxides, and use as surfactants, emulsifiers etc. but not as backbones for graft polymers.
  • (A3)-backbone-type polymers can be obtained in principle by poly-esterification of polyalkylene glycols with lactones yielding - simplified - tri-block-polymers.
  • Triblock copolymers from caprolactone and alkylene oxides with a middle polyalkylene oxide block are synthesized by 1 . formation of a polyalkoxylate from a diol or water by reaction with alkylene oxides, and 2. polymerization of caprolactone onto the polyalkoxylate.
  • Such triblock copolymers with a middle polyethylene oxide block are known since about the 1990s. These polymers are used for drug release and solubilization purposes (Z. Zhu et al., Journal of Polymer Science, Part A: Polymer Chemistry 1997, 35 (4), 709-714; M. Boffito et al., Journal of Biomedical Materials Research, Part A 2015, 103A (3), 1276-1290).
  • WO96/36656 discloses biodegradable oxide-lactone copolymers and copolyesters as already described for (A3) above.
  • W02002046268 (Cognis, now BASF) discloses alkylene oxide-lactone copolymers as already described for (A1).
  • the graft polymers based on conventional polyalkylene oxides show a surprisingly low biodegradation, which is often very much lower than the expected biodegradation percentage, which is calculated on the biodegradation of the pure polyalkylene oxides.
  • the graft polymers being based on such conventional polyalkylene oxides commonly show a decrease in biodegradation compared to the unmodified polyakylene oxides and unmodified polyalkylene glycols, as the degree of modification of polyalkylene oxides (often polyalkylene oxides with two hydroxy-end groups are employed, thus such polyakylene oxides with hydroxy-groups being named commonly “polyalkylene glycols”) with polymerizable monomers by radical grafting onto such backbones increases (i.e. the number of side chains on the backbone increases).
  • the object of the present invention is to provide novel graft polymers based on polyalkylene-oxide-type graft backbones which impart ester-functions.
  • novel graft polymers should have beneficial properties in respect of biodegradability and/or their washing behavior, when being employed within compositions such as cleaning compositions.
  • the graft polymers of the invention comprise a polymer backbone as graft base as a first structural unit and polymeric side chains as a second structural unit.
  • the first structural unit of the graft polymer is a polymer backbone used as a graft base for the inventive graft polymer, wherein said polymer backbone (A) is obtainable by polymerization of at least one sub-unit (a 1 ) and at least one sub-unit (a2).
  • the sub-unit (a1) is made from least one alkylene oxide monomer and/or at least one
  • the alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides, such as ethylene oxide, 1 ,2 propylene oxide, 1 ,2 butylene oxide, 2,3 butylene oxide, 1 ,2- pentene oxide or 2,3 pentene oxide; from 1 ,4-diols or their cyclic or oligomeric analogs, or being based on polymeric ethers of such 1 ,4-diols; from 1 ,6-diols or their cyclic or oligomeric analogs, or being based on polymeric ethers of such 1 ,6-diols; or any of their mixtures in any ratio, either as blocks of certain polymeric units, or as statistical polymeric structures, or a polymers comprising one or more homo-block(s) of a certain monomer and one or more statistical block(s) comprising more than one such monomer, and any combination thereof such as polymers
  • block (co)polymer as used herein means that the respective polymer comprises at least two (i.e. two, three, four, five or more) homo- or co-polymer subunits (“blocks”) linked by covalent bonds.
  • “Two-block” copolymers have two distinct blocks (homo- and/or copolymer subunits), whereas “triblock” copolymers have, by consequence, three distinct blocks (homo- and/or co-polymer subunits) and so on.
  • the number of individual blocks within such block copolymers is not limited; by consequence, a “n-block copolymer” comprises n distinct blocks (homo- and/or co-polymer subunits).
  • the size/length of such a block may vary independently from the other blocks.
  • the smallest length/size of a block is based on two individual monomers (as a minimum), but may be as large as 50 or even 100 or 200, and any number in between 2 and 200.
  • the respective monomers to be employed for preparing the individual blocks of a block copolymer backbone (a1) may be added in sequence. However, it is also possible that there is a transition of the feed from one monomer to the other to produce so called “dirty structures” wherein at the edge/border of the respective block a small number of monomers of the respective neighboring block may be contained within the individual block to be considered (so called “dirty structures” or “dirty passages”).
  • the block copolymer subunits (a1) according to the present invention do not contain any dirty structures at the respective border of the blocks, although for commercial reasons (i.e. mainly cost for efficient use of reactors etc.) small amounts of dirty structures may still be contained although not deliberately being made.
  • At least one monomer in the polymer stems from the use of ethylene oxide.
  • more than one alkylene oxide monomer is comprised in the structure of the polymer-subunit (A1); in such case the polymer backbone is a random copolymer, a block copolymer or a copolymer comprising mixed structures of block units (with each block being a homo-block or a random block itself) and statistical /random parts comprised of two or more alkylene oxides, with one of the monomers being ethylene oxide.
  • the further monomer beside ethylene oxide is propylene oxide (PO) and/or 1 ,2-butylene oxide (BO), preferably only 1 ,2-propylene oxide.
  • the sub-unit (a2) is made from at least one lactone and/or at least one hydroxy acid.
  • the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e. cyclic esters, starting with a-lactone (three ring atoms) followed by p- lactone (four ring atoms), y-lactone (five ring atoms) and so on; such lactones preferably being p-propiolactone, g-butyrolactone, b-valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; and ii) hydroxy acid(s), which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, specifically an a-, p- or y-hydroxy acid derived from the corresponding lactone by hydrolyzation, and lactic acid, glycolic acid, 4-
  • the sub-units (a1) and (a2) may be combined in any order depending on how the starting material are employed and depending on the relative amounts.
  • the polymer backbone (A) obtained from the reaction of (a1) and (a2) can be defined in a very broad range by selecting the desired sub-units (a1) and (a2), and - within sub-unit (a1) by selecting the number of different alkylene oxides, their relative amounts, their reaction order etc, and of course also for (a2) by selecting the compounds, their relative amounts etc., in such way
  • sub-units (a2) can be added during alkylene oxide polymerization (a1 -units) yielding random copolymers; in a variation thereof, polyalkylene oxides having two hydroxy-groups can be added to such polymerisation thus introducing specific (al)-sub-unit-blocks; this variation is useful if the alkylene oxides employed are at least partially different to the alkylene oxides employed for preparing the polyalkylene oxide also employed or if the structure of the polyalkylene oxide (i.e. the order of the alkylene oxide-units therein) is different to what is obtained by reacting the at least one alkylene oxide employed for the co-polymerisation with (a2)-sub-unit and the polyalkylene oxide.
  • this (Al)-backbone can be described as a randomly arranged order of (al)-sub-units and (a2)-sub-units. Depending on the relative amount of (a1) to (a2) and their reactivity the block length of the (a1) and the (a2) is varied.
  • oligo/poly lactone depicts the (a2)-sub-unit, thus made from lactone(s)/hydroxy acid(s);
  • PAG polyalkylene glycol is used here to depict the (al)-sub-unit)
  • the polymer backbone is selected from (A1) a backbone consisting of a randomly arranged order of monomeric, oligomeric and/or polymeric (al)-sub-units and monomeric, oligomeric and/or polymeric (a2)-sub-units, with more than one sub-unit (a1) and/or more than one sub-unit (a2) being present.
  • sub-units (a2) can be oligomerized/polymerized first and the co-polymerized with at least one alkylene oxide yielding mixed random/block structures; depending on the degree of oligomerization of the lactone/hydroxy-acid and if still monomeric lactone /hydroxy acid is present when the alkylene oxide(s) is/are added, the structure can be further varied by tuning the amount and length of (a2)-sub-unit-chains within the (A2)-backbone.
  • polyalkylene oxides having two hydroxygroups can be added to such polymerisation thus also introducing specific (a1 ⁇ sub-unit- blocks; this variation is useful if the alkylene oxides employed are at least partially different to the alkylene oxides employed for preparing the polyalkylene oxide also employed or if the structure of the polyalkylene oxide (i.e. the order of the alkylene oxide-units therein) is different to what is obtained by reacting the at least one alkylene oxide employed for the copolymerisation with (a2)-sub-unit and the polyalkylene oxide.
  • this (A2)-backbone can be described as a tri-block-polymer with an inner (a2)-block and two outer (al)-blocks.
  • lactone is used here to denote the (a2)-sub-units, thus made from lactone(s)/hydroxy acid(s) and can be single monomeric units or oligo- or polymeric units made from monomers in a first reaction step;
  • PAG polyalkylene glycol is used here to depict the (al)-sub-unit)
  • the structure will not be anymore a true tri-block structure, but will in addition contain further, shorter (a2)-units in the chains and thus consist of a multi-block- structure or even shift towards a mixture of block and random-structural arrangement.
  • the polymer backbone is selected from (A2) a backbone consisting of oligo- or polymerized sub-units (a2) as an inner block and two outer blocks of oligomeric and/or polymeric (al)-sub-units, defined as “-[block of (a1)]-[block of (a2)]-[block of (a1 )]-”, and also possibly comprising higher block-polymers such as 5-, 7- and 9- etc.
  • blocks where at the outside of the tri-block structure further blocks of (a1) and (a2) are connected, such as a penta-block “ [block of (a1)] - [block of (a2)] - [block of (a1)]-[block of (a2)] - [block of (a1)] - [block of (a2)] - [block of (a1)] “ and so on.
  • sub-units (a2) can be added after alkylene oxide oligomerization or (almost complete) polymerization yielding block structures containing larger (a2)-chains and larger (a1 )-chains; in case of complete polymerization of (a1) before addition of (a2) the structure resulting can be described as “(a2)-polyalkylene oxide-(a2)”; such structures can be also obtained by directly reacting polyalkylene oxides with (a2).
  • this (A3)-backbone can be described as a tri-block-polymer with an inner (al)-block and two outer (a2)-blocks:
  • oligo/poly lactone depicts the (a2)-sub-unit, thus made from lactone(s)/hydroxy acid(s);
  • PAG polyalkylene glycol is used here to depict the (al)-sub-unit)
  • the polymer backbone is selected from (A3) a backbone consisting of and inner block of oligomeric and/or polymeric (al)-sub-units and two outer blocks of oligo- or polymeric sub-units (a2), in the form of at least an tri-block-polymer defined as “ - [block of (a2)]-[block of (a1)] - [block of (a2)]
  • (A1), (A2) and (A3) are “just” extreme ends of the overall principle of co-polymerizing alkylene oxides, polyalkylene glycols and lactones/hydroxy acids in every thinkable order, ratio and variation of reaction times before adding the other starting materials.
  • the polymer backbone is selected from a backbone obtained by such overall principle of co-polymerizing alkylene oxides, polyalkylene glycols and lactones/hydroxy acids in every thinkable order, ratio and variation of reaction times before adding the other starting materials.
  • (A4) is a structure which starts from an oligo- or polymeric sub-unit (a1) which is end-capped on one side, preferably etherified with alcohols, more preferably short-chain alcohols C1 to C4.
  • This one-sided end-capped oligo-/polymer of sub-unit (a1) is then thereafter reacted with at least one sub-unit (a2) and optionally at least one sub-unit (a1) - wherein the sub-unit (a1) may be different to that/those in the starter block or may be arranged in a different order compared to those in the starter block - to attach to the non-endcapped side of the starter block a new block comprising moieties from the sub-units employed for the (copolymerization, thereby obtaining a di-block-structure of
  • oligo- or polymerization of sub-unit(s) (a1) and (a2) can each be effected with the use of “starter molecules”, which are then incorporated into the oligomers and polymers of sub-unit (a1 ) and (a2).
  • Suitable starter molecules for such polycondensation reaction of lactones and hydroxy acids as well as alkylene oxides are known; such compounds comprise at least two hydroxy-groups accessible for condensation reaction, such asdiols like ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1 ,2- and 1 ,3-propane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol and the like.
  • water is a suitable starter molecule.
  • the backbones (A1) to (A4) may comprise moieties derived from such starter molecule, specifically any one or more of water, ethylene glycol, polyethylene glycol, 1 ,2- and 1 ,3-propane diol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol.
  • starter molecule In case where a compound derived from alkylene oxides is used as starter molecule, such use is already described in the backbone definitions above, and thus such starter molecule derived from alkylene oxide can be added as a molecule or can - in case of oligomers or polymers of alkylene oxide(s) - prepared in a first reaction step, before sub-unit (a2) is added for condensation reaction.
  • the use of starter molecules not derived from alkylene oxides however is also encompassed as an option in any of the embodiments herein for any of the backbones disclosed; preferably, such starter molecule is used for the preparation of any such backbone (A1), (A2) and (A3).
  • Typical reaction procedure to obtain such structures is, firstly, the formation of a oligo- /polyalkoxylate from a starter molecule by reaction with alkylene oxide(s) (i.e. sub-units (a 1 )), and then, secondly, further polycondensation reaction sub-unit(s) (a2) onto the polyalkoxylate. Both reactions can be carried out under typical reaction conditions for alkoxylation reactions (to abtain the oligo-/polyalkoxylate) and for polymerization of sub-unit (a2).
  • the polymerization of sub-unit(s) (a2) is carried out in a known way with various catalysts like transesterification catalysts tin(ll)alkanoates.
  • the alkoxylation of such oligo-/poly-[sub-unit(s) (a2)] is done under typical, known alkoxylation conditions. Due to basic reaction conditions for the alkoxylation, transesterification reaction at ester bonds from oligo-/poly-[sub-unit(s) (a2)]can occur and thus lead to compounds having a mixed random / block structures.
  • the polymer backbone as a graft base comprises at least one sub-unit (a1) and at least one sub-unit (a2), wherein
  • (a1) is a unit comprising, preferably essentially consisting of, moieties derived from at least one alkylene oxide monomer and/or at least one polyalkylene oxide-polymer having two hydroxy-end-groups, the alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,
  • (a2) is a unit comprising, preferably consisting of, at least one lactone and/or at least one hydroxy acid, such sub-unit (a2) being a moiety derived from a single lactone and/or hydroxy-acid or being oligo-or-polymeric units consisting of at least one type of lactone and/or at least one type of hydroxy acid, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e.
  • cyclic esters starting with a-lactone (three ring atoms) followed by p- lactone (four ring atoms), y-lactone (five ring atoms) and so on; such lactones preferably being p-propiolactone, g-butyrolactone, b-valerolactone, g-valerolactone, e- caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; and ii) hydroxy acid(s), which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, specifically an a-, p- or y-hydroxy acid derived from the corresponding lactone by hydrolyzation, and lactic acid, glycolic acid, 4- hydroxybutanoic acid, 6-hydroxy hexanoic acid, 12-hydroxy stearic acid, citric acid; preferably lactic acid or caprolactone, more preferably
  • (A1) by co-polymerization of at least one sub-unit (a1) and at least one sub-unit (a2), wherein optionally at least one oligomer or polymer made from at least one sub-unit (a1) or at least one sub-unit (a2) can be employed within the copolymerization of at least one subunit (a1) and at least one sub-unit (a2) as well;
  • (A4) by first providing an oligo- or polymeric sub-unit (a1) which is bears an end-cap on one side, preferably is etherified with alcohols, more preferably short-chain alcohols C1 to C4, which - as starter-block - is thereafter reacted with at least one sub-unit (a2) and optionally at least one sub-unit (a1) - wherein the sub-unit (a1) may be different to that/those in the starter block or may be arranged in a different order compared to those in the starter block - to attach to the non-end capped side of the starter block a new block comprising moieties from the sub-units employed for the (co-)polymerization, thereby obtaining a di-block-structure of [end-cap]-[sub-unit(s) (a1)]-[sub-unit(s) (a2)], or [end- cap]-[sub-unit(s) (a1)]-[random- ⁇ sub-unit(s) (a2)-sub unit(s
  • the polymer backbone (A) and specifically (A1), (A2) and (A3), may be optionally capped at the end groups, the capping is done by C1 C25 alkyl groups using known techniques, preferably C1 to C4-groups. Such capping will be done after the production of the backbones and may be done preferably prior to the grafting.
  • the capping on one end-group is either to be done prior to the condensation polymerization with sub-unit(s) (a1) and/or sub-unit(s) (a2), as only then a structure (A4) can be obtained.
  • the production of the (A4) starts with a mono-alcohol, which is then reacted with alkylene oxide(s) to obtain the “mono-end-capped” oligo/polymer of sub-unit (a1) (bearing one hydroxy-group at the oligo/poly alkylene oxidechain end), which is then reacted with sub-unit(s) (a2) to obtain (A4).
  • a diol When preparing the oligo-/poly-alkylene oxide as a starting block, a diol may be used as a starter molecule for preparing this oligo/poly alkylene oxide, thus such oligo-Zpolymer of sub unit (a1) may contain in its structure a moiety derived from such diol.
  • Diols for such use and methods to prepare such oligo/poly alkylene oxide comprising diols in their structure are known. Typical diols are ethylene glycol, propylene glycol etc. All of the commonly known diols can in principle be used for such purpose.
  • the polymer backbone as a graft base comprises at least one sub-unit (a1) and at least one sub-unit (a2), wherein
  • (a1) is a unit comprising, preferably essentially consisting of, moieties derived from at least one alkylene oxide monomer and/or at least one polyalkylene oxide-polymer having two hydroxy-end-groups, the alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,
  • (a2) is a unit comprising, preferably consisting of, at least one lactone and/or at least one hydroxy acid, such sub-unit (a2) being a moiety derived from a single lactone and/or hydroxy-acid or being oligo-or-polymeric units consisting of at least one type of lactone and/or at least one type of hydroxy acid, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e.
  • cyclic esters starting with a-lactone (three ring atoms) followed by p- lactone (four ring atoms), y-lactone (five ring atoms) and so on; such lactones preferably being p-propiolactone, g-butyrolactone, b-valerolactone, g-valerolactone, e- caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; and ii) hydroxy acid(s), which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, specifically an a-, p- or y-hydroxy acid derived from the corresponding lactone by hydrolyzation, and lactic acid, glycolic acid, 4- hydroxybutanoic acid, 6-hydroxy hexanoic acid, 12-hydroxy stearic acid, citric acid; preferably lactic acid or caprolactone, more preferably
  • (A1) a backbone consisting of a randomly arranged order of monomeric, oligomeric and/or polymeric (al)-sub-units and monomeric, oligomeric and/or polymeric (a2)-sub-units, with more than one sub-unit (a1) and/or more than one sub-unit (a2) being present;
  • (A2) a backbone consisting of oligo- or polymerized sub-units (a2) as an inner block and two outer blocks of oligomeric and/or polymeric (al)-sub-units, defined as “-[block of (a1)]- [block of (a2)]-[block of (a 1 )]-”, and also possibly comprising higher block-polymers such as 5-, 7- and 9- etc.
  • (A3) a backbone consisting of and inner block of oligomeric and/or polymeric (al)-sub-units and two outer blocks of oligo- or polymeric sub-units (a2), in the form of at least an tri- block-polymer defined as “ - [block of (a2)]-[block of (a1 )] - [block of (a2)] and
  • end-cap on one end an end-cap - such end-cap being a C1 to C18-, preferably C1-C4- alkyl-group attached to said first block via an ether-fu notion;
  • polymer backbones (A), and specifically (A1), (A2) and (A3), are not capped but bear hydroxy-groups at the chain ends.
  • the polyalkoxylate-ester backbone comprises moieties derived from
  • alkylene oxides comprising at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably at least one of EO and PO, with the AO in an amount of from 40 to 95, preferably up to 90, and preferably from 50, more preferably from 60, and even more preferably from 70wt%, and any number and range in between, each based on the total weight of the backbone, the amount of EO being of from 0 to 100wt.%, preferably from 10, more preferably from 20, even more preferably from 30, even more preferably from 40, such as from 50, 60, 70, 80 or even from 90wt%, based on total AO, the PO and/or BO, in an total amount of each from 0 to 100 wt.%, preferably up to 90, more preferably up to 80, even more preferably up to 70, even more preferably up to 60, and most preferably up to 50, and any number in between such as up to 5, 10, 15, 25, 30, 35, 40, 45
  • lactone /hydroxy acid monomer in an amount of from 1 and up to 60, preferably up to 50, more preferably up to 40, most preferably up to 30 wt. %, and preferably from 2, more preferably from 3, even more preferably from 4 and most preferably from 5 wt.%, each based on the total weight of the backbone, preferably only caprolactone;
  • the amount of EO is at least 80 wt%, preferably at least about 85, more preferably at least about 90, even more preferably at least about 95%, and most preferably about 100 wt.% based on total AO;
  • the amount of PO and/or BO is each from about 0 to 50 wt.% based on the total weight of AO, more preferably at most about 30, even more preferably at most about 20%, even more preferably about 10, and most preferably about 0 wt.%, each based on total AO; in a more preferred embodiment, the amounts for PO and BO given in this paragraph before are the total amounts for the sum of PO and BO.
  • the backbone-unit (a1) is made from ethylene oxide only.
  • At least two different alkylene oxides are employed for the preparation of the backbone I are present in the backbone.
  • the polymer backbone consists of
  • alkylene oxides being selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably only EO and PO, the amount of EO being of from 10 to 90, preferably 20 to 80, more preferably 30 to 70, and most preferably 40 to 60wt%, based on total AO, the total amount of PO and BO being from 10 to 90, preferably 20 to 80, more preferably 30 to 70, and most preferably 40 to 60wt%, each based on the total weight of AO, with the total amount of PO and BO adding up to 100wt.% for the sum of PO and BO, and with the total amount of AO adding up to 100wt.%;
  • lactone /hydroxy acid monomer in an amount of from 1 and up to 60, preferably up to 40, more preferably up to 30, even more preferably up to 25, even further more preferably up to 20, and most preferably up to 15 wt. %, and preferably from 2, more preferably from 3, even more preferably from 4 and most preferably from 5 wt.%, each based on the total weight of the backbone, preferably only caprolactone; with the total weight of the sum of sub-units (a1) and sub-units(a2) in the backbone (A) adding up to 100 wt%, and wherein in case of (A1 ), (A2) and (A3) the use of a starter molecule is optional.
  • the polymer backbone consists of
  • alkylene oxides is selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably only EO and PO, more preferably only EO the amount of EO being of from 20 to 100 wt%, based on total AO, the total amount of PO and BO being from 0 to 80 wt.%, preferably up to 50, more preferably up to 30, even more preferably up to 20, and even further preferably up to 10, and most preferably zero, such as 45, 45, 45, 25, 15, 7 and 5, and any number in between, each based on the total weight of AO, with the total amount of PO and BO adding up to 100wt.% for the sum of PO and BO, with the total amount of AO adding up to 100wt.%;
  • lactone /hydroxy acid monomer in an amount of from 5 and up to 50, preferably up to 40, more preferably up to 35, and even more preferably up to 30, and as lower limit preferably from 7, more preferably from 10, even more preferably from 12 wt%, and most preferably from 15, such as 6,8, 9, 11 , 12, 13, 14 and 15 and any number in between as lower limit and such as 30, 33, 37, 45 and any number in between as upper limit, based on the total weight of the backbone, preferably only caprolactone; with the total weight of the sum of sub-units (a1) and sub-units(a2) in the backbone (A) adding up to 100 wt%, and wherein in case of (A1 ), (A2) and (A3) the use of a starter molecule is optional.
  • the backbone for any of the embodiments of the inventive graft polymer as defined herein is a structure chosen from the structures (A1), (A2), (A3) and/or (A4).
  • the second structural unit of the graft polymer are polymeric side chains (B), which are grafted onto the polymer backbone (A), wherein said polymeric sidechains (B) are obtainable by (co-)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogencontaining monomer (B2), optionally further monomer(s) (B3), and optionally further monomers besides (B1), (B2) and (B3).
  • vinyl ester monomer (B1) at least one of vinyl acetate, vinyl propionate and/or vinyl laurate is selected. Besides those, further vinyl ester monomers (B1) may be employed which are known to a person skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and/or vinyl benzoate.
  • At least one nitrogen-containing monomer being selected from the group consisting of vinyllactames, vinyl imidazoles, 1 -vinyltriazole, 4-vinylpyridine, 4- vinylpyridine-N-oxide, 2-vinylpyridine, 1-vinyloxazolidinone, N-vinylformamide, N- vinylacetamide, N-vinyl-N-methylacetamide, and acrylamides such as acrylamide, methacrylamide, N-alkyl-substituted acrylamides, N,N‘-di alkyl (meth) acrylamide; mono- and dialkylamino-alkyl-(meth)acrylates, being preferably a vinyllactame-monomer and/or a vinylimidazole-monomer, the vinyllactam being more preferably selected from N- vinyllactams, such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam
  • Further monomers (B3) may be employed as optional monomers, such monomers being different to (B1) and (B2) and being present only in an amount of preferably less than 10% of the total amount of monomers employed for obtaining the polymeric sidechains (B), and are more preferably present only as impurities but not deliberately added for polymerization.
  • (B3) monomers may be any monomer chosen from 1 -vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinyl pyridine-N-oxide, N-vinyl formamide and its amine if hydrolyzed after polymerization, N-vinyl acetamide, N-vinyl-N-methyl acetamide, alkyl esters of (meth)acrylic acid, and their derivatives.
  • At least one further monomer may be present for the co-polymerization to yield the side chains (B), wherein such further monomer is present only in an amount of less than 2% of the total amount of monomers employed for obtaining the polymeric sidechains (B), and is preferably present only as impurities but not deliberately added for polymerization.
  • monomer (B2) is present, the amounts of monomers are as follows, based on the total WEIGHT OF THE GRAFT POLYMER:
  • (B) is from 10 to 60%, preferably up to 50%, more preferably up to 40%, and preferably from 20%;
  • (B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 9 to 55 %, preferably up to 50, more preferably up to 40, even more preferably up to 35, and even more preferably up to 30%;
  • (B2) (nitrogen-containing monomer) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 1 to 41 %, preferably up to 30, more preferably up to 25 such as 1 to 25 and more preferably 5 to 25, even more preferably up to 15 such as 1 to 15 and more preferably 5 to 15, and further such as up to 10 up to 40, 35, 20, 10, and every number in between 1 and 41 , wherein preferably the amount of (B2) is not higher than the amount of (B1);
  • (B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0, but in all cases at most 10% of the amount of (B1), and not more than the amount of (B2).
  • (B) is from 5 to 60%, preferably up to 50%, and preferably from 20%;
  • (B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is the total amount of (B) minus the total amount of (B3);
  • (B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0.
  • the amount of vinyl ester monomer (B1) is usually not smaller than 10% by weight (in relation to the sum of (B1) and (B2)).
  • optional further monomers (B3) are present only as impurities but not deliberately added for polymerization. More preferably, the amount is less than 1 , more preferably less than 0.5%, even more preferably less than 0.01% by weight based on total weight of monomers (B1), most preferably there is essentially no such monomers (B3), and most preferably even a total absence of any other monomer besides the monomers (B1) and optional monomers (B2). The same applies for the further monomers besides (B1), (B2) and (B3).
  • the graft polymer of the invention comprises polymeric sidechains (B) which are obtained or obtainable by radical polymerization of the at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) and optionally at least one further monomer (B3) in the presence of the polymer backbone (A), wherein at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 80, more preferably at least 90 weight percent, and most preferably essentially only vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B1 being employed).
  • the inventive graft polymer consists of monomers, wherein
  • (B1) at least one vinyl ester, selected from vinyl acetate, vinyl propionate and/or vinyl laurate, in amounts of from 70 to 100% by weight of the total weight of monomers that are grafted onto the backbone (A), preferably only vinyl acetate, and
  • (B2) optionally at least one nitrogen-containing monomer in amounts of from 0 to 30% by weight of the total amount of monomers that are grafted onto the backbone (A), being preferably a N-vinyllactam, such as N-vinylpyrrolidone, N-vinylpiperidone, N- vinylcaprolactam, even more preferably N-vinylpyrrolidone and/or N- vinylcaprolactam, and most preferably N-vinylpyrrolidone, with the vinyl ester monomer(s) (B1) optionally being partially or fully hydrolyzed after polymerization.
  • N-vinyllactam such as N-vinylpyrrolidone, N-vinylpiperidone, N- vinylcaprolactam, even more preferably N-vinylpyrrolidone and/or N- vinylcaprolactam, and most preferably N-vinylpyrrolidone
  • the vinyl ester is not hydrolyzed.
  • At least one vinyllactame, preferably vinylpyrrolidone and/or vinylcaprolactame, more preferably only vinylpyrrolidone, as monomer (B2) is present besides at least one monomer (B1), with monomer (B1) being preferably comprising vinyl acetate, and even more preferably being only vinyl acetate. Even more preferably, vinyl acetate is the only monomer (B1) and vinylyprrolidone is the only monomer (B2).
  • the monomer (B1) may be partially or fully hydrolyzed after the polymerization reaction.
  • monomer (B1) is partially hydrolyzed, and is even more preferably hydrolyzed to up to 80, 70 or 60, 50, 40, 30, 20 or 10 mole percent based on the total amount of monomer(s) (B1).
  • the monomer (B1) is partially hydrolyzed of from 20 %, and is hydrolyzed up to 50%.
  • vinyl acetate is employed as monomer (B1) and vinylpyrrolidone as monomer (B2), and the polymer moiety stemming from vinyl acetate is partially hydrolyzed after polymerisation, preferably in an amount of about 20 to 50, more preferably about 30 to 45, such as about 40mole %, based on total amount of vinyl acetate.
  • the vinyl esters are not hydrolyzed at all.
  • broad ranges and very particularly preferred narrow ranges may be combined in one embodiment of this invention, with the selection of the ranges for one component being chosen independently of that for the other component, in as far as the overall numbers add up to a “100%-polymer”: e.g. the most preferred range for (A) and (B) may be chosen and combined with the broadest possible ranges given for (B1) I (B2) I (B3), and any other possible combination.
  • the inventive graft polymer as detailed before has a polydispersity (PDI) Mw/Mn of at most 10, preferably at most 5, more preferably at most 3, and most preferably in the range from 1 .0 to 2.6, and any number a as upper or lower limit and any range in between such as 1 ,3 to 2,6, 1 to 3 etc.
  • PDI polydispersity
  • M w and M n can be determined using GPC standard methods, such as the one referenced in the experimental section.
  • the molecular weights of the backbones used in this invention can also be calculated, as those reactions proceed basically to completeness. Hence, the calculation of the molecular weights based on the total molar amounts of ingredients employed for the preparation reaction is a viable way as well.
  • the graft polymers of the invention may contain a certain amount of ungrafted polymers (“ungrafted side chains”) made of monomers not being reacted with (i.e. grafted (on-)to) the polymer backbone.
  • ungrafted side chains made of monomers not being reacted with (i.e. grafted (on-)to) the polymer backbone.
  • the amount of such ungrafted polymers may be high or low, depending on the reaction conditions, but is preferably to be lowered and thus is more preferably low. By this lowering, the amount of grafted side chains is preferably increased. Such lowering can be achieved by suitable reaction conditions, such as dosing of monomers and radical initiator and their relative amounts and also in relation to the amount of backbone being present. Such adjustment is in principle known to a person of skill in the present field, and detailed hereinafter for this present invention within the description of a process to obtain the inventive graft polymers.
  • inventive graft polymers as detailed herein before exhibit an improved bio-degradability which is at least 35, more preferably at least 40, even more preferably at least 50, such as 41 , 42, 43, 44, 45 etc., 51 , 52, 53 etc, 55, 60, 65, etc. and any number in between and up to 100%, within 28 days when tested under OECD 301 F.
  • the graft polymer of the invention and/or as detailed before consists of:
  • polymeric sidechains (B) grafted onto the polymer backbone (A), wherein said polymeric sidechains (B) are obtainable by (co-)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), and optionally further monomer(s) (B3), and optionally further monomers, all such monomers being any of the monomers as defined in any of the embodiments herein, in the amounts defined in any of the embodiments herein, including the description, the examples, and the claims.
  • the vinyl ester monomer is vinyl acetate as the only monomer (B1), and more preferably vinylpyrrolidone is the only monomer (B2), and most preferably no other monomers (B3) and further monomers besides the previous ones are present.
  • the vinyl ester is hydrolyzed to about 20 to 50 mole percent, preferably about 30 to 45 mole %, most preferably about 40 mole%.
  • the graft polymer of the invention consists of:
  • (a1) is a unit comprising, preferably essentially consisting of, moieties derived from at least one alkylene oxide monomer and/or at least one polyalkylene oxide-polymer having two hydroxy-end-groups, the alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,
  • (a2) is a unit comprising, preferably consisting of, at least one lactone and/or at least one hydroxy acid, such sub-unit (a2) being a moiety derived from a single lactone and/or hydroxy-acid or being oligo-or-polymeric units consisting of at least one type of lactone and/or at least one type of hydroxy acid, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e.
  • lactones preferably being p-propiolactone, g-butyrolactone, b-valerolactone, g- valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; and ii) hydroxy acid(s), which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, specifically an a-, p- or y- hydroxy acid derived from the corresponding lactone by hydrolyzation, and lactic acid, glycolic acid, 4-hydroxybutanoic acid, 6-hydroxy hexanoic acid, 12-hydroxy stearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone
  • (A1) by co-polymerization of at least one sub-unit (a1) and at least one sub-unit (a2), wherein optionally at least one oligomer or polymer made from at least one sub-unit (a1) or at least one sub-unit (a2) can be employed within the copolymerization of at least one sub-unit (a1) and at least one sub-unit (a2) as well;
  • (A4) by first providing an oligo- or polymeric sub-unit (a1) which is bears an end-cap on one side, preferably is etherified with alcohols, more preferably short-chain alcohols C1 to C4, which - as starter-block - is thereafter reacted with at least one sub-unit (a2) and optionally at least one sub-unit (a1) - wherein the sub-unit (a1) may be different to that/those in the starter block or may be arranged in a different order compared to those in the starter block - to attach to the non-end capped side of the starter block a new block comprising moieties from the sub-units employed for the (co-)polymerization, thereby obtaining a di-block-structure of [end-cap]-[sub-unit(s) (a1)]-[sub-unit(s) (a2)], or [end-cap]-[sub-unit(s) (a1)]-[random- ⁇ sub-unit(s) (a2)-sub unit(s
  • (A1 ) a backbone consisting of a randomly arranged order of monomeric, oligomeric and/or polymeric (al)-sub-units and monomeric, oligomeric and/or polymeric (a2)-sub- units, with more than one sub-unit (a1) and/or more than one sub-unit (a2) being present;
  • (A2) a backbone consisting of oligo- or polymerized sub-units (a2) as an inner block and two outer blocks of oligomeric and/or polymeric (al)-sub-units, defined as “-[block of (a1)]-[block of (a2)]-[block of (a1 )]-”, and also possibly comprising higher block- polymers such as 5-, 7- and 9- etc.
  • (A3) a backbone consisting of and inner block of oligomeric and/or polymeric (a1)-sub- units and two outer blocks of oligo- or polymeric sub-units (a2), in the form of at least an tri-block-polymer defined as “ - [block of (a2)]-[block of (a1 )] - [block of (a2)] and
  • end-cap on one end an end-cap - such end-cap being a C1 to C18-, preferably C1- C4-alkyl-group attached to said first block via an ether-function;
  • an oligo- or polymeric sub-unit (a1) (ii) an oligo- or polymeric sub-unit (a1); and a second block which is attached to said first block at the opposite end of said first block (“opposite” in relation to the end-cap on said first block) via an ether or ester-fu notion, said second block being composed of at least one sub-unit (a2) and optionally at least one sub-unit (a1), wherein the optional sub-unit(s) (a1) in said second block may be different to that/those in the first block or may be arranged in a different order compared to those in the first block, and the order of the sub-unit(s) (A1) and (a2) may be also in any order, including random structure, such di-block-structure having as an idealized structure in case of using only sub-unit(s) (a2) for the second block:
  • sub-units (a1) and (a2) being those as herein defined before; and wherein - optionally - at least one starter molecule is included in the backbone structure;
  • polymeric sidechains (B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60 %, most preferably 20 to 50%, of polymeric sidechains (B) grafted onto the polymer backbone (A), wherein said polymeric sidechains (B) are obtainable by (co-)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), and optionally further monomer(s) (B3), and optionally further monomers, with the percentages as weight percent in relation to the total weight of the graft polymer; wherein the monomers are:
  • (B1) at least one vinyl ester, selected from vinyl acetate, vinyl propionate and/or vinyl laurate and any further vinylester known to a person skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and/or vinyl benzoate;
  • (B3) at least one further monomer, such as any one or more of 1 -vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinyl pyridine-N-oxide, N-vinyl formamide and its amine if hydrolyzed after polymerization, N-vinyl acetamide, N-vinyl-N-methyl acetamide, alkyl esters of (meth)acrylic acid; and
  • at least one further monomer being different from those before, such other monomer being present only in an amount of less than 2% of the total amount of monomers employed for obtaining the polymeric sidechains (B), and are preferably present only as impurities but not deliberately added for polymerization; with the amount(s) preferably as follows:
  • (B) is from 10 to 60%, preferably up to 50%, more preferably up to 40%, and preferably from 20%;
  • (B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 9 to 55 %, preferably up to 50, more preferably up to 40, even more preferably up to 35, and even more preferably up to 30%;
  • (B2) (nitrogen-containing monomer) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 1 to 41 %, preferably up to 30, more preferably up to 25 such as 1 to 25 and more preferably 5 to 25, even more preferably up to 15 such as 1 to 15 and more preferably 5 to 15, and further such as up to 10 up to 40, 35, 20, 10, and every number in between 1 and 41 , wherein preferably the amount of (B2) is not higher than the amount of (B1 ) or
  • (B) is from 5 to 60%, preferably up to 50%, and preferably from 20%;
  • (B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is the total amount of (B) minus the total amount of (B3),
  • (B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0, but in all cases at most 10% of the amount of (B1 ), and not more than the amount of (B2); wherein preferably at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 80, more preferably at least 90 weight percent, and most preferably essentially only vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B1 being employed), and optionally the vinyl ester is hydrolyzed after polymerization.
  • the vinyl ester monomer is vinyl acetate as the only monomer (B 1 ), and more preferably vinylpyrrolidone is the only monomer (B2), and most preferably no other monomers (B3) and further monomers besides the previous ones are present.
  • the vinyl ester is hydrolyzed to about 20 to 50 mole percent, preferably about 30 to 45 mole %, most preferably about 40 mole%.
  • the polymer backbone (A) may bear as the end-groups two hydroxy-groups or may be capped on both ends with C1 to C22-alkyl groups, preferably C1 to C4 alkyl groups;
  • the graft polymer is preferably water-soluble to a certain extent, to be able to employ the polymers within the aqueous environment typically present in the fields of applications as generally targeted with this present invention.
  • inventive polymers should exhibit a medium to good, more preferably a good solubility in the environment of an aqueous formulation as typically employed in such fields for the various kinds of formulations, e.g. dish washing, automatic dish-washing, hard surface cleaning, fabric cleaning, fabric care, cosmetic formulations etc.
  • the graft polymer solution preferably has a viscosity that at reasonably high solid concentrations of the polymer as to be handled in and after production and to be provided to the user, which could be e.g. as a “pure” (then typically liquid) product, dissolved in a solvent, typically an aqueous solution containing water and organic solvents, only water or only organic solvents, the viscosity of such polymer or polymer solution being in a range that allows typical technical process steps such as pouring, pumping, dosing etc.
  • a solvent typically an aqueous solution containing water and organic solvents, only water or only organic solvents
  • the viscosities should be preferably in a range of about up to less than 4000 mPas, more preferably up to 3500 mPas, even more preferably up to 3000 mPas, such as up to 4500, 3750, 3250, 2750 or even 2600 or below such as 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150, or 100 mPas, at concentrations of the polymer (based on the total solid content of the polymer in solution, as defined by weight percent of the dry polymer within the total weight of the polymer solution) of preferably at least 10 wt.%, more preferably at least 20, and even more preferably at least 40 wt.%, and most preferably at least 50 wt.%, such as at least 60, 70, 80 or even 90 wt.%.
  • concentrations of the polymer based on the total solid content of the polymer in solution, as defined by weight percent of the dry polymer within the total weight of the poly
  • the viscosity may be measured at either 25 °C or at elevated temperature, e.g. temperatures of 50 or even 60 °C. By this a suitable handling of the polymer solutions in commercial scales is possible. It is of course evident that depending on the amount of solvent being added the viscosity is lower when the amount of solvent increases and vice versa, thus allowing for adjustment in case desired. It is also evident that the viscosity being measured depends on the temperature at which it is being measured, e.g. the viscosity of a given polymer with a given solid content of e.g. 80 wt.% will be higher when measured at lower temperature and lower when measured at a higher temperature.
  • the solid content is in between 70 and 99 wt.%, more preferably in between 75 and 85 wt.%, with no additional solvent being added but the polymer as prepared. In a more preferred embodiment, the solid content is in between 70 and 99 wt.%, more preferably in between 75 and 95 wt.%, with no additional solvent being added but the polymer as prepared, and the viscosity is lower than 3000 mPas, more preferably 3250, or even below 2750, 2600, 2500, 2000, 1750, 1500, 1250, 1000, 750, 500 or even 250 mPas, when measured at 60 °C. The viscosity may be determined as generally known for such polymers, preferably as described below in the experimental part.
  • the individual performance of a specific polymer needs to be evaluated and thus ranked for each individual formulation in a specific field of application. Due to the broad usefulness of the inventive polymers an exhaustive overview or detailed guidance for each area is not possible, but the present specification and examples give a guidance on how to prepare and select useful polymers of desired properties and how to tune the properties to the desired needs.
  • One such criteria for the area of home care and especially fabric care of course it he performance upon washing, e.g. subjecting a certain material exhibiting stains of certain materials to a defined washing procedure.
  • the examples give some guidance for the application for washing of fabrics, i.e. the general area of fabric care.
  • the invention also encompasses a process for obtaining a graft polymer according to any of the previous embodiments as defined herein and specifically any embodiment in the previous section, but also in any of the examples disclosed herein, wherein at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), optionally further monomer(s) (B3) and optional further monomers (besides (B1), (B2) and (B3)) is/are polymerized in the presence of at least one polymer backbone (A) as defined herein, preferably selected from backbones (A1), (A2), (A3) and (A4) as defined herein, wherein the polymeric sidechains (B) are obtained by radical polymerization, preferably using radical forming compounds to initiate the radical polymerization, wherein each B1 , B2 and B3 (and further monomers besides (B1), (B2) and (B3)) and (A), (A1), (A2), (A3) and (A4) are as defined herein before, in any
  • radical polymerization as such is also known to a skilled person. That person also knows that the inventive process can be carried out in the presence of a radical-forming initiator (C) and/or at least one solvent (D).
  • C radical-forming initiator
  • D solvent
  • radical polymerization as used within the context of the present invention comprises besides the free radical polymerization also variants thereof, such as controlled radical polymerization.
  • Suitable control mechanisms are RAFT, NMP or ATRP, which are each known to the skilled person, including suitable control agents.
  • the process to produce a graft polymer of the invention and/or as detailed before comprises the polymerization of at least one vinyl ester monomer (B1) and optionally at least one nitrogen-containing monomer (B2), optionally at least one further monomer (B3) and optionally further monomer(s) - the latter being preferably present only as impurities, and more preferably are essentially not present -, in the presence of at least one polymer backbone (A), preferably selected from the backbones (A1), (A2), (A3) and (A4) as defined herein before, a free radical-forming initiator (C) and, if desired, up to 50% by weight, based on the sum of components (A), (B), and (C), of at least one solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomers (B1), optional (B2) and optional (
  • no monomer (B2) is employed.
  • no monomer (B2) nor monomer (B3) are employed.
  • monomer(s) (B1) are employed.
  • the amount of further monomer(s) besides (B1), (B2) and (B39 is minimized, preferably they are not present at all.
  • At least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent, and most preferably essentially only (i.e. about 100wt.% or even 100 wt.%) vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B1 being employed).
  • At least one further monomer may be employed for the co-polymerization to yield the side chains (B), wherein such further monomer is present only in an amount of less than 2% of the total amount of monomers employed for obtaining the polymeric sidechains (B), and is preferably employed only as - in practical aspects non-avoidable - impurities but not deliberately added for polymerization, and most preferably is not present at all.
  • (B) is from 10 to 60%, preferably up to 50%, more preferably up to 40%, and preferably from 20%;
  • (B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 9 to 55 %, preferably up to 50, more preferably up to 40, even more preferably up to 35, and even more preferably up to 30%;
  • (B2) (nitrogen-containing monomer) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 1 to 41 %, preferably up to 30, more preferably up to 25 such as 1 to 25 and more preferably 5 to 25, even more preferably up to 15 such as 1 to 15 and more preferably 5 to 15, and further such as up to 10 up to 40, 35, 20, 10, and every number in between 1 and 41 , wherein preferably the amount of (B2) is not higher than the amount of (B1 );
  • (B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0, but in all cases at most 10% of the amount of (B1), and not more than the amount of (B2).
  • B) is from 5 to 60%, preferably up to 50%, and preferably from 20%;
  • (B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is the total amount of (B) minus the total amount of (B3),
  • (B2) nitrogen-containing monomer
  • (B3) further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0.
  • the amount of vinyl ester monomer (B1) employed is usually not smaller than 10% by weight (in relation to the sum of (B1) and (B2)).
  • optional further monomers (B3) are present also only as impurities but not deliberately added for polymerization. More preferably, the amount is less than 1 , more preferably less than 0.5%, even more preferably less than 0.01% by weight based on total weight of monomers (B1), most preferably there is essentially no such monomers (B3), and most preferably even a total absence of any other monomer besides the monomers (B1 ) and optional monomers (B2). The same applies for the further monomers besides (B1), (B2) and (B3).
  • the amounts of monomers employed are as follows, based on the total WEIGHT OF THE GRAFT POLYMER:
  • (A) is from 40 to 90%, preferably from 50%, more preferably from 60%, and preferably at most 80%, of a polymer backbone as defined herein before, preferably at least one of (A1), (A2) and (A3), as a graft base,
  • (B) is from 10 to 60%, preferably up to 50%, more preferably up to 40%, and preferably from 20%;
  • (B1) (vinylester) is from 9 to 55 %, preferably up to 50, more preferably up to 40, even more preferably up to 35, and even more preferably up to 30%;
  • (B2) (at least one vinyllactam, preferably vinylpyrrolidone and/or vinylcaprolactam, more preferably vinylpyrrolidone) is from 1 to 25 %, preferably up to 20, more preferably up to 15, even more preferably up to 10, such as even only up to 5, wherein at most the amount of (B2) is not higher than the amount of (B1 );
  • (B3) (further monomer(s)) is from 0 to 2, preferably at most 1 , more preferably 0, but in all cases at most 10% of the amount of (B1 ), and not more than the amount of (B2);
  • the optional further monomers (B3) and the further monomers besides (B1 ), (B2) and (B3) are preferably present only as impurities but not deliberately added for polymerization; more preferably, the amount is less than 1 , more preferably less than 0.5%, even more preferably less than 0.01% by weight based on total weight of monomers (B1), most preferably there is essentially no such monomers (B3) nor further monomers, and most preferably even a total absence of any other monomer besides the monomers (B1 ) and (B2).
  • the amount of vinyl ester monomer (B1) is usually not smaller than 10% by weight (in relation to the sum of (B1) and (B2)).
  • the amounts of monomers employed are as follows, based on the total WEIGHT OF THE GRAFT POLYMER: (A) is from 40 to 90%, preferably from 50%, more preferably from 80%, of a polymer backbone as defined herein before, preferably at least one of (A1), (A2) and (A3), as a graft base;
  • (B) is from 10 to 60%, preferably up to 50%, and preferably from 20%;
  • (B1) (vinylester) is the total amount of (B) minus the total amount of (B3);
  • (B3) (further monomer(s)) is from 0 to 2, preferably at most 1 , more preferably 0, but in all cases at most 10% of the amount of (B1 ), and not more than the amount of (B2); the amount of vinyl ester monomer (B1 ) is usually not smaller than 10% by weight (in relation to the sum of (B1) and (B2)); the optional further monomers (B3) and the further monomers beside (B1 ), (B2) and (B3) are preferably present only as impurities but not deliberately added for polymerization.
  • the amount is less than 1 , more preferably less than 0.5%, even more preferably less than 0.01 % by weight based on total weight of monomers (B1 ), most preferably there is essentially no such monomers (B3) nor further monomers, and most preferably even a total absence of any other monomer besides the monomers (B1 ).
  • the amount of ((free) radical-forming) initiator (C) is preferably from 0.1 to 5% by weight, in particular from 0.3 to 3.5% by weight, based in each case on the polymeric sidechains (B).
  • the steady-state concentration of radicals present at the mean polymerization temperature is substantially constant and the graft monomers (B), and especially (B1), more preferably (B1) and (B2), even more preferably (B1), (B2) and (B3), are present in the reaction mixture constantly only in low concentration (for example of not more than 5% by weight in total).
  • B1 graft monomers
  • B2 graft monomers
  • B3 graft monomers
  • temperature control is usually not a crucial point, as the temperature is at least partially controlled also by the propagation of the polymerization reaction by controlling the radical concentration and the available amount of polymerizable monomers.
  • additional cooling as described before may become necessary for both variants - batch reaction or bulk reactions with large amounts of monomer present from the start or semi-continuous or continuous polymerization reactions with typically constantly low monomer concentrations - when the scale gets large enough that the ratio from volume to surface of the polymerization mixture becomes very large.
  • the initiator (C) and the graft monomers (B), and especially (B1) and/or (B2) and/or (B3), preferably twice “and”, are advantageously added in such a way that a low and substantially constant concentration of undecomposed initiator and graft monomers (B), and especially a constant but low amount of (B1) and especially even more (B2) (especially in case when vinylpyrrolidone is selected as (B2)), are present in the reaction mixture.
  • the proportion of undecomposed initiator in the overall reaction mixture is preferably ⁇ 15% by weight, in particulars 10% by weight, based on the total amount of initiator metered in during the monomer addition.
  • the process comprises the polymerization of at least one vinyl ester monomer (B1) and optionally at least one nitrogen-containing monomer (B2), optionally at least one other monomer (B3) and optionally at least one further monomer(s), more preferably only monomers (B1) and (B2), in the presence of at least one polymer backbone (A) as defined herein, preferably selected from (A1), (A2) and (A3), a free radicalforming initiator (C) and, if desired, up to 50% by weight, based on the sum of components (A), (B) and (C), of at least one solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomers (B) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the polymer backbone (A), wherein preferably at least 10 weight percent of the total
  • (B1) comprises vinyl acetate, more preferably comprises essentially only vinyl acetate, all in the ranges and preferred ranges given in the section on the “graft polymers of this invention”.
  • (B1) comprises vinyl acetate, more preferably comprises essentially only vinyl acetate, and preferably (B2) comprises a vinyllactam, more preferably comprises vinylpyrrolidone, and even more preferably comprises essentially vinylpyrrolidone, all in the ranges and preferred ranges given in the section on the “graft polymers of this invention”.
  • the mean polymerization temperature for the main polymerization and the postpolymerization is appropriately in the range from 50 to 140°C, preferably from 60 to 120°C and more preferably from 65 to 110°C. Typically, the temperature for the post-polymerization is higher by 5 to 40 °C compared to the polymerization.
  • mean polymerization temperature is intended to mean here that, although the process is substantially isothermal, there may, owing to the exothermicity of the reaction, be temperature variations which are preferably kept within the range of +/- 10°C, more preferably in the range of +/- 5°C.
  • the (radical-forming) initiator (C) at the mean polymerization temperature should have a decomposition half-life of from 40 to 500 min, preferably from 50 to 400 min and more preferably from 60 to 300 min.
  • Suitable initiators (C) whose decomposition half-life in the temperature range from 50 to 140°C is from 20 to 500 min are:
  • O-C2-Ci2-acylated derivatives of tert-C4-Ci2-alkyl hydroperoxides and tert-(Cg-Ci2- aralkyl) hydroperoxides such as tert-butyl peroxyacetate, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5- trimethylhexanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyneodecanoate, 1 ,1 ,3,3-tetramethylbutyl
  • examples of particularly suitable initiators (C) are: at a mean polymerization temperature of from 50 to 60°C: tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, 1 ,1 ,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1 ,3-di(2-neodecanoyl peroxyisopropyl)benzene, di(n-butyl) peroxydi carbon ate and di(2-ethylhexyl) peroxydicarbonate; at a mean polymerization temperature of from 60 to 70°C: tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert
  • Preferred initiators (C) are O-C4-Ci2-acylated derivatives of tert-C4-C5-alkyl hydroperoxides, particular preference being given to tert-butyl peroxypivalate and tert-butyl peroxy-2- ethylhexanoate.
  • Particularly advantageous polymerization conditions can be established effortlessly by precise adjustment of initiator (C) and polymerization temperature.
  • the preferred mean polymerization temperature in the case of use of tert-butyl peroxypivalate is from 60 to 80°C, and, in the case of tert-butyl peroxy-2-ethylhexanoate, from 80 to 100°C.
  • the inventive polymerization reaction can be carried out in the presence of, preferably small amounts of, a solvent (D). It is of course also possible to use mixtures of different solvents (D). Preference is given to using water-soluble or water-miscible organic solvents. However, water as only solvent is in principle also possible but not preferred.
  • a solvent (D) used as a diluent, generally from 1 to 40% by weight, preferably from 1 to 35% by weight, more preferably from 1 .5 to 30% by weight, most preferably from 2 to 25% by weight, based in each case on the sum of the components (A), (B1), optionally (B2), optionally (B3) and optional further monomers, and (C), are used.
  • suitable solvents (D) include: monohydric alcohols, preferably aliphatic Ci-Ci6-alcohols, more preferably aliphatic C2-Ci2-alcohols, most preferably C2-C4-alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol; polyhydric alcohols, preferably C2-C -diols, more preferably C2-Ce-diols, most preferably C2-C4-alkylene glycols, such as ethylene glycol, 1 ,2-propylene glycol and 1 ,3-propylene glycol; alkylene glycol ethers, preferably alkylene glycol mono(Ci-Ci2-alkyl) ethers and alkylene glycol di(Ci-Ce-alkyl) ethers, more preferably alkylene glycol mono- and di(Ci- C2-alkyl) ethers,
  • the solvents (D) are advantageously those solvents, which are also used to formulate the inventive graft polymers for use (for example in washing and cleaning compositions) and can therefore remain in the polymerization product.
  • these solvents are polyethylene glycols having 2-15 ethylene glycol units, polypropylene glycols having 2-6 propylene glycol units and in particular alkoxylation products of Ce-Cs-alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).
  • alkoxylation products of Cs-Ci6-alcohols with a high degree of branching which allow the formulation of polymer mixtures which are free-flowing at 40-70°C and have a very low polymer content at comparatively low viscosity.
  • the branching may be present in the alkyl chain of the alcohol and/or in the polyalkoxylate moiety (copolymerization of at least one propylene oxide, butylene oxide or isobutylene oxide unit).
  • alkoxylation products are 2-ethylhexanol or 2- propylheptanol alkoxylated with 1-15 mol of ethylene oxide, C13/C15 OXO alcohol or Ci2/Ci4 or Cie/Cis fatty alcohol alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide, preference being given to 2-propylheptanol alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide.
  • the polymerization is performed using a mixture of at least one organic solvent and water.
  • the amount of water during the polymerization is low, preferably at most 10 wt.%, more preferably at most 5wt% based on total solvent, more preferably at most 1 %.
  • the polymerization is performed using water as solvent (D).
  • water as only solvent is not preferred.
  • the radical initiator (C) is preferably employed in the form of a concentrated solution in one of the solvents mentioned before.
  • concentration depends on the solubility of the radical initiator. It is preferred, that the concentration is as high as possible to allow to introduce as little as possible of the organic solvent into the polymerization reaction.
  • the concentration is not critical from the viewpoint of residual levels of water.
  • the amount of water during the polymerisation is at most 10 wt.%, preferably at most 5 wt.%, more preferably at most 1 wt.%, based on total weight of graft polymer (at the end of the polymerization) or based on total weight of (A) and (B) (at the start of the polymerization).
  • polymer backbone (A), graft monomer(s) (B), initiator (C) and, if appropriate, solvent (D) are usually heated to the selected mean polymerization temperature in a reactor.
  • the polymerization is carried out in such a way that an excess of polymer (polymer backbone (A) and formed graft polymer) is constantly present in the reactor.
  • the quantitative ratio of polymer to ungrafted monomer and initiator is generally > 10:1 , preferably > 15:1 and more preferably > 20:1.
  • the polymerization process according to the invention can in principle be carried out in various reactor types.
  • reactor types are generally known, and includes any stirred-type reactor such as vessels, but also includes tube reactors, reactor cascades from vessels or various tubes etc.
  • the reactor used is preferably a stirred tank in which the polymer backbone (A), if appropriate together with portions, of generally up to 15% by weight of the particular total amount, of graft monomers (B), initiator (C) and solvent (D), are initially charged fully or partly and heated to the polymerization temperature, and the remaining amounts of (B), (C) and, if appropriate, (D) are metered in, preferably separately.
  • the remaining amounts of (B), (C) and, if appropriate, (D) are metered in preferably over a period of > 2 h, more preferably of > 4 h and most preferably of > 5 h.
  • the entire amount of polymer backbone (A) is initially charged as a melt and the graft monomers (B1) and, if appropriate, (B2) and/or (B3), and also the initiator (C) present preferably in the form of a from 10 to 50% by weight solution in one of the solvents (D), are metered in, the temperature being controlled such that the selected polymerization temperature, on average during the polymerization, is maintained with a range of especially +/- 10°C, in particular +/- 5°C.
  • the procedure is as described above, except that solvent (D) is metered in during the polymerization in order to limit the viscosity of the reaction mixture. It is also possible to commence with the metered addition of the solvent only at a later time with advanced polymerization, or to add it in portions.
  • the polymerization can be affected under standard pressure or at reduced or elevated pressure.
  • the boiling point of the monomers (B1) and/or (B2) (and if employed also monomer (B3)) and/or of any solvent (D) used is exceeded at the selected pressure, the polymerization is carried out with reflux cooling.
  • a post-polymerization process step may be added after the main polymerization reaction.
  • a further amount of initiator dissolved in the solvent(s)
  • a different radical initiator and/or different solvent(s) may be employed as well.
  • the temperature of the post-polymerisation process step may be the same as in the main polymerization reaction (which is preferred in this invention) or may be increased. In case increased, it may be typically higher by about 5 to 40°C, preferably 10 to 20°C.
  • a certain period of time may be waited, where the main polymerization reaction is left to proceed, before the postpolymerisation reaction is started by starting the addition of further radical initiator.
  • solvents having a boiling point of approximately less than 110-120 °C at atmospheric pressure may - as a purification step - be removed partially or essentially complete by thermal or vacuum distillation or stripping with a gas such as steam or nitrogen, such as stripping with steam made from water, all at ambient or reduced pressure, preferably vacuum distillation, whereas higher boiling solvents will usually stay in the polymer products obtained.
  • the graft polymers of the invention prepared using the process as defined herein may contain a certain amount of ungrafted polymers (“ungrafted side chains”) made of vinyl ester(s), e.g. poly vinyl acetate in case only vinyl acetate is employed, and/or - when further monomers are employed - homo- and copolymers of vinyl ester(s) with the other monomers.
  • the amount of such ungrafted vinyl ester-homo- and copolymers may be high or low, depending on the reaction conditions, but is preferably to be lowered and thus low. By this lowering, the amount of grafted side chains is preferably increased.
  • Such lowering can be achieved by suitable reaction conditions, such as dosing of vinyl ester and radical initiator and their relative amounts and also in relation to the amount of backbone being present.
  • suitable reaction conditions such as dosing of vinyl ester and radical initiator and their relative amounts and also in relation to the amount of backbone being present.
  • This adjustment of the degree of grafting and this amount of ungrafted polymers can be used to optimize the performance in areas of specific interest, e.g. certain (e.g. detergent-) formulations, application areas or desired cleaning etc. performance.
  • a drawback is that it is extremely difficult if not even impossible to actually verify such degree of grafting on a polymer, especially with increasing molecular weights of the polymers, as the total amount of grafting sites in a polymer is generally very low compared to the molecular weight; thus, the signal-to-noise-ratio is unfavorable for polymers in view of current analytical tools.
  • the polymeric sidechains (B) of the graft polymer according to the present invention are fully or partially hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mole%, and preferably from 20mole%, more preferably 20 to 50, even more preferably 30 to 45, such as about 40 mole %, based on the total moles of (B1) employed, after the polymerization reaction and thus after the graft polymer as such is obtained.
  • no hydrolysis is performed on the graft polymer after the polymerization process of the polymeric sidechains (B) is finished. Due to this full or at least partial hydrolyzation of the polymeric sidechains (B) of the graft polymers according to the present invention, the respective sidechain units originating from the at least one vinyl ester monomer (B1) are changed from the respective ester function into the alcohol function within the polymeric sidechain (B). It has to be noted that the corresponding vinyl alcohol is not suitable to be employed as monomer within the polymerization process of the polymeric sidechains (B) due to stability aspects of the “vinylalcohol”-monomer. In order to obtain an alcohol function (hydroxy substituent) within the polymeric sidechains (B) of the graft polymers according to the present invention, the alcohol function is typically introduced by hydrolyzing the ester function of the sidechains.
  • each ester function of the polymeric sidechain (B) may be partially or completely replaced by an alcohol function (hydroxy group). In such a case, the polymeric sidechain is fully hydrolyzed (“saponified”).
  • the hydrolysis can be carried out by any method known to a person skilled in the art.
  • the hydrolysis can be induced by addition of a suitable base, such as sodium hydroxide or potassium hydroxide.
  • a suitable base such as sodium hydroxide or potassium hydroxide.
  • vinyl acetate is employed as monomer (B1 ) and vinylpyrrolidone as monomer (B2) and no other monomers are employed besides (B1) and (B2), and the polymer moiety stemming from vinyl acetate is partially hydrolyzed after polymerisation, preferably in an amount of from 20 to 50 mole, more preferably 30 to 45, such as - most preferably - about 40 mole %based on the total moles of (B1) employed.
  • the graft polymer of this invention i.e. the polymer solution obtained from the process, may be also subjected to a means of concentration and/or drying.
  • the graft polymer solution obtained may be concentrated by subjecting the polymer solutions to means for removing part of the volatiles and especially solvent(s) to increase the solid polymer concentration. This may be achieved by distillation processes such as thermal or vacuum distillation, or by stripping using gases such as steam or inert gases such as nitrogen or argon, which is performed until the desired solid content is achieved. Such process can be combined with the purification step as disclosed before wherein the graft polymer solution obtained is purified by removing part orall of the volatile components such as volatile solvents and/or unreacted, volatile monomers, by removing the desired amount of solvent.
  • the graft polymer solution may be also after the main and/or the optional post-polymerization step and the optional purification step further concentrated or dried by subjecting the graft polymer solution to means of removing the volatiles partially or fully, such as - for concentration - distillation processes such as thermal or vacuum distillation, or by stripping using gases such as steam or inert gases such as nitrogen or argon, which is performed until the desired solid content is achieved, and/or drying such as roller-drum drying, spray-drying, vacuum drying or freeze-drying, preferably - mainly for cost-reasons - spray-drying.
  • Such drying process may be also combined with an agglomeration or granulation process such as spray-agglomeration, granulation or drying in a fluidized-bed dryer.
  • the process of the invention encompasses preferably at least one further process step selected from i) to iv), with i) post-polymerisation; ii) purification; iii) concentration; and iv) drying.
  • the process as detailed herein in any of the embodiments defined comprises at least one further process step selected from: i) a post-polymerization process step that is performed after the main polymerization reaction, wherein preferably a further amount of initiator (optionally dissolved in the solvent(s)) is added over a period of 0,5 hour and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, with the radical initiator and the solvent(s) for the initiator typically - and preferred - being the same as the ones for the main polymerization reaction; and wherein after the polymerization reaction and before the post-polymerisation reaction preferably a period is waited when the main polymerization reaction is left to proceed, before the post-polymerisation reaction is started by starting the addition of further radical initiator, such period being preferably from 10 minutes and up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, and most preferably up to 30 minutes; and wherein the temperature of the post-polymerisation process
  • the concentration is performed by removing part of the solvent(s) and optionally also volatiles - by this this step additionally serves as means for purification - to increase the solid polymer concentration - and optionally as well for purification - , by preferably applying a distillation process such as thermal or vacuum distillation, preferably vacuum distillation, and/or applying stripping with gas such as steam or an inert gas such as nitrogen, preferably using steam from water, which is performed until the desired solid content and optionally also purity is achieved, preferably is performed until the desired part or all of the volatile components such as volatile solvents and/or unreacted, volatile monomers, are removed; b.
  • a distillation process such as thermal or vacuum distillation, preferably vacuum distillation, and/or applying stripping with gas such as steam or an inert gas such as nitrogen, preferably using steam from water, which is performed until the desired solid content and optionally also purity is achieved, preferably is performed until the desired part or all of the volatile components such as volatile solvents and/or unreacted, volatile monomers,
  • the drying is performed by subjecting the graft polymer containing at least residual amounts of volatiles such as remaining solvent and/or unreacted monomers etc. to a means of removing the volatiles, such as drying using a roller-drum, a spray-dryer, vacuum drying or freeze-drying, preferably - mainly for cost-reasons - spray-drying; and optionally combining such drying process step with a means of agglomeration or granulation to obtain agglomerated or granulated graft polymer particles, such process being preferably selected from spray-agglomeration, granulation or drying in a fluidized-bed dryer, spray-granulation device and the like.
  • the graft polymers of this invention can be employed in any application to replace conventional graft polymers of the same or very similar composition (in terms of relative amounts of polymer backbone and grafted monomers especially when the type and amounts of grafted monomers is similar or comparable.
  • Such applications are for example: redeposition of soils and removing of stains, avoiding or reducing re-soiling or greying or depositioning of solids, dispersion of actives in formulations of agrochemicals, pigments, colours, inorganic salts etc., inhibiting crystal growth including for inhibiting gas hydrate formation and/or reducing sedimentation and/or agglomeration, improve pigment dispersion stability, hydrophobisation of surfaces, reduction of growth of microbes on surfaces, and/or odor control etc., all compared to corresponding polymers or graft polymers according to the prior art.
  • compositions and formulations include glues of any kind, nonwater and - preferably - water-based liquid formulations or solid formulations, the use as dispersant in dispersions of any kind, such as in oilfield applications, automotive applications, typically where a solid or a liquid is to be dispersed within another liquid or solid.
  • Lacquer, paints and colorants formulations include non-water- and - preferably - water-based lacquer and colourants, paints, finishings.
  • compositions and formulations include formulations and compositions containing agrochemical actives within a liquid, semi-solid, mixed-liquid-solid or solid environment.
  • compositions and formulations include formulations which dissolve or disperse aroma chemicals in liquid or solid compositions, to evenly disperse and/or retain their stability, so as to retain their aroma profile over extended periods of time; encompassed are also compositions that show a release of aroma chemicals over time, such as extended release or retarded release formulations.
  • inventive graft polymers as defined herein obtainable by a process as defined herein or obtained by the process as defined herein, can improve the overall bio-degradation ratio of such formulation, compositions and products by replacing non-biodegradable polymers of similar structures or properties. They may thus be advantageously used - partly also depending on the monomer(s) B employed for grafting and thus adjusted in their performance to the specific needs of the specific applications; such monomer substitution pattern as possibly also derivable from the prior art of analogous graft polymers based on simple PEGs and polyalkylene glycols.
  • the graft polymers according to the present invention lead to an improved biodegradability when being employed within such compositions or products, compared to the previously known graft polymers.
  • another subject matter of the present invention is the use of the graft polymers of the invention and/or obtained by or obtainable by a process of the invention and/or as detailed before, in cleaning compositions, fabric and home care products, in particular cleaning compositions for improved oily and fatty stain removal, removal of solid dirt such as clay, prevention of greying of fabric surfaces, and/or anti-scale agents, wherein the cleaning composition is preferably a laundry detergent formulation and/or a dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.
  • graft polymers of the invention and/or obtained by or obtainable by a process of the invention and/or as detailed before in any of in this chapter before-mentioned applications, such as fabric care and home care products, in cosmetic and personal care formulations, as crude oil emulsion breaker, in technical applications including in pigment dispersions for ink jet inks, in formulations for electro plating, in cementitious compositions, in agrochemical formulations as e.g.
  • dispersants, crystal growth inhibitor and/or solubilizer, in lacquer and colorants formulations, textile and leather treatment products for use during or after production formulations containing inorganic salts such as especially silver salts, mining, metal production and treatment including metal refining and metal quenching, purification of liquids such as waste water from industry, production or consumers, preferably in agrochemical compositions and cleaning compositions and in fabric and home care products, in particular cleaning compositions for improved oily and fatty stain removal, removal of solid dirt such as clay, prevention of greying of fabric surfaces, and/or anti-scale agents and most preferably - for inhibiting the transfer of dyes, wherein the cleaning composition is preferably a laundry detergent formulation, more preferably a liquid laundry detergent formulation.
  • Another subject-matter of the present invention is, therefore, also a cleaning composition, fabric care and home care product, industrial and institutional cleaning product, agrochemical formulations, ora formulation or product for any of the previously mentioned applications and application fields, preferably in laundry detergents, in cleaning compositions and/or in fabric and home care products, each comprising at least one graft polymer as defined above or obtained by or obtainable by a process of the invention and/or as detailed herein.
  • a preferred subject matter of this invention is also the use of at least one inventive graft polymer and/or at least one graft polymer obtained or obtainable by the inventive process in fabric care and home care products, industrial and institutional cleaning product, agrochemical formulations, or a formulation or product for any of the previously mentioned applications and application fields, preferably in cleaning compositions and in laundry treatment, laundry care products and laundry washing products, more preferably a laundry detergent formulation, even more preferably a liquid laundry detergent formulation.
  • the inventive graft polymer is employed in such composition/product/formulation for improved dye transfer inhibition.
  • inventive uses and inventive compositions/products encompass the use of the graft polymer as detailed herein and/or as obtainable from or obtained from the inventive process, such graft polymer resembling that as detailed above describing the polymer structure in any of its embodiments disclosed herein before, including any variations mentioned, and more specifically any of the preferred, more preferred etc. embodiments.
  • Laundry detergents, cleaning compositions and/or fabric and home care products as such are known to a person skilled in the art. Any composition etc. known to a person skilled in the art, in connection with the respective use, can be employed within the context of the present invention.
  • it is a cleaning composition and/or fabric and home care product and/or industrial and institutional cleaning product, comprising at least one graft polymer as defined above.
  • it is a cleaning composition for improved cleaning performance, and/or- (preferably “and”) - improved anti redeposition for example in respect of redeposition of soils and removing of stains, preferably a laundry detergent formulation and/or a manual dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.
  • the graft polymers support the removal of various hydrophobic and hydrophilic soils, such as body soils, food and grease soil, particulate soil such clay or carbon black, grass soil, make-up, motor oil etc. from textile or hard surfaces by the surfactants and thus improve the washing and cleaning performances of the formulations.
  • various hydrophobic and hydrophilic soils such as body soils, food and grease soil, particulate soil such clay or carbon black, grass soil, make-up, motor oil etc.
  • the graft polymers also bring about better dispersion of the removed soil in the washing or cleaning liquor and prevent its redeposition onto the surfaces of the washed or cleaned materials.
  • the removed soil include all typical soil that exist in the laundry process, for example, body soil, food and grease soil, particulate soil such clay or carbon black, grass soil, make-up, motor oil etc.
  • Such anti-redeposion effect can be observed on various fabric types, including cotton, polycotton, polyester, copolymer of poly ether I poly urea (SpandexTM), etc.
  • such anti-redeposition effect is also effective on fabrics that have a fabric enhancer history, or when the fabric wash is carried out in the presence of fabric enhancer or other laundry additives such as freshness beads or bleach.
  • the cleaning composition comprises (besides at least one graft polymer as described above) additionally at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme being selected from lipases.
  • at least one enzyme preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases
  • a cleaning composition such as a fabric and home care product and an industrial and institutional (l&l) cleaning product, comprising at least one graft polymer as defined above, and in particular a cleaning composition for improved primary cleaning, improved whiteness, or both, preferably both (such actions as detailed before).
  • l&l industrial and institutional
  • At least one graft polymer as described herein is present in said inventive cleaning compositions in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1 % to about 10%, and most preferably from about 0.5% to about 5%, in relation to the total weight of such composition or product in relation to the total weight of such composition or product; such cleaning composition may - and preferably does - further comprise a from about 1% to about 70% by weight of a surfactant system.
  • inventive cleaning composition is a fabric and home care product or an industrial and institutional (l&l) cleaning product, preferably a fabric and home care product, more preferably a laundry detergent or manual dish washing detergent, comprising at least one inventive graft polymer, and optionally further comprising at least one surfactant or a surfactant system, providing improved removal, dispersion and/or emulsification of soils and I or modification of treated surfaces and I or whiteness maintenance of treated surfaces.
  • l&l industrial and institutional
  • the cleaning compositions of the present invention comprising at least one inventive graft polymer, and optionally further comprising at least one surfactant or a surfactant system - as detailed before - are those for cleaning and anti redeposition performance within laundry and manual dish wash applications, even more specifically, for improved cleaning and anti redeposition performance (such actions as detailed before) such as those on fabrics and dishware, and may additionally comprise at least one enzyme selected from the list consisting of optionally further comprising at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the for
  • the inventive graft polymer may be used for improved cleaning and anti redeposition performance (such action as detailed before) for instance primary washing and/or soil removal of particulate stains and/or oily and fatty stains, and/or additionally for whiteness maintenance, preferably in laundry care.
  • the inventive graft polymer may be used for reducing the greying of fabric (anti-greying), preferably more than one of the before mentioned actions as present, i.e. more than one of improved cleaning, anti redeposition, primary washing, soil removal of particulate stains and/or oily and fatty stains, whiteness maintenance and/or anti-greying being exhibited by the graft polymers of the invention.
  • the inventive graft polymer may be used for improved dye transfer inhibition, i.e. to prevent the transfer of dyes from one piece of fabric to another piece of fabric, either by direct contact or via the washing liquor.
  • the graft polymer contains at least one monomer (B2) as herein defined for such cases. More preferably, (B2) is at least one vinyllactam, even more preferably at least one vinylpyrrolidone and/or caprolactam, most preferably vinylpyrrolidone.
  • Such graft polymers comprising such (B2) are being defined herein with suitable compositions and processes to obtain such graft polymers.
  • the cleaning composition of the present invention is a liquid or solid laundry detergent composition.
  • the cleaning composition of the present invention is a liquid or solid (e.g. powder or tab/unit dose) detergent composition for manual or automatic dish wash, preferably a liquid manual dish wash detergent composition.
  • a liquid or solid detergent composition for manual or automatic dish wash preferably a liquid manual dish wash detergent composition.
  • Such compositions are known to a person of skill in the art.
  • the cleaning composition of the present invention is a hard surface cleaning composition that may be used for cleaning various surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass.
  • inventive graft polymers may be utilized in cleaning compositions comprising a surfactant system comprising C10-C15 alkyl benzene sulfonates (LAS) as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.
  • LAS alkyl benzene sulfonates
  • inventive graft polymers may be utilized in cleaning compositions, such as laundry detergents of any kind, and the like, comprising C8-C18 linear or branched alkyl ethersulfates with 1-5 ethoxy-units as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.
  • inventive graft polymers may be utilized in cleaning compositions, such as laundry detergents of any kind, and the like, comprising C12-C18 alkyl ethoxylate surfactants with 5-10 ethoxy-units as the primary surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non- ionic surfactants, or mixtures thereof.
  • the graft polymer is a component of a cleaning composition, such as preferably a laundry or a dish wash formulation, more preferably a liquid laundry or manual dish wash formulation, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant.
  • a cleaning composition such as preferably a laundry or a dish wash formulation, more preferably a liquid laundry or manual dish wash formulation, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant.
  • this invention also encompasses a composition comprising a graft polymer as described herein before, further comprises an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.
  • an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.
  • this invention also encompasses a method of preserving an aqueous composition against microbial contamination or growth, such composition comprising a graft polymer as described herein before, such composition being preferably a detergent composition, such method comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents as disclosed hereinafter, such antimicrobial agent preferably being 2-phenoxyethanol.
  • this invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising a graft polymer as described herein before, such composition further comprising 4,4’-dichoro 2- hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition.
  • this invention also encompasses a method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising a graft polymer as described herein before, such composition further comprising 4,4’-dichoro 2- hydroxydiphenylether.
  • a cleaning composition more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising a graft polymer as described herein before, such composition further comprising 4,4’-dichoro 2- hydroxydiphenylether.
  • the graft polymers according to the present invention may be used, for example, within cleaning compositions and/or fabric and home care products. They lead to an at least comparable and preferably even improved performance within such compositions or products, where the inventive graft polymers can replace similar graft polymers which however are not biodegradable or such ones exhibiting a much lower biodegradation.
  • the articles “a” and “an” when used in a claim or an embodiment, are understood to mean one or more of what is claimed or described.
  • the terms “include(s)” and “including” are meant to be non-limiting, and thus encompass more than the specific item mentioned after those words.
  • the term “about” as used herein encompasses the exact number “X” mentioned as e.g. “about X%” etc., and small variations of X, including from minus 5 to plus 5 % deviation from X (with X for this calculation set to 100%), preferably from minus 2 to plus 2 %, more preferably from minus 1 to plus 1 %, even more preferably from minus 0,5 to plus 0,5 % and smaller variations.
  • the value X given itself is already “100%” (such as for purity etc.) then the term “about” clearly can and thus does only mean deviations thereof which are smaller than “100”.
  • free of water means that the composition contains no more than 5 wt.-% of water based on the total amount of solvent, in another embodiment no more than 1 wt.-% of water based on the total amount of solvent, in a further embodiment the solvent contains no water at all.
  • compositions of the present disclosure can “comprise” (i.e. contain other ingredients), “consist essentially of’ (comprise mainly or almost only the mentioned ingredients and other ingredients in only very minor amounts, mainly only as impurities), or “consist of’ (i.e. contain only the mentioned ingredients and in addition may contain only impurities not avoidable in an technical environment, preferably only the ingredients) the components of the present disclosure.
  • the terms “substantially free of....” or“ substantially free from...” or “(containing/comprising) essentially no....” may be used herein; this means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1 %, or even less than 0.1 %, or even more less than 0.01 %, or even 0%, by weight of the composition.
  • the term “obtainable by” means that corresponding products do not necessarily have to be produced (i.e. obtained) by the corresponding method or process de-scribed in the respective specific context, but also products are comprised which exhibit all features of a product produced (obtained) by said corresponding method or process, wherein said products were actually not produced (obtained) by such method or process.
  • the term “obtainable by” also comprises the more limiting term “obtained by”, i.e. products which were actually produced (obtained) by a method or process described in the respective specific context.
  • the term “inventive compound” may be used instead of the “inventive (graft) polymer(s)” and “(graft) polymer(s) of this (present) invention”, meaning those compounds being disclosed herein as invention, defined by their structure and/or their process to produce or obtainable by the process defined herein.
  • cleaning composition includes compositions and formulations designed for cleaning soiled material. Such compositions and formulations include those designed for cleaning soiled material or surfaces of any kind.
  • compositions for “industrial and institutional cleaning” includes such cleaning compositions being designed for use in industrial and institutional cleaning, such as those for use of cleaning soiled material or surfaces of any kind, such as hard surface cleaners for surfaces of any kind, including tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, lacquered surfaces.
  • fabric care composition is meant to include compositions and formulations designed for treating fabric.
  • Such compositions include but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein and detailed herein below when describing the compositions.
  • compositions may be used as a pre-laundering treatment, a post- laundering treatment, or may be added during the rinse or wash cycle of the laundering operation, and as further detailed herein below when describing the use and application of the inventive graft polymers and compositions comprising such graft polymers.
  • compositions for Fabric and Home Care include cleaning compositions including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, light duty liquid detergents compositions, heavy duty liquid detergent compositions, detergent gels commonly used for laundry, bleaching compositions, laundry additives, fabric enhancer compositions, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein.
  • compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse orwash cycle of the laundering operation, preferably during the wash cycle of the laundering or dish washing operation. More preferably, such Composition for Fabric and Home Care is a laundry cleaning composition, a laundry care product or laundry washing product, most preferably a liquid laundry detergent formulation or liquid laundry detergent product.
  • the cleaning compositions of the invention may be in any form, namely, in the form of a “liquid” composition including liquid-containing composition types such as paste, gel, emulsion, foam and mousse; a solid composition such as powder, granules, micro-capsules, beads, noodles, pearlised balls, agglomerates, tablets, granular compositions, sheets, pastilles, beads, fibrous articles, bars, flakes; or a mixture thereof; ;types delivered in single- , udal- or multi-compartment pouches or containers; single-phase or multi-phase unit dose; a spray orfoam detergent; premoistened wipes (i.e.
  • the cleaning composition in combination with a nonwoven material such as that discussed in US 6,121 ,165, Mackey, et al.
  • dry wipes i.e., the cleaning composition in combination with a nonwoven materials, such as that discussed in US 5,980,931 , Fowler, et al.
  • activated with water by a user or consumer and other homogeneous, non-homogeneous or single-phase or multiphase cleaning product forms.
  • the composition can be encapsulated in a single or multi-compartment pouch.
  • a multicompartment pouch may have at least two, at least three, or at least four compartments.
  • a multi-compartmented pouch may include compartments that are side-by-side and/or superposed.
  • the composition contained in the pouch or compartments thereof may be liquid, solid (such as powders), or combinations thereof.
  • Non- limiting examples of “liquids”/”liquid compositions” include light duty and heavy duty liquid detergent compositions, fabric enhancers, detergent gels commonly used for laundry, bleach and laundry additives. Gases, e.g., suspended bubbles, or solids, e.g. particles, may be included within the liquids.
  • liquid cleaning compositions of the present invention preferably have a viscosity of from 50 to 10000 mPa*s; liquid manual dish wash cleaning compositions (also liquid manual “dish wash compositions”) have a viscosity of preferably from 100 to 10000 mPa*s, more preferably from 200 to 5000 mPa*s and most preferably from 500 to 3000 mPa*s at 20 11s and 20 °C; liquid laundry cleaning compositions have a viscosity of preferably from 50 to 3000 mPa*s, more preferably from 100 to 1500 mPa*s and most preferably from 200 to 1000 mPa*s at 20 11s and 20 °C.
  • the liquid cleaning compositions of the present invention may have any suitable pH-value.
  • the pH of the composition is adjusted to between 4 and 14. More preferably the composition has a pH of from 6 to 13, even more preferably from 6 to 10, most preferably from 7 to 9.
  • the pH of the composition can be adjusted using pH modifying ingredients known in the art and is measured as a 10% product concentration in demineralized water at 25 °C.
  • NaOH may be used and the actual weight% of NaOH may be varied and trimmed up to the desired pH such as pH 8.0.
  • a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.
  • Cleaning compositions such as fabric and home care products and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, are known to a person skilled in the art. Any composition etc. known to a person skilled in the art, in connection with the respective use, can be employed within the context of the present invention by including at least one inventive polymer, preferably at least one polymer in amounts suitable for expressing a certain property within such a composition, especially when such a composition is used in its area of use.
  • One aspect of the present invention is also the use of the inventive polymers as additives for detergent formulations, particularly for liquid detergent formulations, preferably concentrated liquid detergent formulations, or single mono doses for laundry.
  • cleaning compositions their ingredients including (adjunct) cleaning additives, their general compositions and more specific compositions are known, as for example illustrated in the publications 800542 and 800500 as published by Protegas, Liechtenstein, and also from WO 2022/136409 and WO 2022/136408, wherein in any of the before prior art documents the graft polymer within the general compositions and also each individualized specific cleaning composition disclosed in the beforementioned publications may be replaced partially or completely by the graft polymer of this present invention having the same function.
  • formulations for cleaning compositions are disclosed; all such composition types - the general compositions and also each individualized specific cleaning composition - can be equally applied also to those cleaning compositions contemplated herein.
  • the present invention also encompasses any and all of such disclosed compositions of the before-mentioned prior art-disclosures but further comprising at least one of the inventive graft polymer in addition to or as a replacement for any already ins such prior artcomposition contained polymer or any such compound, which can be replaced by such inventive graft polymer - such replacements known to a person of skill in the art - , with the content of the inventive graft polymer being present in said formulations at a concentration of generally from 0,05 to 20 wt.%, preferably up to 15 wt.
  • % more preferably up to 10 wt.%, even more preferably up to 5 wt.%, and more preferably from 0,1 , and even further more preferably from 0,5 wt.%, such as preferably 0.1 to 5 weight%, and in case of a dye transfer inhibition activity as main activity preferably at a concentration of 0.5 to 2 weight%.
  • the cleaning compositions of the invention may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as “adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before.
  • adjunct cleaning additives also abbreviated herein as “adjuncts”
  • Suitable adjunct cleaning additives include builders, cobuilders, a surfactant system, fatty acids and/or salts thereof, structurants, thickeners and rheology modifiers, clay/soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, amphiphilic copolymers (including those that are free of vinyl pyrrolidone), chelating agents, enzymes, enzyme stabilizing systems, encapsulated benefit agents such as encapsulated perfume, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, catalytic materials, brighteners, malodor control agents, pigments, dyes, opacifiers, pearlescent agents, hueing agents, dye transfer inhibiting agents, fabric softeners, carriers, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-
  • the adjunct(s) may be present in the composition at levels suitable for the intended use of the composition. Typical usage levels range from as low as 0.001 % by weight of composition for adjuncts such as optical brighteners to 50% by weight of composition for builders.
  • Liquid cleaning compositions additionally may comprise besides a surfactant system and graft polymer - and preferably do comprise at least one of - rheology control/modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.
  • Solid compositions additionally may comprise - and preferably do comprise at least one of - fillers, bleaches, bleach activators and catalytic materials.
  • Suitable examples of such cleaning adjuncts and levels of use are found in WO 99/05242, U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.
  • a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
  • the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above and below in more detail.
  • the surfactant system may be composed from one surfactant or from a combination of surfactants selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
  • a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
  • the cleaning compositions of the invention preferably comprise a surfactant system in an amount sufficient to provide desired cleaning properties.
  • the cleaning composition comprises, by weight of the composition, from about 1% to about 70% of a surfactant system.
  • the liquid cleaning composition comprises, by weight of the composition, from about 2% to about 60% of the surfactant system.
  • the cleaning composition comprises, by weight of the composition, from about 5% to about 30% of the surfactant system.
  • the surfactant system may comprise a detersive surfactant selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
  • anionic surfactants contribute usually by far the largest share of surfactants within such formulation.
  • inventive cleaning compositions for use in laundry comprise at least one anionic surfactant and optionally further surfactants selected from any of the surfactants classes described herein, preferably from non-ionic surfactants and/or amphoteric surfactants and/or zwitterionic surfactants and/or cationic surfactants.
  • Nonlimiting examples of anionic surfactants - which may be employed also in combinations of more than one surfactant - useful herein include C9-C20 linear alkylbenzenesulfonates (LAS), C10-C20 primary, branched chain and random alkyl sulfates (AS); C10-C18 secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) wherein x is from 1 to 30; C10-C18 alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99
  • suitable anionic surfactants are alkali metal and ammonium salts of C8-Ci2-alkyl sulfates, of Ci2-Cis-fatty alcohol ether sulfates, of Ci2-Cis-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-Ci2-alkylphenols (ethoxylation: 3 to 50 mol of ethylene oxide/mol), of Ci2-Ci8-alkylsulfonic acids, of C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, of Cw-Cis-alkylarylsulfonic acids, preferably of n-C -Cis-alkylbenzene sulfonic acids, of C10-C18 alkyl alkoxy carboxylates and of soaps such as for example Cs-C24-carboxylic acids.
  • Preference is given to the alkal
  • anionic surfactants are selected from n-C -Cis- alkylbenzene sulfonic acids and from fatty alcohol polyether sulfates, which, within the context of the present invention, are in particular sulfuric acid half-esters of ethoxylated C12- Cis-alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), preferably of n-Ci2-Cis- alkanols.
  • alcohol polyether sulfates derived from branched (i.e. synthetic) Cn-Ci8-alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol) may be employed.
  • the alkoxylation group of both types of alkoxylated alkyl sulfates is an ethoxylation group and an average ethoxylation degree of any of the alkoxylated alkyl sulfates is 1 to 5, preferably 1 to 3.
  • the laundry detergent formulation of the present invention comprises from at least 1 wt% to 50 wt%, preferably in the range from greater than or equal to about 2 wt% to equal to or less than about 30 wt%, more preferably in the range from greater than or equal to 3 wt% to less than or equal to 25 wt%, and most preferably in the range from greater than or equal to 5 wt% to less than or equal to 25 wt% of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.
  • anionic surfactants are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10-C18 alkylsulfates.
  • Non-limiting examples of non-ionic surfactants - which may be employed also in combinations of more than one other surfactant - include: C8-C18 alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF; C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as discussed in U.S.
  • C8-C18 alkyl ethoxylates such as, NEODOL® non-ionic surfactants from Shell
  • ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF
  • non-ionic surfactants are in particular alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides).
  • Examples of (additional) amphoteric surfactants are so-called amine oxides.
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (A)
  • R1 is selected from linear C1 -C10-alkyl, preferably ethyl and particularly preferably methyl,
  • R2 is selected from C8-C22-alkyl, for example n-C8H17, n-C10H21 , n-C12H25, n- C14H29, n-C16H33 or n-C18H37,
  • R3 is selected from C1-C10-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl or isodecyl, m and n are in the range from zero to 300, where the sum of n and m is at least one.
  • m is in the range from 1 to 100 and n is in the range from 0 to 30.
  • compounds of the general formula (A) may be block copolymers or random copolymers, preference being given to block copolymers.
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (B)
  • R 1 is identical or different and selected from linear Ci-C4-alkyl, preferably identical in each case and ethyl and particularly preferably methyl,
  • R 4 is selected from Ce-C2o-alkyl, in particular n-CsHn, n-C H2i, n-Ci2H25, n-Ci4H29, n-CieHss, n-CisH37, a is a number in the range from zero to 6, preferably 1 to 6, b is a number in the range from zero to 20, preferably 4 to 20, d is a number in the range from 4 to 25.
  • At least one of a and b is greater than zero.
  • compounds of the general formula (B) may be block copolymers or random copolymers, preference being given to block copolymers.
  • non-ionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable non-ionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. An overview of suitable further non-ionic surfactants can be found in EP-A 0 851 023 and in DE- A 198 19 187.
  • non-ionic surfactants are selected from C12/14 and C16/18 fatty alkoholalkoxylates, C13/15 oxoalkoholalkoxylates, C13- alkoholalkoxylates, and 2-propylheptylalkoholalkoxylates, each of them with 3 - 15 ethoxy units, preferably 5-10 ethoxy units, or with 1-3 propoxy- and 2-15 ethoxy units.
  • Non-limiting examples of amphoteric surfactants - which may be employed also in combinations of more than one other surfactant - include: water-soluble amine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. See WO 01/32816, US 4,681 ,704, and US 4,133,779. Suitable surfactants include thus so-called amine oxides, such as lauryl dimethyl amine oxide (“lauramine oxide”).
  • amphoteric surfactants are amine oxides.
  • Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amido propyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides and especially coco dimethyl amino oxides.
  • Amine oxides may have a linear or mid-branched alkyl moiety.
  • the amine oxide is characterized by the formula
  • R1-N(R2)(R3)-O wherein R1 is a C8-18 alkyl and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl.
  • the linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • Preferred amine oxides include linear C , linear C10-C12, and linear C12-C14 alkyl dimethyl amine oxides.
  • mid-branched means that the amine oxide has one alkyl moiety having n1 carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms.
  • the alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety.
  • This type of branching for the amine oxide is also known in the art as an internal amine oxide.
  • the total sum of n1 and n2 is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16.
  • the number of carbon atoms for the one alkyl moiety (n1) should be approximately the same number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric.
  • symmetric means that (n1-n2) is less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt%, more preferably at least 75 wt% to 100 wt% of the mid-branched amine oxides for use herein.
  • the amine oxide further comprises two moieties, independently selected from a C1-C3 alkyl, a C1-C3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups.
  • the two moieties are selected from a C1-C3 alkyl, more preferably both are selected as a C1 alkyl.
  • amphoteric surfactants are selected from C8-C18 alkyl-dimethyl aminoxides and C8-C18 alkyl-di(hydroxyethyl)aminoxide.
  • Cleaning compositions may also contain zwitterionic surfactants - which may be employed also in combinations of more than one other surfactant.
  • Suitable zwitterionic surfactants include betaines, such as alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as the phosphobetaines.
  • betaines and sulfobetaines are the following (designated in accordance with INCI): Almond amidopropyl of betaines, Apricotamidopropyl betaines, Avocadamidopropyl of betaines, Babassuamidopropyl of betaines, Behenamidopropyl betaines, Behenyl of betaines, Canol amidopropyl betaines, Capryl/Capramidopropyl betaines, Carnitine, Cetyl of betaines, Cocamidoethyl of betaines, Cocamidopropyl betaines, Cocamidopropyl Hydroxysultaine, Coco betaines, Coco Hydroxysultaine, Coco/Oleam idopropyl betaines, Coco Sultaine, Decyl of betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl G
  • Preferred betaines are, for example, Ci2-Ci8-alkylbetaines and sulfobetaines.
  • the zwitterionic surfactant preferably is a betaine surfactant, more preferable a Cocoamidopropylbetaine surfactant.
  • Non-limiting examples of cationic surfactants - which may be employed also in combinations of more than one other surfactant - include: the quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as discussed in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as discussed in US patents Nos. 4,228,042, 4,239,6604,260,529 and US 6,022,844; and amino surfactants as discussed in US 6,221 ,825 and WO 00/47708, specifically amido propyldimethyl amine (APA).
  • compositions according to the invention may comprise at least one builder.
  • builders are complexing agents, hereinafter also referred to as complexing agents, ion exchange compounds, dispersing agents, scale inhibiting agents and precipitating agents.
  • Builders are selected from citrate, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarboxylates.
  • citrate includes the mono- and the dialkali metal salts and in particular the mono- and preferably the trisodium salt of citric acid, ammonium or substituted ammonium salts of citric acid as well as citric acid.
  • Citrate can be used as the anhydrous compound or as the hydrate, for example as sodium citrate dihydrate. Quantities of citrate are calculated referring to anhydrous trisodium citrate.
  • phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate.
  • the composition according to the invention is free from phosphates and polyphosphates, with hydrogenphosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate (“phosphate-free”).
  • phosphate-free should be understood within the context of the present invention as meaning that the content of phosphate and polyphosphate is in total in the range from 10 ppm to 0.2% by weight of the respective composition, determined by gravimetry.
  • carbonates include alkali metal carbonates and alkali metal hydrogen carbonates, preferred are the sodium salts. Particularly preferred is Na2COa.
  • phosphonates are hydroxyalkanephosphonates and aminoalkane- phosphonates.
  • the hydroxyalkanephosphonates the 1-hydroxyethane-1 ,1- diphosphonate (HEDP) is of particular importance as builder. It is preferably used as sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9).
  • Suitable aminoalkanephosphonates are preferably ethylene diaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and also their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salts of DTPMP.
  • amino carboxylates and polycarboxylates are nitrilotriacetates, ethylene diamine tetraacetate, diethylene triamine pentaacetate, triethylene tetraamine hexaacetate, propylene diamines tetraacetic acid, ethanol-diglycines, methylglycine diacetate, and glutamine diacetate.
  • amino carboxylates and polycarboxylates also include their respective non-substituted or substituted ammonium salts and the alkali metal salts such as the sodium salts, in particular of the respective fully neutralized compound.
  • Silicates in the context of the present invention include in particular sodium disilicate and sodium metasilicate, alumosilicates such as for example zeolites and sheet silicates, in particular those of the formula a-Na2Si20s, P-Na2Si20s, and 5-Na2Si20s.
  • compositions according to the invention may contain one or more builder selected from materials not being mentioned above.
  • builders are a-hydroxypropionic acid and oxidized starch.
  • builder is selected from polycarboxylates.
  • polycarboxylates includes non-polymeric polycarboxylates such as succinic acid, C2- Ci6-alkyl disuccinates, C2-Ci6-alkenyl disuccinates, ethylene diamine N,N’-disuccinic acid, tartaric acid diacetate, alkali metal malonates, tartaric acid monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid.
  • Oligomeric or polymeric polycarboxylates are for example polyaspartic acid and its alkali metal salts, in particular its sodium salt, (meth)acrylic acid homopolymers and (meth)acrylic acid copolymers and their alkali metal salts, in particular their sodium salts.
  • Suitable co-monomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
  • a suitable polymer is in particular polyacrylic acid, which preferably has a weight-average molecular weight M w in the range from 2000 to 40 000 g/mol, preferably 2000 to 10 000 g/mol, in particular 3000 to 8000 g/mol.
  • copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid or or anhydrides thereof such as maleic anhydride.
  • Suitable copolymers are in particular copolymers of acrylic acid and maleic acid of a weight average molecular weight Mw in the range of 2000 to 100000, preferably 3000 to 80000.
  • the preferred weight-average molecular weight Mw of the polyaspartic acid lies in the range between 1000 g/mol and 20 000 g/mol, preferably between 1500 and 15 000 g/mol and particularly preferably between 2000 and 10 000 g/mol.
  • Suitable hydrophobic co-monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with ten or more carbon atoms or mixtures thereof, such as, for example, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene, C22-a-olefin, a mixture of C20- C24-a-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.
  • Suitable hydrophilic co-monomers are monomers with sulfonate or phosphonate groups, and also non-ionic monomers with hydroxyl function or alkylene oxide groups.
  • allyl alcohol isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate.
  • Polyalkylene glycols here can comprise 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
  • Particularly preferred sulfonic-acid-group-containing monomers here are 1-acrylamido-1- propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3- methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2- propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1 -sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfo
  • Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.
  • oligomeric or polymeric polycarboxylates comprise graft polymers of (meth)acrylic acid or maleic acid onto polysaccharides such as degraded starch, carboxymethylated polysaccharides such as carboxymethylated cellulose, carboxymethylated inulin or carboxymethylated starch or polyepoxysuccinic acid and their alkali metal salts,, in particular their sodium salts.
  • amphoteric polymers can also be used as builders.
  • compositions according to the invention can comprise, for example, in the range from in total 0.1 to 90 % by weight, preferably 5 to 80% by weight, preferably up to 70% by weight, of builder(s), especially in the case of solid formulations.
  • Liquid formulations according to the invention preferably comprise in the range of from 0.1 to 20 % by weight of builder, such as up to 85, 75, 65, 60, 55, 50, 45, 40, 35, 30, 35, 15, or 10 % by weight.
  • Formulations according to the invention can comprise one or more alkali carriers.
  • Alkali carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired.
  • a preferred alkali metal is in each case potassium, particular preference being given to sodium.
  • a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.
  • the laundry formulation according to the invention comprises additionally at least one enzyme.
  • Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types.
  • Such enzyme(s) can be incorporated at levels sufficient to provide an effective amount for cleaning.
  • the preferred amount is in the range from 0.001 % to 5 % of active enzyme by weight in the detergent composition according to the invention.
  • enzyme stabilizing systems may be used such as for example calcium ions, boric acid, boronic acid, propylene glycol and short chain carboxylic acids.
  • short chain carboxylic acids are selected from monocarboxylic acids with 1 to 3 carbon atoms per molecule and from dicarboxylic acids with 2 to 6 carbon atoms per molecule.
  • Preferred examples are formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, HOOC(CH2)3COOH, adipic acid and mixtures from at least two of the foregoing, as well as the respective sodium and potassium salts.
  • the at least one enzyme is a detergent enzyme.
  • the enzyme is classified as an oxidoreductase (EC 1), a transferase (EC).
  • EC 1 oxidoreductase
  • EC 2 transferase
  • EC- numbering is according to Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology including its supplements published 1993-1999.
  • the enzyme is a hydrolase (EC
  • the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, DNase, phosphodiesterases, phytases, carbohydrases, galactanases, xanthanases, xyloglucanases, oxidoreductase, perhydrolases, amino
  • the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the foregoing types.
  • the enzyme is a protease, preferably, a serine protease, more preferably, a subtilisin protease.
  • the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101 E (according to BPN’ numbering).
  • the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881 A1.
  • composition of the present invention can comprise one type of enzyme or more than one enzyme of different types, e.g., an amylase and a protease, or more than one enzyme of the same type, e.g., two or more different proteases, or mixtures thereof, e.g., an amylase and two different proteases.
  • the enzyme(s) can be incorporated into the composition at levels sufficient to provide an effective amount for achieving a beneficial effect, preferably for primary washing effects and/or secondary washing effects, like anti-greying or antipilling effects (e.g., in case of cellulases).
  • the enzyme is present in the composition at levels from about 0.00001% to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001% to about 1 %, or even more preferably from about 0.001% to about 0.5% enzyme protein by weight of the composition.
  • the enzyme-containing composition further comprises an enzyme stabilizing system.
  • the enzyme-containing composition described herein comprises from about 0.001 % to about 10%, from about 0.005% to about 8%, or from about 0.01 % to about 6%, by weight of the composition, of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme.
  • the enzyme stabilizing system comprises at least one compound selected from the group consisting of polyols (preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2- propanediol, or sorbitol), inorganic salts (preferably, CaCI2, MgCI2, or NaCI), short chain (preferably, C1-C3) carboxylic acids or salts thereof (preferably, formic acid, formate (preferably, sodium formate), acetic acid, acetate, or lactate), borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • polyols preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2- propanediol, or sorbitol
  • the enzyme stabilizing system comprises a combination of at least two of the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids and preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • boronic acids preferably, 4-formyl phenylboronic acid (4-FP
  • protease inhibitors may be added, preferably selected from borate, boric acid, boronic acids (preferably, 4-FPBA), peptide aldehydes (preferably, peptide aldehydes like Z- VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • compositions according to the invention may comprise one or more bleaching agent (bleaches).
  • Preferred bleaches are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term “persulfate” in each case includes the salt of the peracid H2SO5 and also the peroxodisulfate.
  • the alkali metal salts can in each case also be alkali metal hydrogen carbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulfate.
  • the dialkali metal salts are preferred in each case.
  • Formulations according to the invention can comprise one or more bleach catalysts.
  • Bleach catalysts can be selected from oxaziridinium-based bleach catalysts, bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron- , cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.
  • Formulations according to the invention can comprise one or more bleach activators, for example tetraacetyl ethylene diamine, tetraacetylmethylene diamine, tetraacetylglycoluril, tetraacetylhexylene diamine, acylated phenolsulfonates such as for example n-nonanoyl- or isononanoyloxybenzene sulfonates, N-methylmorpholinium-acetonitrile salts (“MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N- nonanoylsuccinimide, 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • bleach activators for example tetraacetyl ethylene di
  • Formulations according to the invention can comprise one or more corrosion inhibitors.
  • corrosion inhibitors include triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
  • formulations according to the invention comprise in total in the range from 0.1 to 1 .5% by weight of corrosion inhibitor.
  • Formulations according to the invention may also comprise further cleaning polymers and/or soil release polymers and/or anti-graying polymers.
  • the further cleaning polymers may include, without limitation, “multifunctional polyethylene imines” (for example BASF’s Sokalan® HP20) and/or “multifunctional diamines” (for example BASF’s Sokalan® HP96).
  • multifunctional polyethylene imines are typically ethoxylated polyethylene imines with a weight-average molecular weight M w in the range from 3000 to 250000, preferably 5000 to 200000, more preferably 8000 to 100000, more preferably 8000 to 50000, more preferably 10000 to 30000, and most preferably 10000 to 20000 g/mol.
  • Suitable multifunctional polyethylene imines have 80 wt% to 99 wt%, preferably 85 wt% to 99 wt%, more preferably 90 wt% to 98 wt%, most preferably 93 wt% to 97 wt% or 94 wt% to 96 wt% ethylene oxide side chains, based on the total weight of the materials.
  • Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell.
  • Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight M w in the range of 500 to 5000 g/mol.
  • ethoxylated polymer Preferably employed is a molecular weight from 500 to 1000 g/mol, even more preferred is a M w of 600 to 800 g/mol.
  • the ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.
  • EO ethylene oxide
  • Suitable multifunctional diamines are typically ethoxylated C2 to C12 alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated.
  • Typical multifunctional diamines have a weight-average molecular weight M w in the range from 2000 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g/mol.
  • ethoxylated hexamethylene diamine may be employed, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.
  • EO ethylene oxide
  • Suitable further multifunctional polyethylene imines, multifunctional di- and oligoamines include those as claimed in WO2021/254828, WO2022/136408A1 , WO2022/136409A1 , WO2021/165468, W02023/021103, W02023/021104, W02023/021105 and
  • the cleaning compositions may contain at least one multifunctional polyethylene imine and/or at least one multifunctional di- and/or oligoamine, specifically any of the claimed polymers from WO2021/254828, WO2022/136408A1 , WO2022/136409A1 , WO2021/165468, W02023/021103,
  • the multifunctional polyethylene imines or multifunctional di- or oligomines or mixtures thereof according to the descriptions above may be added to the laundry detergents and cleaning compositions in amounts of generally from 0.05 to 15 wt%, preferably from 0.1 to 10 wt% and more preferably from 0.25 to 5 wt% and even as low as up to 2 wt.%, based on the particular overall composition, including other components and water and/or solvents.
  • one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one inventive polymer and (ii) at least one compound selected from multifunctional polyethylene imines and multifunctional di-and oligoamines and mixtures thereof.
  • the ratio of the at least one inventive polymer and (ii) the at least one compound selected from multifunctional polyethylene imines and multifunctional di- and oligoamines and mixtures thereof is from 10:1 to 1 :10, preferably from 5:1 to 1 :5 and more preferably from 3:1 to 1 :3.
  • Suitable anti-graying polymers comprise copolymers of acrylic or maleic acid and styrene, graft polymers of acrylic acid onto maltodextrin or carboxymethylated cellulose and their alkali metal salts,, in particular their sodium salts.
  • Laundry formulations comprising the inventive polymer may also comprise at least one complexing agent.
  • Preferred complexing agents are methylglycinediacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and salts thereof.
  • Particularly preferred complexing agents are methylglycinediacetic acid and salts thereof. According to the invention, preference is given to 1 to 50% (wiirde ichcomb auf 20 Gew.%) by weight of complexing agents.
  • MGDA and GLDA can be present as racemate or as enantiomerically pure compound.
  • GLDA is preferably selected from L-GLDA or enantiomerically enriched mixtures of L-GLDA in which at least 80 mol%, preferably at least 90 mol%, of L-GLDA is present.
  • complexing agent is racemic MGDA.
  • complexing agent is selected from L-MGDA and from enantiomer mixtures of L- and D-MGDA in which L-MGDA predominates and in which the L/D molar ratio is in the range from 55:45 to 95:5, preferably 60:40 to 85:15.
  • the L/D molar ratio can be determined for example by polarimetry or by chromatographic means, preferably by HPLC with a chiral column, for example with cyclodextrin as stationary phase or with an optically active ammonium salt immobilized on the column. For example, it is possible to use an immobilized D-penicillamine salt.
  • MGDA or GLDA is preferably used as the salt.
  • Preferred salts are ammonium salts and alkali metal salts, particularly preferably the potassium and in particular the sodium salts. These can for example have the general formula (CA I) or (CA II):
  • Laundry formulations comprising the inventive polymer may also comprise at least one antimicrobial agent.
  • An antimicrobial agent is a chemical compound that kills microorganisms or inhibits their growth or reproduction. Microorganisms can be bacteria, yeasts or molds.
  • a preservative is an antimicrobial agent which may be added to aqueous products and compositions to maintain the original performance, characteristics and integrity of the products and compositions by killing contaminating microorganisms or inhibiting their growth.
  • composition/formulation may contain one or more antimicrobial agents and/or preservatives as listed in patent WO2021/115912 A1 (“Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes”) on pages 35 to 39.
  • antimicrobial agents and/or preservatives are any of the following antimicrobial agents and/or preservatives:
  • the composition contains 2-phenoxyethanol in a concentration of 0.1 to 2% or 4,4’-dichloro 2-hydroxydiphenyl ether (DCPP) in a concentration of 0.005 to 0.6%
  • DCPP 4,4’-dichloro 2-hydroxydiphenyl ether
  • the inventive laundry formulation may comprise at least one antimicrobial agent from the above list and/or a combination thereof, and/or a combination with at least one further antimicrobial agent not listed here.
  • Formulations according to the invention may also comprise water and/or additional organic solvents, e.g. ethanol or propylene glycol, and/or fillers such as sodium sulfate.
  • additional organic solvents e.g. ethanol or propylene glycol
  • fillers such as sodium sulfate.
  • Further optional ingredients may be but are not limited to viscosity modifiers, cationic surfactants, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, and dye transfer inhibiting agents.
  • Another aspect of the present invention is also a dish wash composition, comprising at least one inventive polymer as described above.
  • an aspect of the present invention is also the use of the inventive polymer as described above, in dish wash applications, such as manual or automated dish wash applications.
  • Dish wash compositions according to the invention can be in the form of a liquid, semi-liquid, cream, lotion, gel, or solid composition, solid embodiments encompassing, for example, powders and tablets.
  • Liquid compositions are typically preferred for manual dish wash applications, whereas solid formulations and pouch formulations (where the pouches may contain also solids in addition to liquid ingredients) are typically preferred for automated dish washing compositions; however, in some areas of the world also liquid automated dish wash compositions are used and are thus of course also encompassed by the term “dish wash composition”.
  • dish wash compositions are intended for direct or indirect application onto dishware and metal and glass surfaces, such as drinking and other glasses, beakers, dish and cooking ware like pots and pans, and cutlery such as forks, spoons, knives and the like.
  • the inventive method of cleaning dishware, metal and/or glass surfaces comprises the step of applying the dish wash cleaning composition, preferably in liquid form, onto the surface, either directly or by means of a cleaning implement, i.e., in neat form.
  • the composition is applied directly onto the surface to be treated and/or onto a cleaning device or implement such as a dish cloth, a sponge or a dish brush and the like without undergoing major dilution (immediately) prior to the application.
  • the cleaning device or implement is preferably wet before or after the composition is delivered to it.
  • the composition can also be applied in diluted form. Both neat and dilute application give rise to superior cleaning performance, i.e.
  • the formulations of the invention containing at least one inventive polymer exhibit excellent degreasing properties.
  • the effort of removing fat and/or oily soils from the dishware, metal and/or glass surfaces is decreased due to the presence of the inventive polymer, even when the level of surfactant used is lower than in conventional compositions.
  • the composition is formulated to provide superior grease cleaning (degreasing) properties, long-lasting suds and/or improved viscosity control at decreased temperature exposures; preferably at least two, more preferably all three properties are present in the inventive dish wash composition.
  • Optional - preferably present - further benefits of the inventive manual dish wash composition include soil removal, shine, and/or hand care; more preferably at least two and most preferably all three further benefits are present in the inventive dish wash composition.
  • the inventive polymer is one component of a manual dish wash formulation that additionally comprises at least one surfactant, preferably at least one anionic surfactant.
  • the inventive polymer is one component of a manual dish wash formulation that additionally comprises at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric surfactants and/or zwitterionic surfactants.
  • the manual dish wash formulations contain at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or mixtures thereof, to aid in the foaming, detergency, and/or mildness of the detergent composition.
  • Preferred anionic surfactants for dish wash compositions are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10-C18 alkylsulfates.
  • the manual dish wash detergent formulation of the present invention comprises from at least 1 wt% to 50 wt%, preferably in the range from greater than or equal to about 3 wt% to equal to or less than about 35 wt%, more preferably in the range from greater than or equal to 5 wt% to less than or equal to 30 wt%, and most preferably in the range from greater than or equal to 5 wt% to less than or equal to 20 wt% of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.
  • Dish wash compositions according to the invention may comprise at least one amphoteric surfactant.
  • amphoteric surfactants for dish wash compositions are already mentioned above for laundry compositions.
  • Preferred amphoteric surfactants for dish wash compositions are selected from C8-C18 alkyldimethyl aminoxides and C8-C18 alkyl-di(hydroxyethyl)aminoxide.
  • the manual dish wash detergent composition of the invention preferably comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of an amphoteric surfactant, preferably an amine oxide surfactant.
  • the composition of the invention comprises a mixture of the anionic surfactants and alkyl dimethyl amine oxides in a weight ratio of less than about 10:1 , more preferably less than about 8:1 , more preferably from about 5:1 to about 2:1 .
  • amphoteric surfactant provides good foaming properties in the dish wash composition.
  • Dish wash compositions according to the invention may comprise at least one zwitterionic surfactant.
  • Suitable zwitterionic surfactants for dish wash compositions are already mentioned above for laundry compositions.
  • Preferred zwitterionic surfactants for dish wash compositions are selected from betaine surfactants, more preferable from Cocoamidopropylbetaine surfactants.
  • the zwitterionic surfactant is Cocamidopropylbetaine.
  • the manual dish wash detergent composition of the invention optionally comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of a zwitterionic surfactant, preferably a betaine surfactant.
  • Dish wash compositions according to the invention may comprise at least one cationic surfactant.
  • Suitable cationic surfactants for dish wash compositions are already mentioned above for laundry compositions.
  • Cationic surfactants when present in the composition, are present in an effective amount, more preferably from 0.1 wt% to 5 wt%, preferably 0.2 wt% to 2 wt% of the composition.
  • Dish wash compositions according to the invention may comprise at least one non-ionic surfactant.
  • non-ionic surfactants for dish wash compositions are already mentioned above for laundry compositions.
  • Preferred non-ionic surfactants are the condensation products of Guerbet alcohols with from 2 to 18 moles, preferably 2 to 15, more preferably 5-12 of ethylene oxide per mole of alcohol.
  • Other preferred non-ionic surfactants for use herein include fatty alcohol polyglycol ethers, alkylpolyglucosides and fatty acid glucamides.
  • the manual hand dish detergent composition of the present invention may comprise from 0.1 wt% to 10 wt%, preferably from 0.3 wt% to 5 wt%, more preferably from 0.4 wt% to 2 wt% of the composition, of a linear or branched C10 alkoxylated non-ionic surfactant having an average degree of alkoxylation of from 2 to 6, preferably from 3 to 5.
  • the linear or branched C10 alkoxylated non-ionic surfactant is a branched C10 ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 2 to 6, preferably of from 3 to 5.
  • the composition comprises from 60 wt% to 100 wt%, preferably from 80 wt% to 100 wt%, more preferably 100 wt% of the total linear or branched C10 alkoxylated non-ionic surfactant of the branched C10 ethoxylated non-ionic surfactant.
  • the linear or branched C10 alkoxylated non-ionic surfactant preferably is a 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5.
  • a suitable 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of 4 is Lutensol® XP40, commercially available from BASF SE, Ludwigshafen, Germany.
  • the use of a 2- propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5 leads to improved foam levels and long-lasting suds.
  • one aspect of the present invention is a manual dish wash detergent composition, in particular a liquid manual dish wash detergent composition, comprising (i) at least one inventive polymer, and (ii) at least one further 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5.
  • Dish wash compositions according to the invention may comprise at least one hydrotrope in an effective amount, to ensure the compatibility of the liquid manual dish wash detergent compositions with water.
  • Suitable hydrotropes for use herein include anionic hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium, potassium, and ammonium cumene sulfonate, and mixtures thereof, and related compounds, as disclosed in U.S. Patent 3,915,903.
  • the liquid manual dish wash detergent compositions of the present invention typically comprise from 0.1 wt% to 15 wt% of the total liquid detergent composition of a hydrotrope, or mixtures thereof, preferably from 1 wt% to 10 wt%, most preferably from 2 wt% to 5 wt% of the total liquid manual dish wash composition.
  • Dish wash compositions according to the invention may comprise at least one organic solvent.
  • organic solvents examples include C4-C14 ethers and diethers, glycols, alkoxylated glycols, C6-C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
  • the liquid dish wash compositions will contain from 0.01 wt% to 20 wt%, preferably from 0.5 wt% to 15 wt%, more preferably from 1 wt% to 10 wt%, most preferably from 1 wt% to 5 wt% of the liquid detergent composition of a solvent.
  • solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present.
  • the absolute values of the viscosity may drop but there is a local maximum point in the viscosity profile.
  • the dish wash compositions herein may further comprise from 30 wt% to 90 wt% of an aqueous liquid carrier, comprising water, in which the other essential and optional ingredients are dissolved, dispersed or suspended. More preferably the compositions of the present invention comprise from 45 wt% to 85 wt%, even more preferably from 60 wt% to 80 wt% of the aqueous liquid carrier.
  • the aqueous liquid carrier may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature (25 °C) and which may also serve some other function besides that of an inert filler.
  • Dish wash compositions according to the invention may comprise at least one electrolyte. Suitable electrolytes are preferably selected from inorganic salts, even more preferably selected from monovalent salts, most preferably sodium chloride.
  • the liquid manual dish wash compositions according to the invention may comprise from 0.1 wt% to 5 wt%, preferably from 0.2 wt% to 2 wt% of the composition of an electrolyte.
  • Manual dish wash formulations comprising the inventive polymer may also comprise at least one antimicrobial agent.
  • the antimicrobial agent may be added to the inventive hand dish wash compositon in a concentration of 0.0001 wt% to 10 wt% relative to the total weight of composition.
  • the formulation contains 2-phenoxyethanol in a concentration of 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt% and/or 4, 4’-dichloro 2-hydroxydiphenyl ether in a concentration of 0.001 wt% to 1 wt%, more preferably 0.002 wt% to 0.6 wt% (in all cases relative to the total weight of the composition).
  • Further additional ingredients are such as but not limited to conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, emollients, humectants, skin rejuvenating actives, carboxylic acids, scrubbing particles, bleach and bleach activators, perfumes, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, antibacterial agents, pH adjusters including NaOH and alkanolamines such as mono-ethanolamines and buffering means.
  • the cleaning formulations typically have a pH of about 7 or higher, and additionally often contain also enzymes - which are included into such cleaning formulations to degrade biodegradable stuff such as grease, proteins, polysaccharides etc which are present in the stains and dirt which shall be removed by the cleaning compositions - some consideration is needed to be taken to formulate those bio-degradable polymers of the invention.
  • Such formulations suitable are in principle known, and include the formulation in solids - where he enzymes and the polymers can be separated by coatings or adding them in separate particles which are mixed - and liquids and semiliquids, where the polymers and the enzymes can be separated by formulating them in different compartments, such as different compartments of multi-chamber-pouches or bottles having different chambers, from which the liquids are poured out at the same time in a predefined amount to assure the application of the right amount per individual point of use of each component from each chamber.
  • Such multi-compartment-pouches and bottles etc are known to a person of skill as well.
  • the liquid formulations disclosed in this chapter may comprise 0 to 2 % 2-phenoxyethanol, preferably about 1 %, in addition to all other mentioned ingredients.
  • the above and below disclosed liquid formulations may comprise 0-0,2% 4,4’-dichoro 2- hydroxydiphenylethe, preferably about 0,15 %, in addition to all other mentioned ingredients.
  • the bleach-free solid laundry compositions may comprise 0-0,2% 4,4’-dichoro 2- hydroxydiphenylethe, preferably about 0,15 %, in addition to all other mentioned ingredients.
  • the formulations disclosed in this chapter may - in addition to all other mentioned ingredients -comprise one or more enzymes selected from those disclosed herein above, more preferably a protease and/or an amylase, wherein even more preferably the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101 E (according to BPN’ numbering) and wherein the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881A1 , such enzyme(s) preferably being present in the formulations at levels from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, or even more preferably from about 0.001% to about 0.5% enzyme protein by weight of the composition.
  • enzymes selected from those disclosed herein above, more preferably a protease and/or an amylase, wherein even more preferably the
  • compositions shown below including those in the tables disclose general cleaning compositions of certain types, which correspond to typical compositions correlating with typical washing conditions as typically employed in various regions and countries of the world.
  • the at least one inventive polymer may be added to such formulation (s) in suitable amounts as outlined herein.
  • compositions are a comparative composition.
  • inventive graft polymer especially in the amounts that are described herein as preferred, more preferred etc ranges, such compositions are considered to fall within the scope of the present invention.
  • the graft polymer according to the present invention is used in a laundry detergent.
  • Liquid laundry detergents according to the present invention are composed of:
  • Preferred liquid laundry detergents according to the present invention are composed of:
  • At least one inventive polymer 5 - 40 % of anionic surfactants selected from C10-C15- LAS and C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units
  • nonioic surfactants selected from C10-C18-alkyl ethoxylates containing 3 - 10 ethoxy-units
  • soluble organic builders/ cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxy-di- and hydroxytricaboxylic acids, aminopolycarboxylates and polycarboxylic acids 0,05 - 5 % of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system
  • Solid laundry detergents (like e.g. powders, granules or tablets) according to the present invention are composed of:
  • Preferred solid laundry detergents according to the present invention are composed of: 0,5 - 10 % of at least one inventive polymer
  • anionic surfactants selected from C10-C15- LAS, C10-C18 alkylsulfates and C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units
  • non-ionic surfactants selected from C10-C18-alkyl ethoxylates containing 3 - 10 ethoxy-units
  • inorganic builders and fillers selected from sodium carbonate, sodium bicarbonate, zeolites, soluble silicates, sodium sulfate
  • cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, aminopolycarboxylates and polycarboxylic acids
  • an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system
  • the polymer according to the present invention is used in a manual dish wash detergent.
  • Liquid manual dish wash detergents are composed of: 0,05 - 10 % of at least one inventive polymer 1 - 50% of surfactants 0,1 - 50 % of other adjuncts water to add up 100 %.
  • Preferred liquid manual dish wash detergents according to the present invention are composed of: 0,2 - 5 % of at least one inventive polymer 5 - 40 % of anionic surfactants selected from C10-C15- LAS, C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units, and C10-C18 alkylsulfate
  • a non-ionic surfactant preferably a C10-Guerbet alcohol alkoxylate
  • an enzyme preferably Amylase, and preferably also an enzyme stabilizing system
  • Liquid laundry frame formulations according to the invention are Liquid laundry frame formulations according to the invention:
  • liquid detergent formulations LD1 , LD2 and LD3 are shown in the following three tables: (numbers: wt.% active) Liquid detergent 1- LD1 “excellent” detergent;
  • All previous three tables on LD1 , LD2, LD3: *”graft polymer” (poly ethylene glycol of Mn 6000 g/mol as graft base, grafted with 40 weigth % vinyl acetate (based on total polymer weight; produced following general disclosure of W02007138054A1).
  • Liquid manual dish wash frame formulations according to the invention are Liquid manual dish wash frame formulations according to the invention:
  • the at least one graft polymer is present at a concentration of from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1 % to about 10%, and most preferably from about 0.5% to about 5%, in relation to the total weight of such composition or product in relation to the total weight of such composition or product, each in weight % in relation to the total weight of such composition or product, and all numbers in between, and including all ranges resulting from selecting any of the lower limits mentioned and including further 0.2, 0.3, 0.4, 1 , 1 ,5, 2, 2.5, 3, 3.5 and 4, and combing with any of the upper limits mentioned and including 19, 18, 17, 16, 14, 13, 12, 11 , 9, 8, 7, and 6.
  • At least one graft polymer as described herein and/or the at least one graft polymer obtained or obtainable by the inventive process as detailed before is present - when acting solely as dye transfer inhibiting agent - in said inventive compositions and products at a concentration of from about 0.05% to about 20%, preferably 0,05 to 10%, more preferably from about 0,1 % to 8%, even more preferably from about 0.2% to about 6%, and further more preferably from about 0,2% to about 4%, and most preferably in amounts of up to 2%, each in weight % in relation to the total weight of such composition or product, and further including all ranges resulting from selecting any of the lower limits and any of the upper limits and all numbers in between those mentioned.
  • the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity Mw/Mn of the inventive graft polymers can be determined by gel permeation chromatography in dimethylacetamide.
  • the mobile phase (eluent) to be used is dimethylacetamide comprising 0.5 wt% LiBr.
  • the concentration of graft polymer in tetrahydrofuran is 4.0 mg per mL. After filtration (pore size 0.2 pm), 100 pL of this solution are to be injected into the GPC system.
  • Four columns (heated to 60°C) may be used for separation (PLgel precolumn, 3 PLgel MIXED-E column).
  • the GPC system is operated at a flow rate of 1 mL per min.
  • a DRI Agilent 1100 may be used as the detection system.
  • Polyethylene glycol) (PEG) standards (PL) having a molecular weight Mn from 106 to 1 378 000 g/mol may be used for the calibration.
  • backbone prepared as backbone for inventive graft polymers; their abbreviations of the structures are:
  • Caprolactone is oligomerized before alkylene oxide polymerization yielding mixed random/block structures, and backbones are obtained by alkoxylation of polycaprolactones.
  • a starter molecule can be used (such as in case of backbone I and J: neopentylglycol, “NPG”).
  • NPG neopentylglycol
  • Caprolactone is added after alkylene oxide polymerization yielding block structures polycaprolactone- polyalkylene oxide -polycaprolactone
  • Inventive graft polymers 1-21 are synthesized based on backbone A-J.
  • VAc Vinyl acetate
  • VL Vinyl laurate
  • VP Vinyl pyrrolidone
  • Example 1 a polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone
  • Example 1 b (Backbone A): polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone and ethoxylated with 70 moles ethylene oxide
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone A (455.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (2.81 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 (245.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 9,20 g/h and 00:10 h to 06:10 h: 4.34 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 40.8 g/h).
  • Feed 3 (1.79 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 745 g of a polymer solution.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone A (450.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (10.08 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 36.89 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 (450.50 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 15,7 g/h and 00:10 h to 06:10 h: 7.39 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 75.0 g/h).
  • Feed 3 (3.19 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 11.66 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 961 g of a polymer solution.
  • Example 3 a (Backbone C): polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone and ethoxylated with 102.2 moles ethylene oxide
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone C (455.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (2.81 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 (245.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 9,20 g/h and 00:10 h to 06:10 h: 4.34 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 40.8 g/h).
  • Feed 3 (1.79 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 745 g of a polymer solution.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone C (400.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (7.24 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 31.90 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 600.00 g of vinyl acetate
  • a variable feed rate of Feed 1 0:00 h to 00:10 h: 13,1 g/h and 00:10 h to 06:10 h: 5.13 g/h
  • a constant feed rate of Feed 2 (00:10 h to 06:10 h: 83.4 g/h).
  • Feed 3 (4.80 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 21.12 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 1065 g of a polymer solution.
  • Example 5 a polyethylene glycol (molecular weight 1500 g/mol), ethoxylated with 44 moles ethylene oxide
  • Example 5 b (Backbone D): polyethylene glycol (molecular weight 1500 g/mol), ethoxylated with 44 moles ethylene oxide and modified with 6 moles caprolactone
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone D (455.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (2.81 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 (245.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 9,20 g/h and 00:10 h to 06:10 h: 4.34 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 40.8 g/h).
  • Feed 3 (1.79 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 745 g of a polymer solution.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone D (679.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (10.87 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 39.76 g of tripropylene glycol) and 10 min upon the start of Feed 1
  • Feed 2 (a mixture of 242.50 g of vinyl acetate and 48.50 g of vinyl laurate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 16,9 g/h and 00:10 h to 06:10 h: 7.97 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 48.5 g/h).
  • Feed 3 (3.43 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 12.56 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 1036 g of a polymer solution.
  • Example 7 a (Backbone E): polyethylene glycol (molecular weight 1500 g/mol), modified with 3 moles caprolactone
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone E (540.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (7.56 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 27.67 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 135.00 g of vinyl acetate
  • a variable feed rate of Feed 1 0:00 h to 00:10 h: 11 ,8 g/h and 00:10 h to 06:10 h: 5.55 g/h
  • a constant feed rate of Feed 2 (00:10 h to 06:10 h: 22.5 g/h).
  • Feed 3 (2.39 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 8.74 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 721 g of a polymer solution.
  • Example 8 a polyethylene glycol (molecular weight 600 g/mol), ethoxylated with 47.2 moles ethylene oxide
  • Example 8 b (Backbone F): polyethylene glycol (molecular weight 600 g/mol), ethoxylated with 47.2 moles ethylene oxide and modified with 10 moles caprolactone
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone F (397.29 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (3.16 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 35.56 g of propane-1 ,2-diol) and 10 min upon the start of Feed 1
  • Feed 2 (238.37 g of vinyl acetate)
  • Feed 3 158.92 g of N- Vinylpyrrolidone
  • Feed 4 (2.03 g of tert-Butyl peroxy- 2-ethylhexanoate dissolved in 22.80 g of propane-1 , 2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 721 g of a polymer solution.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone F (50.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (1.12 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 4.10 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 (50.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 1 ,74 g/h and 00:10 h to 06:10 h: 0.82 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 8.33 g/h).
  • Feed 3 (0.35 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 1 .30 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 107 g of a polymer solution
  • Example 10 a polyethylene glycol (molecular weight 600 g/mol), ethoxylated with 47.2 moles ethylene oxide and modified with 3 moles caprolactone) (Backbone G)ln a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 669.8 g polyethylene glycol (molecular weight 600 g/mol), ethoxylated with 47.2 moles ethylene oxide (example 8a) and 0.8 g tin(ll)ethylhexanoate were placed and heated to 80°C.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone G (75.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (1.68 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 6.15 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 (75.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 2.61 g/h and 00:10 h to 06:10 h: 1 .23 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 12.50 g/h).
  • Feed 3 (0.53 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 1 .94 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 160 g of a polymer solution
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone G (97.50 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (0.60 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 6.92 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1
  • Feed 2 (30.00 g of vinyl acetate) and Feed 3 (22.50 g of N- Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 2.51 g/h and 00:10 h to 06:10 h: 3.75 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 5.00 g/h) and Feed 3 (00:10 h to 06:10 h: 3.75 g/h).
  • Feed 4 (0.38 g of tert-Butyl peroxy- 2-ethylhexanoate dissolved in 4.44 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 162 g of polymer a solution.
  • Example 12 a Neopentylglycol, modified with 8 moles caprolactone
  • Example 12 b Neopentylglycol, modified with 8 moles caprolactone and ethoxylated with 46 moles ethylene oxide) (Backbone H)
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone H (79.80 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (1.49 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 13.17 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 (53.20 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.89 g/h and 00:10 h to 06:10 h: 0.23 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 8.87 g/h).
  • Feed 3 (0.34 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 2.99 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 150 g of a polymer solution Example 13 (Inv. 13)
  • Example 13 a Neopentylglycol, modified with 8 moles caprolactone and alkoxylated with a mixture of 40 moles ethylene oxide and 4 moles propylene oxide (Backbone I)
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone I (78.00 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (1.35 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 11.88 g of tripropylene glycol) and 10 min upon the start of Feed 1 ,
  • Feed 2 (42.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.41 g/h and 00:10 h to 06:10 h: 0.23 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 7.09 g/h).
  • Feed 3 (0.31 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 2.70 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 136 g of a polymer solution
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone I (97.50 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (1.22 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1
  • Feed 2 (45.00 g of vinyl acetate) and Feed 3 (7.50 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.49 g/h and 00:10 h to 06:10 h: 1.25 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 7.50 g/h) and Feed 3 (00:10 h to 06:10 h: 1.25 g/h).
  • Feed 4 (0.38 g of tert-Butyl peroxy-2- ethylhexanoate dissolved in 3.80 g of propane-1 , 2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 165 g of a polymer solution.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone 1(97.50 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (1.22 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1
  • Feed 2 (37.50 g of vinyl acetate) and Feed 3 (15.00 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.49 g/h and 00:10 h to 06:10 h: 2.12 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 6.25 g/h) and Feed 3 (00:10 h to 06:10 h: 2.50 g/h).
  • Feed 4 (0.38 g of tert-Butyl peroxy-2- ethylhexanoate dissolved in 3.80 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 167 g of a polymer solution.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone I (97.50 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (1.22 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1
  • Feed 2 (30.00 g of vinyl acetate) and Feed 3 (22.50 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.49 g/h and 00:10 h to 06:10 h: 2.12 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 5.00 g/h) and Feed 3 (00:10 h to 06:10 h: 3.75 g/h).
  • Feed 4 (0.38 g of tert-Butyl peroxy-2- ethylhexanoate dissolved in 3.80 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 165 g of a polymer solution.
  • Example 17 a Neopentylglycol, modified with 2 moles caprolactone
  • Example 17 b Neopentylglycol, modified with 2 moles caprolactone and ethoxylated with 40 moles ethylene oxide (Backbone J)
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone J(97.50 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (1 .68 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 6.15 g of tripropylene glycol) and 10 min upon the start of Feed 1
  • Feed 2 (37.50 g of vinyl acetate) and Feed 3 (15.00 g of Vinyl laurate) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 2.61 g/h and 00:10 h to 06:10 h: 1.23 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 6.25 g/h) and Feed 3 (00:10 h to 06:10 h: 2.50 g/h).
  • Feed 4 (0.54 g of tert-Butyl peroxy-2- ethylhexanoate dissolved in 1.96 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 159 g of a polymer solution.
  • Example 8 b 110.00 g
  • Water 49.86 g
  • Feed 1 aqueous sodium hydroxide, 50%, 11.50 g
  • the mixture was stirred at 80°C for 1 h to yield 250 g of a polymer solution.
  • Example 19 a polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone and 70 moles ethylene oxide (Backbone B):
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone B (480.0 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (2.97 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 26.1 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1
  • Feed 2 (258.5 g of vinyl acetate) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 9.70 g/h and 00:10 h to 06:10 h: 4.58 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 43.08 g/h).
  • Feed 3 (1 .88 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 16.6 g of propane-1 , 2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 781 g of a polymer solution.
  • Example 20 (Inv. 20)
  • Example 20 a polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone and 70 moles ethylene oxide (Backbone K):
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone K (350.0 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (4.02 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 33.0 g of propane-1 ,2-diol) and 10 min upon the start of Feed 1
  • Feed 2 (650.0 g of vinyl acetate) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 12.4 g/h and 00:10 h h to 06:10 h: 5.83 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 108.3 g/h).
  • Feed 3 (2.55 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 21.0 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 1059 g of a polymer solution.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone K (550.0 g) under nitrogen atmosphere and heated to 90°C.
  • Feed 1 (3.40 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 30.0 g of propane-1 ,2-diol) and 10 min upon the start of Feed 1
  • Feed 2 (296.2 g of vinyl acetate) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 11.1 g/h and 00:10 h h to 06:10 h: 5.25 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 49.4 g/h).
  • Feed 3 (2.55 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 21.0 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 899 g of a polymer solution.
  • Comparative graft polymer 1 based on PEG ester backbone was synthesized via the following steps 1.3: Step 1 : Oxidation of PAG
  • Polyalkylene oxides (PAG) with two primary OH end groups (called “diol”) were oxidized to mixtures containing at least a polyalkylene oxide with two COOH end groups (called “diacid”) and a polyalkylene oxide with one primary OH and one COOH end group (called “monoacid”), and, optionally, also remaining polyalkylene oxide with two primary OH end groups.
  • the mixtures were prepared as follows.
  • Platinum on charcoal (5.0 wt.-% Pt on C, water content: 59.7 wt.-%, 283 g, 29.2 mmol Pt) was suspended in a mixture of polyalkylene oxide comprising two primary OH end groups and water (details see Table 1), heated to 52°C and stirred at 800 rpm.
  • Oxygen was passed through the stirred mixture (20 nL/h) via a glass tube, equipped with a glass frit and the temperature was allowed to rise to 60°C.
  • Oxygen dosage and temperature were maintained for the period mentioned in table 1 , the oxygen dosage was then stopped and the mixture was allowed to cool down to room temperature.
  • K-value measures the relative viscosity of dilute polymer solutions and is a relative measure of the average molecular weight. As the average molecular weight of the polymer increases for a particular polymer, the K-value tends to also increase.
  • the K-value is determined in a 3% by weight NaCI solution at 23°C and a polymer concentration of 1 % polymer according to the method of H. Fikentscher in “Cellulosechemie”, 1932, 13, 58.
  • Step 3 Synthesis of comparative graft polymer 1
  • the polymer backbone B1 (350.0 g) is dosed in a vessel equipped with a stainless-steel anchor stirrer (and 2 other necks) and heated to 95°C. 1.00 g of a 14wt% solution of t- butylperoxy-2-ethylhexanoate in tripropylene glycol was added within 1 min. Afterwards, the dosage of vinyl-acetate (350.0 g) was started and continued over 7.5 h with constant feed rate. At the same time the Initiator solution (50.0 g) t-butylperoxy-2-ethylhexanoate was dosed as a 14wt% solution in tripropylene glycol with a constant feed rate within 8.5 h. For completion of the reaction, the mixture is stirred for another 180 minutes. Finally, volatile components were stripped for 90 minutes at 120°C with nitrogen at a feed rate of 6 L N2/h.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with 660 g of PEG (Mn 6000 g/mol) under nitrogen atmosphere and melted at 90 °C.
  • Feed 2 (440 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90 °C.
  • the temperature was increased to 95 °C and Feed 3 consisting of 2.81 g of tertbutyl peroxy-2-ethy I hexanoate, dissolved in 23.21 g of 1 ,2-propanediol, were dosed within 56 min with constant flow rate at 95 °C.
  • the mixture was stirred for one hour at 95 °C upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95 °C and 500 mbar.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with 700 g of PEG (Mn 6000 g/mol) under nitrogen atmosphere and melted at 90 °C.
  • Feed 1 containing 12.24 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 50.30 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90 °C. 5.56 wt.-% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h.
  • Feed 2 (300 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90 °C.
  • the temperature was increased to 95 °C and Feed 3 consisting of 4.80 g of tertbutyl peroxy-2-ethylhexanoate, dissolved in 19.70 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 95 °C.
  • the mixture was stirred for one hour at 95 °C upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95 °C and 500 mbar.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with 600 g of PEG (Mn 4000 g/mol) under nitrogen atmosphere and melted at 90 °C.
  • Feed 2 400 g of vinyl acetate
  • Feed 3 consisting of 4.90 g of tertbutyl peroxy-2-ethylhexanoate, dissolved in 41.00 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 95 °C.
  • the mixture was stirred for one hour at 95 °C upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95 °C and 500 mbar.
  • a polymerization vessel equipped with stirrer and reflux condenser was initially charged with 400 g of PEG (Mn 6000 g/mol) under nitrogen atmosphere and melted at 90 °C.
  • Feed 2 (600 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90 °C.
  • the temperature was increased to 95 °C and Feed 3 consisting of 3.16 g of tertbutyl peroxy-2-ethylhexanoate, dissolved in 15.70 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 95 °C.
  • the mixture was stirred for one hour at 95 °C upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95 °C and 500 mbar.
  • test substance is inoculated into wastewater taken from Mannheim Wastewater Treatment Plant and incubated in a closed flask at 25°C for 28 days. The consumption of oxygen during this time is measured as the change in pressure inside the flask using an OxiTop C (WTW). Evolved CO2 is absorbed using an NaOH solution. The amount of oxygen consumed by the microbial population during biodegradation of the test substance, after correction using a blank, is expressed as a % of the ThOD (Theoretical Oxygen Demand).
  • ThOD Theoretical Oxygen Demand
  • the inventive graft polymers typically show a higher percentage of biodegradation at 28 day of the OECD 301 F test.
  • Aqueous solutions of the inventive graft polymer 5 (Inv. 5) and comparative polymer 1 (9 wt%) were prepared and the mixtures were stored at 54 °C for two weeks.
  • the objective of the Suds Mileage Index test is to compare the evolution over time of suds volume generated for different test formulations at specified water hardness, solution temperatures and formulation concentrations, while under the influence of periodic soil injections. Data are compared and expressed versus a reference composition as a suds mileage index (reference composition has suds mileage index of 100).
  • the steps of the method are as follows:
  • a defined amount of a test composition is dispensed through a plastic pipette at a flow rate of 0.67 mL/ sec at a height of 37 cm above the bottom surface of a sink (dimension: 300 mm diameter and 288 mm height) into a water stream (water hardness: 15 gpg, water temperature:35°C) that is filling up the sink to 4 L with a constant pressure of 4 bar.
  • Steps 3-5 are repeated until the measured total suds volume reaches a minimum level of 400 cm 3 .
  • the amount of added soil that is needed to get to the 400 cm 3 level is considered as the suds mileage for the test composition.
  • test composition is tested 4 times per testing condition (i.e., water temperature, composition concentration, water hardness, soil type).
  • the average suds mileage is calculated as the average of the 4 replicates foreach sample.
  • Soil composition is produced through standard mixing of the components described in Table 3.
  • Whiteness maintenance also referred to as whiteness preservation, is the ability of a detergent to keep white items from whiteness loss when they are washed in the presence of soil.
  • White garments can become dirty/dingy looking overtime when soils are removed from dirty clothes and suspended in the wash water, then these soils can re-deposit onto clothing, making the clothing less white each time they are washed.
  • the whiteness benefit of polymers of the present disclosure is evaluated using automatic Tergotometer with 10 pots for laundry formulation testing.
  • SBL2004 test soil strips supplied by WFK T estgewebe GmbH are used to simulate consumer soil levels (mix of body soil, food, dirt etc.). On average, every 1 SBL2004 strip is loaded with 8g soil. The SBL2004 test soil strips were cut into 5x5 cm squares for use in the test.
  • White Fabric swatches of Table 4 below purchased from WFK Testgewebe GmbH are used as whiteness tracers. Before the wash test, L, a, b values of all whiteness tracers are measured using Konica Minolta CM-3610D spectrophotometer.
  • ballast loads are comprised of cotton and polycotton knit swatches at 5x5 cm size.
  • Cycle 1 Desired amount of detergent is fully dissolved by mixing with 1 L water (at defined hardness) in each tergotometer port. 60 grams of fabrics, including whiteness tracers (4 types, each with 4 replicates), 21 pieces 5x5 cm SBL2004, and ballast are washed and rinsed in the tergotometer pot under defined conditions.
  • wash concentration is 2000ppm. Additional 47 ppm PVOH film is also added to the tergotometer pot.
  • the wash temperature is 30°C, water hardness is 20gpg.
  • Cycle 2 The whiteness tracers and ballast from each pot are then washed and rinsed again together with a new set of SBL2004 (5x5cm, 21 pieces) follow the process of cycle 1. All other conditions remain the same as cycle 1 .
  • Cycle 3 The whiteness tracers and ballast from each pot are then washed and rinsed again together with a new set of SBL2004 (5x5cm, 21 pieces) follow the process of cycle 1. All other conditions remain the same as cycle 1 .
  • Cycle 4 The whiteness tracers and ballast from each port are then washed and rinsed again together with a new set of SBL2004 (5x5cm, 21 pieces) follow the process of cycle 1. All other conditions remain the same as cycle 1 .
  • AWI(CIE) WI(CIE)(afterwash) - WI(CIE)(before wash).
  • test stains suitable for this test are:
  • the stains are analysed using Image Analysis System for Laundry stain removal testing before and after the wash.
  • SBL2004 test soil strips supplied by WFK T estgewebe GmbH are used to simulate consumer soil levels (mix of body soil, food, dirt etc.). On average, every 1 SBL2004 strip is loaded with 8g soil. The SBL2004 test soil strips were cut into 5x5 cm squares for use in the test.
  • ballast loads are comprised of knitted cotton swatches at 5x5 cm size. 4 cycles of the wash are performed:
  • Desired amount of detergent is fully dissolved by mixing with 1 L water (at defined hardness) in each tergotometer port. 60 grams of fabrics, stains (2 internal replicates of each stain in each pot), 13 pieces 5x5 cm SBL2004, and ballast are washed and rinsed in the tergotometer pot under defined conditions.
  • wash concentration is 2000ppm. Additional 47 ppm PVOH film is also added to the tergotometer pot. The wash temperature is 30°C, water hardness is 7gpg. The test has four external replicates.
  • Stain Removal Index are automatically calculated from the L, a, b values using the formula shown below. The higher the SRI, the better the stain removal.
  • Subscript ‘b’ denotes data for the stain before washing
  • Subscript ‘a’ denotes data for the stain after washing
  • amphiphilic alkoxylated polyethyleneimine (total MW: about 28000 g/mol) with a polyethyleneimine backbone of MW 600 and alkoxylation chains each chain comprising 24 internal EO units and 16 terminal PO units.
  • inventive polymers can deliver strong suds mileage benefit.
  • a concentrated dye solution is extracted from dyed test fabrics and used to determine the ability of a polymer to prevent dye re-deposition onto white test fabrics.
  • Dyed knit test fabrics are prepared at 3% dye loading as a percentage of the weight of the fiber using a 20: 1 liquor ratio (70 g/L sodium sulfate salt and 15 g/L soda ash) with identical auxiliary chemicals, time, temperature, and post-dye scour.
  • Knit fabrics are cut into 3” x 3” swatches (7.6 cm x 7.6 cm), and 4 fabric squares are layered on top of each other and fold in half and transferred into a 40 mL glass scintillation vial (Qorpak VWR supplier part #18087-086) using forceps.
  • Deionized water 38 mL is added to the vial, and vials are placed in heating blocks (Multi Temperature Zone Reaction Blocks, KEM Scientific, SN: 26197) on top of an orbital Shaker (VWR Standard Analog Shaker, Model: 3500, SN: 191011001 , NA CAT No: 89032-092) and heated at set temperature of 50 °C, and speed setting of 2 for a minimum 24h to extract available dye.
  • heating blocks Multi Temperature Zone Reaction Blocks, KEM Scientific, SN: 26197
  • an orbital Shaker VWR Standard Analog Shaker, Model: 3500, SN: 191011001 , NA CAT No: 89032-092
  • Vials are removed from heat and extracted dye solution and fabrics are transferred into a syringe with the depressor removed fitted with a glass fiber filter (Nalgene glass fiber syringe filters, 25 mm diameter, 1.1 micron, Thermo Scientific, Cat#722-2000, Lot 1705032503).
  • the depressor is re-inserted and depress contents into new scintillation vial.
  • UV-VIS Spectrum is measured and absorbance at Imax is recorded. Concentrated extracts are diluted to 0.25 absorbance units (AU) at Imax.
  • White Acceptor Fabrics (2 x 2.75 cm, 100% cotton knit, WFK CK-19502) that have been measured for L*ab using a spectrophotometer such as a Konica Minolta are added to each solution making sure fabrics are submersed in solution. Vials are shaken on a mechanical shakerat room temperature for 30 min wash time. Vials are removed from the shaker, fabrics are removed using forceps, and liquid is removed using a countertop spin dryer after spinning for 1 .5 min. Fabrics are rinsed by placing fabrics into new 20 mL vials containing 3.5 mL, 15 gpg water and shaken on mechanical wrist shaker for 15 min at room temperature.
  • Fabrics are removed from each vial using forceps, and liquid removed using a countertop spin dryer after 1 .5 min of spinning. After spinning, fabrics are dried on racks in the food dehydrator at 52 °C for 1 hour. Washed and dried fabrics are measured for L*ab and the color change difference between unwashed and washed is recorded as dE2000 (G. Sharma, W. Wu, E.N. Dalal, "THE CIEDE2000 COLOUR-DIFFERENCE FORMULA: Implementation Notes, Supplementary Test Data, and Mathematical Observations," submitted to COLOR
  • Water soluble unit dose detergent composition E and F, and heavy-duty liquid detergent composition G, H below are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients (Table 7 / Table 8).
  • Table 7 The whiteness maintenance of the inventive and comparative polymers is evaluated according to the method for evaluating whiteness performance of polymers by directly comparing the whiteness performance of reference composition E and test composition F. AWI(CIE) of composition F vs composition E is reported in Table 9 as an indication of polymer whiteness performance benefit. As shown in Table 9, the inventive polymer delivers significant whiteness benefit.
  • the stain removal performance of the inventive and comparative polymers is evaluated according to the method for evaluating whiteness performance of polymers by directly comparing the whiteness performance of reference composition E and test composition F.
  • ASRI of composition F vs composition E is reported in Table 10 as an indication of polymer whiteness performance benefit.
  • the inventive polymer delivers significant stain removal benefit on sebum stains and black todd clay.
  • the inventive graft polymers contain VP (especially when VP is more than 5%) show particular strong black todd clay stain removal benefit.
  • the dye re-deposition performance of the inventive polymers is evaluated according to the dye re-deposition method by comparing performance of reference composition G having no polymer to test compositions H.
  • the color change before and after washing is reported as dE2000 in Table 11 / Table 12 as an indication of polymer dye re-deposition benefit.
  • the inventive polymer delivers significant dye transfer benefit as shown by the decrease in dye re-deposition with a lower dE2000 on Reactive Red 120 and Reactive Red 239 compared to the same detergent without any polymer.
  • the dye transfer benefit increases and biodegradability is maintained above 60%.
  • Inventive 16 has a 4.3 units less Reactive Red 120 transfer and 1 .5 unit less dye transfer on Reactive Red 239.
  • Table 12 shows that the inventive polymer based on grafting type F also delivers a significant and noticeable dye transfer benefit relative to the reference detergent with no polymer.
  • Inventive 8 and Inventive 18 delivers significant dye transfer benefit as shown by the decrease in dye re-deposition with a lower dE2000 on Reactive Red 120 and Reactive Red 239 and Reactive Blue 171.
  • the Inventive polymer 18 has even less dye transfer than inventive 8 since the vinyl acetate is 40% hydrolyzed making it more hydrophilic.
  • Vinyl acetate is 40% hydrolyzed.

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Abstract

The present invention relates to novel graft polymers comprising a polymer backbone (A) as a graft base having polymeric sidechains (B) grafted thereon. The polymeric sidechains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) optionally at least one nitrogen-containing monomer (B2), optionally further monomer(s) (B3). The polymer backbone (A) comprises polyalkylene-oxide-derived moieties and moieties derived from lactone(s) and/or hydroxy acid(s), those moieties being mixed such that the polymer backbone contains ester-functions within the polymer chains. The present invention further relates to a process for obtaining such a graft polymer, the process is preferably carried out by free-radical polymerization. The present invention also relates to the use of such a graft polymer within, for example, fabric and home care products. Also claimed are compositions and products, such as fabric and home care products, containing such graft polymer.

Description

Biodegradable Graft Polymers
The present invention relates to novel graft polymers comprising a polymer backbone (A) as a graft base having polymeric sidechains (B) grafted thereon. The polymeric sidechains (B) are obtainable by (co-)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), and optionally further monomer(s) (B3), and optionally further monomers. The polymer backbone (A) is made from at least two sub-units (a1) and (a2), wherein (a1) is derived from at least one alkylene oxide monomer, and (a2) is a unit derived from at least one lactone and/or at least one hydroxy acid.
The present invention further relates to a process for obtaining such a graft polymer, the process is preferably carried out by polycondensation. Furthermore, the present invention relates to the use of such a graft polymerwithin, for example, fabric and home care products. Another subject-matter of the present invention are compositions comprising at least one graft polymer, such as fabric and home care products.
Various states have already introduced initiatives to ban microplastics especially in cosmetic products. Beyond this ban of insoluble microplastic there is an intense dialog on future requirements for soluble polymers used in consumer products. It is therefore highly desirable to identify new better biodegradable ingredients for such applications. This problem is predominantly serious for polymers produced by radical polymerization based on carbon- only backbones (a backbone not containing heteroatoms such as oxygen), since a carbon- only backbone is particularly difficult to degrade for microorganisms. Even radically produced graft polymers of industrial importance with a polyethylene glycol backbone show only limited biodegradation in wastewater. However, the polymers described by the current Invention are preferably produced by radical graft polymerization and provide enhanced biodegradation properties compared to the state-of-the-art.
Polyalkylene oxides are important polymers with a wide range of applications. They have been extensively used as basis to produce graft polymers which are widely employed in consumer formulations, including cleaning compositions for household and other uses.
Similarly, graft polymers of a vinylester being grafted onto polyalkylene oxide-polymers such as vinylacetate-graft-polyethylene glycol are known polymers. Their application in the detergent area as well as many other application areas are known as well.
Those polymers however lack biodegradability or at least suffer from very limited biodegradability.
However, a certain amount - if not all - of such consumer products is rinsed finally away after their use and may, if not biodegraded or otherwise removed in the sewage treatment plant, end up in the rivers or sea. Thus, biodegradability is one of the upcoming very important features not only in the area of detergents, as a biodegradable polymer can avoid the issue of building up in the environment.
Such issues will no longer be acceptable according to applicable laws in certain countries, which are expected to be made into law within the very near future if not already implemented and valid.
On the other hand, the functionalities imparted by such polymers is of utmost importance as well, as they allow for high cleaning efficiencies and thus among other advantages also for a low use of cleaning additives for a single cleaning run, and thus allow for saving material used and hence avoid also the pollution of the environment. AS those specialty polymers also allow for cleaning at lower temperatures, in shorter times and with lower amounts of water, they are needed for an environment-friendly cleaning process.
Hence, providing bio-degradable polymers for the area of detergents is of utmost importance to solve the problem of pollution of the environment without compromising cleaning efficiency, as such lower cleaning efficiency would also pollute the environment more than unavoidable.
One such widely known polymer is a graft polymer of vinyl acetate on PEG6000 with a wt. ratio 60% (VAc) to 40% (PEG) known and employed widely for its cleaning and whiteness benefits in liquid laundry formulations (liquid and gel-like detergents).
The poor biodegradability of polyalkylene oxides decreases in the range from a few hundred g/mol molecular weight up to a few thousand g/mol molecular weight. Even more so, graft polymers based on such polyalkylene oxides are usually even poorer in their biodegradation likely due to the grafting.
Prior art Graft polymers
US 2019/0390142 relates to fabric care compositions that include a graft copolymer, which may be composed of (a) a polyalkylene oxide, such as polyethylene oxide (PEG); (b) N- vinylpyrrolidone(VP); and (c) a vinyl ester, such as vinyl acetate. However, US 2019/0390142 does not disclose a graft polymer as presently required.
W02020/005476 discloses a fabric care composition comprising a graft copolymer and a so- called treatment adjunct, the graft copolymer comprising a polyalkylene oxide as backbone based on ethylene oxide, propylene oxide, or butylene oxide, preferably poly ethylene oxide, and N-vinylpyrrolidone and vinyl ester as grafted side chains on the backbone and with backbone and both monomers in a certain ratio.
W02020/264077 discloses cleaning compositions containing a combination of enzymes with a polymer such composition being suitable for removal of stains from soiled material.
This publication discloses a so-called “suspension graft copolymer” which is selected from the group consisting of poly (vinylacetate)-g-poly (ethylene glycol), poly(vinylpyrrolidone)- poly(vinyl acetate)-g-poly(ethylene glycol), and combinations thereof. The graft polymer as defined in this invention however is not disclosed.
US31816566 discloses graft polymers of so-called “lactone polyesters” and blends thereof with PVC. The lactone polyesters are either homo-polymers of epsilon-caprolactone or copolesters thereof with epsilon-alkyl-epsilon-caprolactones. No polymers are disclosed being made from lactones and alkyleneoxides as in the present invention used as graft bases. The lactone polyesters of US31816566 were grafted with ethylenically unsaturated monomers, among a long list also “vinyl esters of aliphatic acids” are mentioned, with vinyl formate, vinyl acetate and vinyl propionate being exemplified in this list. The 22 examples show graft polymerization using acrylic acid, butylacrylate, dimethylaminomethacrylate, styrene, acrylonitrile, and methylmethacrylate as the only monomers actually being employed, all only as single monomer and no monomer mixtures being employed. Only one example (example 12) uses vinyl acetate as monomer and poly-epsilon-caprolactone as graft base (i.e. a graft base not comprising any alkylene oxide), employing 200 gram of backbone and 30 gram of vinyl acetate, i.e. and amount by weight of 15 wt.% vinyl acetate based on graft base equal to 13 wt.% of vinyl acetate based on total polymer weight. US31816566 does not disclose anything on the biodegradation of such polymer; the only use discloses is as plasticizer in PVC-polymer. Graft polymers of the types shown in this invention are not disclosed nor pointed at.
WO2022/136409 of BASF discloses amphiphilic alkoxylated polyalkylene imines or amines; no graft polymers are discloses comprising a polymer as graft backbone made from lactones and alkylene oxides being grafted in a radical polymerization with olefinically unsaturated monomers comprising at least a vinyl ester. Hence, his publication is completely unrelated to the present invention except to the fact that it also targets polymeric structures for use in areas similar to those of the present invention, and in that those products comprise lactone and alkylene oxides. The lactones and alkylene oxides are polymerized to produce lactonealkylene oxide-copolymers which are attached to the amine groups of the starting compound polyethylene imine or polyamine. No graft polymerization is performed after the formation of those side chains. Thus, the structures and their preparation are completely different as well as the properties and thus the function in the application of such compounds. Graft polymers of the types shown in this invention are not disclosed nor pointed at.
US2022/0056380 discloses cleaning compositions focusing on specific enzymes, thus there is no focus on a specific polymer as such, its structure or preparation or properties. Among the many ingredients of such compositions also graft polymers are mentioned as an ingredient. The graft polymers however are the typically, known graft polymers (such as the preferred mentioned “Sokalan® HP22 of BASF” - all of which do not contain a lactone in the backbone of the polymer, thus such backbone being made only of alkylene oxides. Those alkylene oxides - and especially the preferred polymers of molecular weight of the backbones of around 6000 g/mol are not very much biodegradable at all, with the graft polymers being made with the use of such polyalkylene oxide-backbones having an even poorer biodegradation as shown in this present invention. Graft polymers of the types shown in this invention are not disclosed nor pointed at. All the prior art graft polymers use no polymers made from lactones and alkylene oxides as backbone; thus, the biodegradation of those polyalkylene oxides is low or neglectable, whereas the polyesters might show good biodegradation but a poor performance in the intended application areas, and also are typically not well suited for graft polymerization.
The task of improving the biodegradation of graft polymers based on backbones with polyalkylene oxide-units in the backbone was tackled already in - at the time of filing this present invention - un-published patent application PCT/EP2022/065983 (now published as WO2022/263354), which discloses graft polymers based on backbones comprising as functional units ester-fu notions and polyalkylene oxide-units. The backbones are prepared by oxidizing polyalkylene oxides in a first reaction, and then esterifying the oxidized PEG- mixtures either with itself or with additionally added polyalkylene oxides. The backbones are then grafted with vinyl acetate.
The polymers in this disclosure suffer from the two-step-synthesis for the backbone: the oxidation as first reaction step is expensive and lengthy, and the composition obtained from the oxidation is difficult to control, as - depending on the time taken for the reaction - the content of the mixture changes. Typically, the mixture obtained contains non-oxidized starting material, polyalkylene oxides with one hydroxy-group being oxidized to carboxyl-function and polyalkylene oxides with both ends being oxidized. Hence, the flexibility of designing the backbone is highly limited.
The patent application does also not disclose the use of nitrogen-containing monomers for preparing the graft polymers.
Prior Art on Backbones
This present invention discloses the uses of three main types of polymeric backbones comprising (oligo-Zpoly-)alkylene oxide-moieties and (oligo-/poly-)lactone/hydroxy acid- derived moieties.
Such backbones are named (A1), (A2) and (A3) (see definitions below), and are in principle known so far:
(A1)
W02002046268 (Cognis, now BASF) discloses biodegradable polymers as surfactants, emulsifier etc., obtained by reacting an organic initiator with 1. alkylene oxides, 2. mixture of alkylene oxides and lactones. “Organic initiator” is defined on page 4 as mono- or polyfunctional alcohol or amine.
To obtain copolymers from alkylene oxides and caprolactone, suitable starters are reacted with a premixed combination of alkylene oxides and caprolactone.
To obtain (Al)-backbone-type copolymers from alkylene oxides and lactones such as caprolactone, suitable starters are reacted with a premixed combination of alkylene oxides and caprolactone.
Alcohols with 2 hydroxy groups (diols) are used as starters. Examples for such diols are: ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1 ,3-propylene diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, and the like.
Used alkylene oxides in combination with caprolactone are: ethylene oxide, 1 ,2-propylene oxide or 1 ,2-butylene oxide, 2,3-butylene oxide, 1 ,2-pentylene oxide, preferred ethylene oxide and propylene oxide.
The copolymerization of alkylene oxides and caprolactone is carried out under typical conditions for alkoxylation reactions. Basic catalysts are used like potassium hydroxide, sodium hydroxide, sodium methoxide, potassium methoxide.
(A2)-backbone-type polymers can be obtained in principle by alkoxylation of polylactones. Polylactones are for example accessible by polymerization of lactones such as caprolactone onto starters having 2 hydroxy-groups such as diols like ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1 ,3-propylene diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, and the like.
Polymerization of caprolactone is carried out with various catalysts like transesterification catalysts tin(ll)alkanoates.
The alkoxylation of such polycaprolactones is done under typical alkoxylation conditions. Due to basic reaction conditions for the alkoxylation, transesterification reaction at ester bonds from polycaprolactone can occur.
US4281172 describes acrylic acid esters from polyester-polyether copolymers. To obtain these structures, a polylactone ester from mono-, di-, tri-, or tetraols, is reacted with alkylene oxides.
The polylactone esters are synthesized according to US3169945 from a hydroxy group - containing component with various catalysts, including Ti or Sn catalysts or alkali metal hydroxides.
The alkoxylation reaction is catalyzed with BF3-etherate or potassium hydroxide etc.
JP07149883 describes the process to obtain polyester-polyols from a compound with at least two active hydrogen, reacted with a lactone, followed by reaction with alkylene oxide. Both reactions are carried out with the same catalyst. Catalysts are alkali metal hydroxides or alkali metal alcoholates.
WO9636656 claims biodegradable alkylene oxide-lactone copolymers. The polymers are synthesized from a di- or polyfunctional starter, that are reacted with alkylene oxide and lactones in a copolymerization reaction, followed by an end-cap with an alkylene oxide block. Catalysts are alkali metal hydroxide or earth alkali metal hydroxide or Lewis acid. The patent application describes improved biodegradability of claimed polymers over polyalkylene oxides, and use as surfactants, emulsifiers etc. but not as backbones for graft polymers.
(A3)-backbone-type polymers can be obtained in principle by poly-esterification of polyalkylene glycols with lactones yielding - simplified - tri-block-polymers. Triblock copolymers from caprolactone and alkylene oxides with a middle polyalkylene oxide block are synthesized by 1 . formation of a polyalkoxylate from a diol or water by reaction with alkylene oxides, and 2. polymerization of caprolactone onto the polyalkoxylate.
Both reactions can be carried out under typical reaction conditions for alkoxylation reactions (polyalkoxylate) and for caprolactone polymerization (polycaprolactone block).
Such triblock copolymers with a middle polyethylene oxide block are known since about the 1990s. These polymers are used for drug release and solubilization purposes (Z. Zhu et al., Journal of Polymer Science, Part A: Polymer Chemistry 1997, 35 (4), 709-714; M. Boffito et al., Journal of Biomedical Materials Research, Part A 2015, 103A (3), 1276-1290).
(A4)-type backbones are known as well:
WO96/36656 discloses biodegradable oxide-lactone copolymers and copolyesters as already described for (A3) above.
W02002046268 (Cognis, now BASF) discloses alkylene oxide-lactone copolymers as already described for (A1).
Not known however are the use of such polymers as backbones for graft polymers, introducing via the backbone an improved biodegradation into such graft polymers.
Object of Invention
It was recognized that the graft polymers based on conventional polyalkylene oxides (without ester-groups in the backbone) show a surprisingly low biodegradation, which is often very much lower than the expected biodegradation percentage, which is calculated on the biodegradation of the pure polyalkylene oxides.
The graft polymers being based on such conventional polyalkylene oxides commonly show a decrease in biodegradation compared to the unmodified polyakylene oxides and unmodified polyalkylene glycols, as the degree of modification of polyalkylene oxides (often polyalkylene oxides with two hydroxy-end groups are employed, thus such polyakylene oxides with hydroxy-groups being named commonly “polyalkylene glycols”) with polymerizable monomers by radical grafting onto such backbones increases (i.e. the number of side chains on the backbone increases). This is sometimes attributed to the blocking of the biodegradation mechanism, as it seems that the polyalkylene oxides/glycols are degraded starting from their respective end group then following the polymer chain along. Thus, any additional branching on a carbon-atom of the backbone - which occurs when a polymeric side chain is grafted onto such backbone - impedes and possibly completely stops degradation. As a result, it is suggested that the higher the degree of grafting (i.e. the more side chains are attached to the backbone) the lower is the biodegradation percentage of such graft polymer. Unfortunately it is also commonly observed that with higher degree of branching the performance increases in the desired applications, as only with a higher amount of side chains the chemical structure of the backbone is changed enough that the new graft polymer exerts its specific properties compared to the separated properties of the unmodified backbone in simple mixture with the (u n atta ch ed/u ng rafted) homopolymer which would make up the side chain of the graft polymer. Hence, the difficulty of combining the conflicting properties of a suitable graft polymer with superior application performance with the biodegradation percentage of the unmodified backbone (i.e. an unmodified polyalkylene oxide/glycol) has not been met up to date when polyalkylene oxides are used as backbones.
Although the unpublished patent application PCT/EP2022/065983 (now published as WO2022/263354) has provided a first solution to the problem of lacking biodegradation of the polyalkylene oxide-backbones, the practical aspects of the solution found is still not satisfactory, as the two-step-reaction is lengthy and costly, as two completely different types of chemical reactions are employed (oxidation and polymerization) and the structural variations are not easily controlled as the oxidation leads to mixtures of compounds being diols (i.e. the starting material polyalkylene glycols), mono-ol-mono-carbonic acid (i.e. partially oxidized polyalkylene glycol) and di-carboxyl-polylakylene oxide (i.e. fully oxidized polyalkylene glycol). Structures as the ones used here are not obtainable by the method disclosed in that document. Similarly, nitrogen-containing monomers are not disclosed.
Hence, there was a need to improve the biodegradation of conventional graft polymers based on polyalkylene oxides by improving the biodegradability of the graft base and keeping the general structure of the graft polymer and thus maintaining the application performance or even improve it, and to improve the cost and efficiency of the unpublished patent application PCT/EP2022/065983 (now published as WO2022/263354) by reducing the production process to just one reaction step employing only one reaction type and improving the variability of the chemical structure at the same time.
Even though polymers of the type (A1), (A2) and (A3) as defined herein are known, the use of such polymers as backbones to prepare graft polymers is not yet known.
Thus, the object of the present invention is to provide novel graft polymers based on polyalkylene-oxide-type graft backbones which impart ester-functions.
Furthermore, these novel graft polymers should have beneficial properties in respect of biodegradability and/or their washing behavior, when being employed within compositions such as cleaning compositions.
Graft polymers
The graft polymers of the invention comprise a polymer backbone as graft base as a first structural unit and polymeric side chains as a second structural unit.
First structural unit (Backbone)
The first structural unit of the graft polymer is a polymer backbone used as a graft base for the inventive graft polymer, wherein said polymer backbone (A) is obtainable by polymerization of at least one sub-unit (a 1 ) and at least one sub-unit (a2).
The sub-unit (a1) is made from least one alkylene oxide monomer and/or at least one
, the alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides, such as ethylene oxide, 1 ,2 propylene oxide, 1 ,2 butylene oxide, 2,3 butylene oxide, 1 ,2- pentene oxide or 2,3 pentene oxide; from 1 ,4-diols or their cyclic or oligomeric analogs, or being based on polymeric ethers of such 1 ,4-diols; from 1 ,6-diols or their cyclic or oligomeric analogs, or being based on polymeric ethers of such 1 ,6-diols; or any of their mixtures in any ratio, either as blocks of certain polymeric units, or as statistical polymeric structures, or a polymers comprising one or more homo-block(s) of a certain monomer and one or more statistical block(s) comprising more than one such monomer, and any combination thereof such as polymers having several different blocks of two or more different monomers, or blocks of two or more different monomers, blocks of statistical mixtures of two or more monomers etc.
The term “block (co)polymer” as used herein means that the respective polymer comprises at least two (i.e. two, three, four, five or more) homo- or co-polymer subunits (“blocks”) linked by covalent bonds. “Two-block” copolymers have two distinct blocks (homo- and/or copolymer subunits), whereas “triblock” copolymers have, by consequence, three distinct blocks (homo- and/or co-polymer subunits) and so on. The number of individual blocks within such block copolymers is not limited; by consequence, a “n-block copolymer” comprises n distinct blocks (homo- and/or co-polymer subunits). Within the individual blocks the size/length of such a block may vary independently from the other blocks. The smallest length/size of a block is based on two individual monomers (as a minimum), but may be as large as 50 or even 100 or 200, and any number in between 2 and 200. The respective monomers to be employed for preparing the individual blocks of a block copolymer backbone (a1) may be added in sequence. However, it is also possible that there is a transition of the feed from one monomer to the other to produce so called “dirty structures” wherein at the edge/border of the respective block a small number of monomers of the respective neighboring block may be contained within the individual block to be considered (so called “dirty structures” or “dirty passages”). However, it is preferred that the block copolymer subunits (a1) according to the present invention do not contain any dirty structures at the respective border of the blocks, although for commercial reasons (i.e. mainly cost for efficient use of reactors etc.) small amounts of dirty structures may still be contained although not deliberately being made.
Preferably at least one monomer in the polymer stems from the use of ethylene oxide.
In another embodiment, more than one alkylene oxide monomer is comprised in the structure of the polymer-subunit (A1); in such case the polymer backbone is a random copolymer, a block copolymer or a copolymer comprising mixed structures of block units (with each block being a homo-block or a random block itself) and statistical /random parts comprised of two or more alkylene oxides, with one of the monomers being ethylene oxide. Preferably the further monomer beside ethylene oxide is propylene oxide (PO) and/or 1 ,2-butylene oxide (BO), preferably only 1 ,2-propylene oxide.
The sub-unit (a2) is made from at least one lactone and/or at least one hydroxy acid.
The at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e. cyclic esters, starting with a-lactone (three ring atoms) followed by p- lactone (four ring atoms), y-lactone (five ring atoms) and so on; such lactones preferably being p-propiolactone, g-butyrolactone, b-valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; and ii) hydroxy acid(s), which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, specifically an a-, p- or y-hydroxy acid derived from the corresponding lactone by hydrolyzation, and lactic acid, glycolic acid, 4-hydroxybutanoic acid, 6-hydroxy hexanoic acid, 12-hydroxy stearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone.
The sub-units (a1) and (a2) may be combined in any order depending on how the starting material are employed and depending on the relative amounts.
As a result, the polymer backbone (A) obtained from the reaction of (a1) and (a2) can be defined in a very broad range by selecting the desired sub-units (a1) and (a2), and - within sub-unit (a1) by selecting the number of different alkylene oxides, their relative amounts, their reaction order etc, and of course also for (a2) by selecting the compounds, their relative amounts etc., in such way
1) to obtain first defined (al)-subunits which are then reacted with (a2)-sub units,
2) to directly react monomeric alkylene oxides from sub-unit (a1) with monomeric sub-units (a2); or
3) to combine approach 1) and 2) before.
Hence, three principal backbone-structures can be defined and obtained:
(A1): sub-units (a2) can be added during alkylene oxide polymerization (a1 -units) yielding random copolymers; in a variation thereof, polyalkylene oxides having two hydroxy-groups can be added to such polymerisation thus introducing specific (al)-sub-unit-blocks; this variation is useful if the alkylene oxides employed are at least partially different to the alkylene oxides employed for preparing the polyalkylene oxide also employed or if the structure of the polyalkylene oxide (i.e. the order of the alkylene oxide-units therein) is different to what is obtained by reacting the at least one alkylene oxide employed for the co-polymerisation with (a2)-sub-unit and the polyalkylene oxide.
In a simplifying approach this (Al)-backbone can be described as a randomly arranged order of (al)-sub-units and (a2)-sub-units. Depending on the relative amount of (a1) to (a2) and their reactivity the block length of the (a1) and the (a2) is varied.
Structures like the one shown below can be obtained by this approach:
Poly [random-{lactone}-{alkylene oxide}]
(“oligo/poly lactone” depicts the (a2)-sub-unit, thus made from lactone(s)/hydroxy acid(s);
“PAG” = polyalkylene glycol is used here to depict the (al)-sub-unit)
Hence, in one preferred embodiment, the polymer backbone is selected from (A1) a backbone consisting of a randomly arranged order of monomeric, oligomeric and/or polymeric (al)-sub-units and monomeric, oligomeric and/or polymeric (a2)-sub-units, with more than one sub-unit (a1) and/or more than one sub-unit (a2) being present.
(A2): sub-units (a2) can be oligomerized/polymerized first and the co-polymerized with at least one alkylene oxide yielding mixed random/block structures; depending on the degree of oligomerization of the lactone/hydroxy-acid and if still monomeric lactone /hydroxy acid is present when the alkylene oxide(s) is/are added, the structure can be further varied by tuning the amount and length of (a2)-sub-unit-chains within the (A2)-backbone.
As with (A1), in a further variation thereof, also polyalkylene oxides having two hydroxygroups can be added to such polymerisation thus also introducing specific (a1 ^sub-unit- blocks; this variation is useful if the alkylene oxides employed are at least partially different to the alkylene oxides employed for preparing the polyalkylene oxide also employed or if the structure of the polyalkylene oxide (i.e. the order of the alkylene oxide-units therein) is different to what is obtained by reacting the at least one alkylene oxide employed for the copolymerisation with (a2)-sub-unit and the polyalkylene oxide.
In a simplifying approach, this (A2)-backbone can be described as a tri-block-polymer with an inner (a2)-block and two outer (al)-blocks.
(Switching the order to the opposite leads to structure (A3); see below.)
Structures like the one shown below (in its most simple version) can be obtained by this approach:
[PAG]-[oligo/poly lactone]-[PAG]
(“lactone” is used here to denote the (a2)-sub-units, thus made from lactone(s)/hydroxy acid(s) and can be single monomeric units or oligo- or polymeric units made from monomers in a first reaction step; “PAG” = polyalkylene glycol is used here to depict the (al)-sub-unit)
In case the (a2)-sub-unit-starting material has not completely reacted when the alkylene oxide(s) are added, the structure will not be anymore a true tri-block structure, but will in addition contain further, shorter (a2)-units in the chains and thus consist of a multi-block- structure or even shift towards a mixture of block and random-structural arrangement.
Hence, in one preferred embodiment the polymer backbone is selected from (A2) a backbone consisting of oligo- or polymerized sub-units (a2) as an inner block and two outer blocks of oligomeric and/or polymeric (al)-sub-units, defined as “-[block of (a1)]-[block of (a2)]-[block of (a1 )]-“, and also possibly comprising higher block-polymers such as 5-, 7- and 9- etc. blocks where at the outside of the tri-block structure further blocks of (a1) and (a2) are connected, such as a penta-block “ [block of (a1)] - [block of (a2)] - [block of (a1)]-[block of (a2)] - [block of (a1)] - [block of (a2)] - [block of (a1)] “ and so on.
(A3): sub-units (a2) can be added after alkylene oxide oligomerization or (almost complete) polymerization yielding block structures containing larger (a2)-chains and larger (a1 )-chains; in case of complete polymerization of (a1) before addition of (a2) the structure resulting can be described as “(a2)-polyalkylene oxide-(a2)”; such structures can be also obtained by directly reacting polyalkylene oxides with (a2). By only oligomerizing the alkylene oxide(s) first and then reacting the mixtures containing alkylene-oxide(s)-oligomers and monomeric alkylene oxides with (a2) or by polymerizing (a2) with alkylene oxide(s) and with polyalkylene oxide(s) more complex structures can be obtained.
In a simplifying approach, this (A3)-backbone can be described as a tri-block-polymer with an inner (al)-block and two outer (a2)-blocks:
(Switching the order to the opposite leads to structure (A2); see above.)
[oligo/poly lactone]-[PAG]-[oligo/poly lactone]
(“oligo/poly lactone” depicts the (a2)-sub-unit, thus made from lactone(s)/hydroxy acid(s);
“PAG” = polyalkylene glycol is used here to depict the (al)-sub-unit)
Hence, in one preferred embodiment, the polymer backbone is selected from (A3) a backbone consisting of and inner block of oligomeric and/or polymeric (al)-sub-units and two outer blocks of oligo- or polymeric sub-units (a2), in the form of at least an tri-block-polymer defined as “ - [block of (a2)]-[block of (a1)] - [block of (a2)]
Similarly as for case of (A2), in case the (a2)-sub-unit-starting material has not completely reacted, the structure will not be anymore a true tri-block structure, but will in addition contain further, shorter (al)-units in the chains and thus consist of a multi-block-structure or even shift towards a mixture of block and random-structural arrangement.
Similarities of (A1), (A2) and (A3)
The more unreacted species of (a2) (in case of (A2)-backbone) or the more unreacted species of (a1) (in case of (A3)-backbone) are present when the respective other sub-unit- species are added, the difference between (A2) and(A3) diminishes.
To the extreme, the result of that would be a true co-polymerization of sub-units (a1) and (a2) and thus would be similar or even identical also to (A1).
Hence, (A1), (A2) and (A3) are “just” extreme ends of the overall principle of co-polymerizing alkylene oxides, polyalkylene glycols and lactones/hydroxy acids in every thinkable order, ratio and variation of reaction times before adding the other starting materials.
Hence, in one preferred embodiment, the polymer backbone is selected from a backbone obtained by such overall principle of co-polymerizing alkylene oxides, polyalkylene glycols and lactones/hydroxy acids in every thinkable order, ratio and variation of reaction times before adding the other starting materials.
(A4):
(A4) is a structure which starts from an oligo- or polymeric sub-unit (a1) which is end-capped on one side, preferably etherified with alcohols, more preferably short-chain alcohols C1 to C4. This one-sided end-capped oligo-/polymer of sub-unit (a1) is then thereafter reacted with at least one sub-unit (a2) and optionally at least one sub-unit (a1) - wherein the sub-unit (a1) may be different to that/those in the starter block or may be arranged in a different order compared to those in the starter block - to attach to the non-endcapped side of the starter block a new block comprising moieties from the sub-units employed for the (copolymerization, thereby obtaining a di-block-structure of
[end-cap]-[sub-unit(s) (a1)]-[sub-unit(s) (a2)], or
[end-cap]-[sub-unit(s) (a1)]-[random-{sub-unit(s) (a2)-sub unit(s) (a1)}].
It is to be emphasized that the oligo- or polymerization of sub-unit(s) (a1) and (a2) can each be effected with the use of “starter molecules”, which are then incorporated into the oligomers and polymers of sub-unit (a1 ) and (a2). Suitable starter molecules for such polycondensation reaction of lactones and hydroxy acids as well as alkylene oxides are known; such compounds comprise at least two hydroxy-groups accessible for condensation reaction, such asdiols like ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1 ,2- and 1 ,3-propane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol and the like. For the condensation of alkylene oxides also water is a suitable starter molecule.
Hence, the backbones (A1) to (A4) may comprise moieties derived from such starter molecule, specifically any one or more of water, ethylene glycol, polyethylene glycol, 1 ,2- and 1 ,3-propane diol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol.
In case where a compound derived from alkylene oxides is used as starter molecule, such use is already described in the backbone definitions above, and thus such starter molecule derived from alkylene oxide can be added as a molecule or can - in case of oligomers or polymers of alkylene oxide(s) - prepared in a first reaction step, before sub-unit (a2) is added for condensation reaction. The use of starter molecules not derived from alkylene oxides however is also encompassed as an option in any of the embodiments herein for any of the backbones disclosed; preferably, such starter molecule is used for the preparation of any such backbone (A1), (A2) and (A3).
Typical reaction procedure to obtain such structures is, firstly, the formation of a oligo- /polyalkoxylate from a starter molecule by reaction with alkylene oxide(s) (i.e. sub-units (a 1 )), and then, secondly, further polycondensation reaction sub-unit(s) (a2) onto the polyalkoxylate. Both reactions can be carried out under typical reaction conditions for alkoxylation reactions (to abtain the oligo-/polyalkoxylate) and for polymerization of sub-unit (a2).
The polymerization of sub-unit(s) (a2) is carried out in a known way with various catalysts like transesterification catalysts tin(ll)alkanoates.
The alkoxylation of such oligo-/poly-[sub-unit(s) (a2)] is done under typical, known alkoxylation conditions. Due to basic reaction conditions for the alkoxylation, transesterification reaction at ester bonds from oligo-/poly-[sub-unit(s) (a2)]can occur and thus lead to compounds having a mixed random / block structures. In a preferred embodiment, the polymer backbone as a graft base comprises at least one sub-unit (a1) and at least one sub-unit (a2), wherein
(a1) is a unit comprising, preferably essentially consisting of, moieties derived from at least one alkylene oxide monomer and/or at least one polyalkylene oxide-polymer having two hydroxy-end-groups, the alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,
(a2) is a unit comprising, preferably consisting of, at least one lactone and/or at least one hydroxy acid, such sub-unit (a2) being a moiety derived from a single lactone and/or hydroxy-acid or being oligo-or-polymeric units consisting of at least one type of lactone and/or at least one type of hydroxy acid, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e. cyclic esters, starting with a-lactone (three ring atoms) followed by p- lactone (four ring atoms), y-lactone (five ring atoms) and so on; such lactones preferably being p-propiolactone, g-butyrolactone, b-valerolactone, g-valerolactone, e- caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; and ii) hydroxy acid(s), which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, specifically an a-, p- or y-hydroxy acid derived from the corresponding lactone by hydrolyzation, and lactic acid, glycolic acid, 4- hydroxybutanoic acid, 6-hydroxy hexanoic acid, 12-hydroxy stearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone, wherein the polymer backbone is obtained
(A1) by co-polymerization of at least one sub-unit (a1) and at least one sub-unit (a2), wherein optionally at least one oligomer or polymer made from at least one sub-unit (a1) or at least one sub-unit (a2) can be employed within the copolymerization of at least one subunit (a1) and at least one sub-unit (a2) as well;
(A2) by first oligo-/polymerizing sub-unit(s) (a2) and then polymerizing the product with subunits) (a1);
(A3) By first oligo-Zpolymerizing sub-unit(s) (a1) and then co-polymerizing the product with sub-unit(s) (a2); or
(A4) by first providing an oligo- or polymeric sub-unit (a1) which is bears an end-cap on one side, preferably is etherified with alcohols, more preferably short-chain alcohols C1 to C4, which - as starter-block - is thereafter reacted with at least one sub-unit (a2) and optionally at least one sub-unit (a1) - wherein the sub-unit (a1) may be different to that/those in the starter block or may be arranged in a different order compared to those in the starter block - to attach to the non-end capped side of the starter block a new block comprising moieties from the sub-units employed for the (co-)polymerization, thereby obtaining a di-block-structure of [end-cap]-[sub-unit(s) (a1)]-[sub-unit(s) (a2)], or [end- cap]-[sub-unit(s) (a1)]-[random-{sub-unit(s) (a2)-sub unit(s) (a1)}]; wherein in case more than one sub-unit (a1) and/or more than one sub-unit (a2) are present already in an employed oligomer or polymer, those sub-units can be arranged in any order within such employed oligomer or polymer, and wherein in case more than one sub-unit (a1) and/or more than one sub-unit (a2) are present for the polymerization, those sub-units (and the optional oligomer/polymers if employed) can be arranged in any order within the obtained backbone, and wherein - optionally - at least one starter molecule is included in the backbone structure.
The polymer backbone (A) and specifically (A1), (A2) and (A3), may be optionally capped at the end groups, the capping is done by C1 C25 alkyl groups using known techniques, preferably C1 to C4-groups. Such capping will be done after the production of the backbones and may be done preferably prior to the grafting.
In case of (A4), the capping on one end-group is either to be done prior to the condensation polymerization with sub-unit(s) (a1) and/or sub-unit(s) (a2), as only then a structure (A4) can be obtained. In another, more preferred approach, the production of the (A4) starts with a mono-alcohol, which is then reacted with alkylene oxide(s) to obtain the “mono-end-capped” oligo/polymer of sub-unit (a1) (bearing one hydroxy-group at the oligo/poly alkylene oxidechain end), which is then reacted with sub-unit(s) (a2) to obtain (A4).
When preparing the oligo-/poly-alkylene oxide as a starting block, a diol may be used as a starter molecule for preparing this oligo/poly alkylene oxide, thus such oligo-Zpolymer of sub unit (a1) may contain in its structure a moiety derived from such diol. Diols for such use and methods to prepare such oligo/poly alkylene oxide comprising diols in their structure are known. Typical diols are ethylene glycol, propylene glycol etc. All of the commonly known diols can in principle be used for such purpose.
In another preferred embodiment, the polymer backbone as a graft base comprises at least one sub-unit (a1) and at least one sub-unit (a2), wherein
(a1) is a unit comprising, preferably essentially consisting of, moieties derived from at least one alkylene oxide monomer and/or at least one polyalkylene oxide-polymer having two hydroxy-end-groups, the alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,
(a2) is a unit comprising, preferably consisting of, at least one lactone and/or at least one hydroxy acid, such sub-unit (a2) being a moiety derived from a single lactone and/or hydroxy-acid or being oligo-or-polymeric units consisting of at least one type of lactone and/or at least one type of hydroxy acid, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e. cyclic esters, starting with a-lactone (three ring atoms) followed by p- lactone (four ring atoms), y-lactone (five ring atoms) and so on; such lactones preferably being p-propiolactone, g-butyrolactone, b-valerolactone, g-valerolactone, e- caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; and ii) hydroxy acid(s), which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, specifically an a-, p- or y-hydroxy acid derived from the corresponding lactone by hydrolyzation, and lactic acid, glycolic acid, 4- hydroxybutanoic acid, 6-hydroxy hexanoic acid, 12-hydroxy stearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone, wherein the polymer backbone as a graft base (A), which the polymer backbone is selected from
(A1) a backbone consisting of a randomly arranged order of monomeric, oligomeric and/or polymeric (al)-sub-units and monomeric, oligomeric and/or polymeric (a2)-sub-units, with more than one sub-unit (a1) and/or more than one sub-unit (a2) being present;
(A2) a backbone consisting of oligo- or polymerized sub-units (a2) as an inner block and two outer blocks of oligomeric and/or polymeric (al)-sub-units, defined as “-[block of (a1)]- [block of (a2)]-[block of (a 1 )]-“, and also possibly comprising higher block-polymers such as 5-, 7- and 9- etc. blocks where at the outside of the tri-block structure further blocks of (a1) and (a2) are connected, such as a penta-block “ [block of (a1)] - [block of (a2)] - [block of (a1)]-[block of (a2)] - [block of (a1)] - [block of (a2)] - [block of (a1)] “ and so on;
(A3) a backbone consisting of and inner block of oligomeric and/or polymeric (al)-sub-units and two outer blocks of oligo- or polymeric sub-units (a2), in the form of at least an tri- block-polymer defined as “ - [block of (a2)]-[block of (a1 )] - [block of (a2)] and
(A4) a backbone consisting of a first block with
(i) on one end an end-cap - such end-cap being a C1 to C18-, preferably C1-C4- alkyl-group attached to said first block via an ether-fu notion; and
(ii) an oligo- or polymeric sub-unit (a1); and a second block which is attached to said first block at the opposite end of said first block (“opposite” in relation to the end-cap on said first block) via an ether or ester-function, said second block being composed of at least one sub-unit (a2) and optionally at least one sub-unit (a1), wherein the optional sub-unit(s) (a1) in said second block may be different to that/those in the first block or may be arranged in a different order compared to those in the first block, and the order of the sub-unit(s) (A1) and (a2) may be also in any order, including random structure, such di-block-structure having as an idealized structure in case of using only sub-unit(s) (a2) for the second block: [end-cap]-[sub-unit(s) (a1)]-[sub-unit(s) (a2)] or in case of using sub-unit(s) (a1 ) and (a2) for the second block:
[end-cap]-[sub-unit(s) (a1)]-[random-{sub-unit(s) (a2)-sub unit(s) (a1)}; and wherein - optionally - at least one starter molecule is included in the backbone structure
In a preferred embodiment the polymer backbones (A), and specifically (A1), (A2) and (A3), are not capped but bear hydroxy-groups at the chain ends.
Preferably, the polyalkoxylate-ester backbone comprises moieties derived from
(i) alkylene oxides (AO) comprising at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably at least one of EO and PO, with the AO in an amount of from 40 to 95, preferably up to 90, and preferably from 50, more preferably from 60, and even more preferably from 70wt%, and any number and range in between, each based on the total weight of the backbone, the amount of EO being of from 0 to 100wt.%, preferably from 10, more preferably from 20, even more preferably from 30, even more preferably from 40, such as from 50, 60, 70, 80 or even from 90wt%, based on total AO, the PO and/or BO, in an total amount of each from 0 to 100 wt.%, preferably up to 90, more preferably up to 80, even more preferably up to 70, even more preferably up to 60, and most preferably up to 50, and any number in between such as up to 5, 10, 15, 25, 30, 35, 40, 45, 55, 65, 75, 85 or up to 95, and more preferably from 10, even more preferably from 20, even further more preferably from 30, such as from 40, 50, 60, 70, 80 or even from 90wt%, each based on the total weight of AO, with the total amount of PO and BO adding up to 100wt.% for the sum of PO and BO, with the total amount of AO adding up to 100wt.%;
(ii) lactone /hydroxy acid monomer in an amount of from 1 and up to 60, preferably up to 50, more preferably up to 40, most preferably up to 30 wt. %, and preferably from 2, more preferably from 3, even more preferably from 4 and most preferably from 5 wt.%, each based on the total weight of the backbone, preferably only caprolactone;
With the total weight of the sum of sub-units (a1 ) and sub-units(a2) in the backbone (A) adding up to 100 wt%.
More preferably, the amount of EO is at least 80 wt%, preferably at least about 85, more preferably at least about 90, even more preferably at least about 95%, and most preferably about 100 wt.% based on total AO; the amount of PO and/or BO is each from about 0 to 50 wt.% based on the total weight of AO, more preferably at most about 30, even more preferably at most about 20%, even more preferably about 10, and most preferably about 0 wt.%, each based on total AO; in a more preferred embodiment, the amounts for PO and BO given in this paragraph before are the total amounts for the sum of PO and BO. In an even more preferred embodiment, the backbone-unit (a1) is made from ethylene oxide only.
In an alternative but preferred embodiment, at least two different alkylene oxides are employed for the preparation of the backbone I are present in the backbone.
Hence, in one more preferred embodiment, the polymer backbone consists of
(i) alkylene oxides (AO) being selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably only EO and PO, the amount of EO being of from 10 to 90, preferably 20 to 80, more preferably 30 to 70, and most preferably 40 to 60wt%, based on total AO, the total amount of PO and BO being from 10 to 90, preferably 20 to 80, more preferably 30 to 70, and most preferably 40 to 60wt%, each based on the total weight of AO, with the total amount of PO and BO adding up to 100wt.% for the sum of PO and BO, and with the total amount of AO adding up to 100wt.%;
(ii) lactone /hydroxy acid monomer in an amount of from 1 and up to 60, preferably up to 40, more preferably up to 30, even more preferably up to 25, even further more preferably up to 20, and most preferably up to 15 wt. %, and preferably from 2, more preferably from 3, even more preferably from 4 and most preferably from 5 wt.%, each based on the total weight of the backbone, preferably only caprolactone; with the total weight of the sum of sub-units (a1) and sub-units(a2) in the backbone (A) adding up to 100 wt%, and wherein in case of (A1 ), (A2) and (A3) the use of a starter molecule is optional.
Hence, in one more preferred, alternative embodiment, the polymer backbone consists of
(i) alkylene oxides (AO) is selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably only EO and PO, more preferably only EO the amount of EO being of from 20 to 100 wt%, based on total AO, the total amount of PO and BO being from 0 to 80 wt.%, preferably up to 50, more preferably up to 30, even more preferably up to 20, and even further preferably up to 10, and most preferably zero, such as 45, 45, 45, 25, 15, 7 and 5, and any number in between, each based on the total weight of AO, with the total amount of PO and BO adding up to 100wt.% for the sum of PO and BO, with the total amount of AO adding up to 100wt.%;
(ii) lactone /hydroxy acid monomer in an amount of from 5 and up to 50, preferably up to 40, more preferably up to 35, and even more preferably up to 30, and as lower limit preferably from 7, more preferably from 10, even more preferably from 12 wt%, and most preferably from 15, such as 6,8, 9, 11 , 12, 13, 14 and 15 and any number in between as lower limit and such as 30, 33, 37, 45 and any number in between as upper limit, based on the total weight of the backbone, preferably only caprolactone; with the total weight of the sum of sub-units (a1) and sub-units(a2) in the backbone (A) adding up to 100 wt%, and wherein in case of (A1 ), (A2) and (A3) the use of a starter molecule is optional.
In an even more preferred embodiment, the backbone for any of the embodiments of the inventive graft polymer as defined herein is a structure chosen from the structures (A1), (A2), (A3) and/or (A4).
Second structural unit (grafted side chains)
The second structural unit of the graft polymer are polymeric side chains (B), which are grafted onto the polymer backbone (A), wherein said polymeric sidechains (B) are obtainable by (co-)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogencontaining monomer (B2), optionally further monomer(s) (B3), and optionally further monomers besides (B1), (B2) and (B3).
As vinyl ester monomer (B1), at least one of vinyl acetate, vinyl propionate and/or vinyl laurate is selected. Besides those, further vinyl ester monomers (B1) may be employed which are known to a person skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and/or vinyl benzoate. As optional monomer (B2) at least one nitrogen-containing monomer being selected from the group consisting of vinyllactames, vinyl imidazoles, 1 -vinyltriazole, 4-vinylpyridine, 4- vinylpyridine-N-oxide, 2-vinylpyridine, 1-vinyloxazolidinone, N-vinylformamide, N- vinylacetamide, N-vinyl-N-methylacetamide, and acrylamides such as acrylamide, methacrylamide, N-alkyl-substituted acrylamides, N,N‘-di alkyl (meth) acrylamide; mono- and dialkylamino-alkyl-(meth)acrylates, being preferably a vinyllactame-monomer and/or a vinylimidazole-monomer, the vinyllactam being more preferably selected from N- vinyllactams, such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone, N-vinylcaprolactam, and most preferably N-vinylpyrrolidone, and the vinylimidazole being preferably N-vinyl imidazole, 2-methyl-1 -imidazole, more preferably N-vinyl imidazole, may be employed.
Further monomers (B3) may be employed as optional monomers, such monomers being different to (B1) and (B2) and being present only in an amount of preferably less than 10% of the total amount of monomers employed for obtaining the polymeric sidechains (B), and are more preferably present only as impurities but not deliberately added for polymerization. (B3) monomers may be any monomer chosen from 1 -vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinyl pyridine-N-oxide, N-vinyl formamide and its amine if hydrolyzed after polymerization, N-vinyl acetamide, N-vinyl-N-methyl acetamide, alkyl esters of (meth)acrylic acid, and their derivatives.
Besides monomers (B1), (B2) and (B3) at least one further monomer, being different from those before, may be present for the co-polymerization to yield the side chains (B), wherein such further monomer is present only in an amount of less than 2% of the total amount of monomers employed for obtaining the polymeric sidechains (B), and is preferably present only as impurities but not deliberately added for polymerization.
In case monomer (B2) is present, the amounts of monomers are as follows, based on the total WEIGHT OF THE GRAFT POLYMER:
(B) is from 10 to 60%, preferably up to 50%, more preferably up to 40%, and preferably from 20%;
(B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 9 to 55 %, preferably up to 50, more preferably up to 40, even more preferably up to 35, and even more preferably up to 30%;
(B2) (nitrogen-containing monomer) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 1 to 41 %, preferably up to 30, more preferably up to 25 such as 1 to 25 and more preferably 5 to 25, even more preferably up to 15 such as 1 to 15 and more preferably 5 to 15, and further such as up to 10 up to 40, 35, 20, 10, and every number in between 1 and 41 , wherein preferably the amount of (B2) is not higher than the amount of (B1);
(B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0, but in all cases at most 10% of the amount of (B1), and not more than the amount of (B2).
The amount of further monomer(s) besides (B1), (B2) and (B3) is as detailed before. In case monomer (B2) is not present, the amounts of monomers are as follows, based on the total WEIGHT OF THE GRAFT POLYMER:
(B) is from 5 to 60%, preferably up to 50%, and preferably from 20%;
(B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is the total amount of (B) minus the total amount of (B3);
(B2) (nitrogen-containing monomer) is 0%;
(B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0.
The amount of further monomer(s) besides (B1), (B2) and (B3) is as detailed before.
In a preferred embodiment, the amount of vinyl ester monomer (B1) is usually not smaller than 10% by weight (in relation to the sum of (B1) and (B2)).
Preferably, optional further monomers (B3) are present only as impurities but not deliberately added for polymerization. More preferably, the amount is less than 1 , more preferably less than 0.5%, even more preferably less than 0.01% by weight based on total weight of monomers (B1), most preferably there is essentially no such monomers (B3), and most preferably even a total absence of any other monomer besides the monomers (B1) and optional monomers (B2). The same applies for the further monomers besides (B1), (B2) and (B3).
In a preferred embodiment, the graft polymer of the invention comprises polymeric sidechains (B) which are obtained or obtainable by radical polymerization of the at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) and optionally at least one further monomer (B3) in the presence of the polymer backbone (A), wherein at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 80, more preferably at least 90 weight percent, and most preferably essentially only vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B1 being employed).
In an even more preferred embodiment of the previous embodiment, essentially no other monomer (B3) is employed.
In an even more preferred embodiment of the previous embodiment, essentially no other monomers (B2) nor (B3) are employed.
In a preferred embodiment, the inventive graft polymer consists of monomers, wherein
(B) the monomers are:
(B1) at least one vinyl ester, selected from vinyl acetate, vinyl propionate and/or vinyl laurate, in amounts of from 70 to 100% by weight of the total weight of monomers that are grafted onto the backbone (A), preferably only vinyl acetate, and
(B2) optionally at least one nitrogen-containing monomer in amounts of from 0 to 30% by weight of the total amount of monomers that are grafted onto the backbone (A), being preferably a N-vinyllactam, such as N-vinylpyrrolidone, N-vinylpiperidone, N- vinylcaprolactam, even more preferably N-vinylpyrrolidone and/or N- vinylcaprolactam, and most preferably N-vinylpyrrolidone, with the vinyl ester monomer(s) (B1) optionally being partially or fully hydrolyzed after polymerization.
In a preferred embodiment thereof, the vinyl ester is not hydrolyzed.
In an alternative embodiment, at least one vinyllactame, preferably vinylpyrrolidone and/or vinylcaprolactame, more preferably only vinylpyrrolidone, as monomer (B2) is present besides at least one monomer (B1), with monomer (B1) being preferably comprising vinyl acetate, and even more preferably being only vinyl acetate. Even more preferably, vinyl acetate is the only monomer (B1) and vinylyprrolidone is the only monomer (B2).
In an alternative embodiment of the embodiments in the paragraph immediately before, the monomer (B1) may be partially or fully hydrolyzed after the polymerization reaction. In a preferred embodiment thereof, monomer (B1) is partially hydrolyzed, and is even more preferably hydrolyzed to up to 80, 70 or 60, 50, 40, 30, 20 or 10 mole percent based on the total amount of monomer(s) (B1).
Preferably the monomer (B1) is partially hydrolyzed of from 20 %, and is hydrolyzed up to 50%. In a most preferred embodiment of the embodiments before, vinyl acetate is employed as monomer (B1) and vinylpyrrolidone as monomer (B2), and the polymer moiety stemming from vinyl acetate is partially hydrolyzed after polymerisation, preferably in an amount of about 20 to 50, more preferably about 30 to 45, such as about 40mole %, based on total amount of vinyl acetate.
In an alternative, even more preferred embodiment of two paragraphs immediately before, the vinyl esters are not hydrolyzed at all.
It is to be understood that the amounts for (A), (B), (B1), (B2), (B3) and further monomers besides the ones before may be selected from the various detailed ranges given independently, i.e. lower and upper borders may be combined also from two different ranges given for one aspect to result in a numerical range not specified explicitly in numbers, such combined range for e.g. (A), (B), (B1), (B2) and (B3) however being explicitly intended to be encompassed by this present intention.
Also, broad ranges and very particularly preferred narrow ranges may be combined in one embodiment of this invention, with the selection of the ranges for one component being chosen independently of that for the other component, in as far as the overall numbers add up to a “100%-polymer”: e.g. the most preferred range for (A) and (B) may be chosen and combined with the broadest possible ranges given for (B1) I (B2) I (B3), and any other possible combination.
Preferably, for all selections possible to be made for (A)/(B) and (B1) / (B2) I (B3)), the same selections are to be made, e.g. all “preferred” ranges are chosen, or - more preferably - all “more preferred” ranges are chosen, or - most preferably - all “most preferable” ranges are chosen.
The inventive graft polymer as detailed before has a polydispersity (PDI) Mw/Mn of at most 10, preferably at most 5, more preferably at most 3, and most preferably in the range from 1 .0 to 2.6, and any number a as upper or lower limit and any range in between such as 1 ,3 to 2,6, 1 to 3 etc. (with Mw = weight average molecular weight in g/mol, and Mn = number average molecular weight in g/mol; with the PDI being unitless), with lower numbers being preferred, but depending on the Mn of the polymer backbone employed (the higher the Mn of (A) also typically the higher the PDI) and also on the amount of (B) (the higher the amount of (B) relative to the amount of (A) typically the higher the PDI).
The respective values of Mw and Mn can be determined using GPC standard methods, such as the one referenced in the experimental section. However, the molecular weights of the backbones used in this invention can also be calculated, as those reactions proceed basically to completeness. Hence, the calculation of the molecular weights based on the total molar amounts of ingredients employed for the preparation reaction is a viable way as well.
The graft polymers of the invention may contain a certain amount of ungrafted polymers (“ungrafted side chains”) made of monomers not being reacted with (i.e. grafted (on-)to) the polymer backbone.
The amount of such ungrafted polymers may be high or low, depending on the reaction conditions, but is preferably to be lowered and thus is more preferably low. By this lowering, the amount of grafted side chains is preferably increased. Such lowering can be achieved by suitable reaction conditions, such as dosing of monomers and radical initiator and their relative amounts and also in relation to the amount of backbone being present. Such adjustment is in principle known to a person of skill in the present field, and detailed hereinafter for this present invention within the description of a process to obtain the inventive graft polymers.
It has been found that the inventive graft polymers as detailed herein before exhibit an improved bio-degradability which is at least 35, more preferably at least 40, even more preferably at least 50, such as 41 , 42, 43, 44, 45 etc., 51 , 52, 53 etc, 55, 60, 65, etc. and any number in between and up to 100%, within 28 days when tested under OECD 301 F.
The ratios of (A) to (B) for the embodiments herein are:
(A) 20 to 95%, preferably 30 to 90%, more preferably 40 to 85%, most preferably 50 to 80% of a polymer backbone as a graft base, and
(B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60 %, most preferably 20 to 50%, of polymeric sidechains (B) grafted onto the polymer backbone (A),
With each percentage being on the total weight of the graft polymer, and the total of (a) plus (B) being 100 wt.%.
Any and each of the sub-units (a1), (a2), the polymer backbones as graft bases (A), (A1), (A2), (A3) and (A4) as defined by their structure or their preparation, and the monomers (B), (B1), (B2), (B3), and further monomers besides (B1), (B2), (B3) are the ones as defined herein and specifically those defined before in all of their embodiments, preferred embodiment etc, and in the examples; any such embodiment for the sub-units (a1 ), (a2), the polymer backbones as graft bases (A), (A1 ), (A2), (A3) and (A4) as defined by their structure or their preparation, and the monomers (B), (B1), (B2), (B3), and further monomers besides (B1), (B2), (B3) may be chosen individually and combined, provided that such selection is possible and not ruled out herein, i.e. the totals need to add up as required and the embodiments are compatible (i.e. an embodiment requiring (B2) obviously not be combined with an embodiment requiring the absence of (B).
In a more preferred embodiment, the graft polymer of the invention and/or as detailed before consists of:
(A) at least on polymer backbone as graft base, such graft bases being any of the previously defined polymer backbones in any of the embodiments, preferably any of (a 1 ), (A2), (A3) and (A4) as previously defined, in the amounts defined in any of the embodiments herein, including the description, the examples, and the claims, and
(B) polymeric sidechains (B) grafted onto the polymer backbone (A), wherein said polymeric sidechains (B) are obtainable by (co-)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), and optionally further monomer(s) (B3), and optionally further monomers, all such monomers being any of the monomers as defined in any of the embodiments herein, in the amounts defined in any of the embodiments herein, including the description, the examples, and the claims.
In one embodiment of the previous embodiment, the vinyl ester monomer is vinyl acetate as the only monomer (B1), and more preferably vinylpyrrolidone is the only monomer (B2), and most preferably no other monomers (B3) and further monomers besides the previous ones are present.
In a preferred embodiment of the previous embodiment, the vinyl ester is hydrolyzed to about 20 to 50 mole percent, preferably about 30 to 45 mole %, most preferably about 40 mole%.
In a specific embodiment, the graft polymer of the invention consists of:
(A) 20 to 95%, preferably 30 to 90%, more preferably 40 to 85%, most preferably 50 to 80% of a polymer backbone as a graft base, with the percentages as weight percent in relation to the total weight of the graft polymer; which comprises at least one sub-unit (a1) and at least one sub-unit (a2), wherein
(a1) is a unit comprising, preferably essentially consisting of, moieties derived from at least one alkylene oxide monomer and/or at least one polyalkylene oxide-polymer having two hydroxy-end-groups, the alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,
(a2) is a unit comprising, preferably consisting of, at least one lactone and/or at least one hydroxy acid, such sub-unit (a2) being a moiety derived from a single lactone and/or hydroxy-acid or being oligo-or-polymeric units consisting of at least one type of lactone and/or at least one type of hydroxy acid, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e. cyclic esters, starting with a-lactone (three ring atoms) followed by P-lactone (four ring atoms), y-lactone (five ring atoms) and so on; such lactones preferably being p-propiolactone, g-butyrolactone, b-valerolactone, g- valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; and ii) hydroxy acid(s), which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, specifically an a-, p- or y- hydroxy acid derived from the corresponding lactone by hydrolyzation, and lactic acid, glycolic acid, 4-hydroxybutanoic acid, 6-hydroxy hexanoic acid, 12-hydroxy stearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone, wherein the polymer backbone is either obtained
(A1) by co-polymerization of at least one sub-unit (a1) and at least one sub-unit (a2), wherein optionally at least one oligomer or polymer made from at least one sub-unit (a1) or at least one sub-unit (a2) can be employed within the copolymerization of at least one sub-unit (a1) and at least one sub-unit (a2) as well;
(A2) by first oligo-/polymerizing sub-unit(s) (a2) and then polymerizing the product with sub-unit(s) (a1);
(A3) By first oligo-/polymerizing sub-unit(s) (a1) and then co-polymerizing the product with sub-unit(s) (a2); or
(A4) by first providing an oligo- or polymeric sub-unit (a1) which is bears an end-cap on one side, preferably is etherified with alcohols, more preferably short-chain alcohols C1 to C4, which - as starter-block - is thereafter reacted with at least one sub-unit (a2) and optionally at least one sub-unit (a1) - wherein the sub-unit (a1) may be different to that/those in the starter block or may be arranged in a different order compared to those in the starter block - to attach to the non-end capped side of the starter block a new block comprising moieties from the sub-units employed for the (co-)polymerization, thereby obtaining a di-block-structure of [end-cap]-[sub-unit(s) (a1)]-[sub-unit(s) (a2)], or [end-cap]-[sub-unit(s) (a1)]-[random-{sub-unit(s) (a2)-sub unit(s) (a1)}]; wherein in case more than one sub-unit (a1) and/or more than one sub-unit (a2) are present already in an employed oligomer or polymer, those sub-units can be arranged in any order within such employed oligomer or polymer, and wherein in case more than one sub-unit (a1) and/or more than one sub-unit (a2) are present for the polymerization, those sub-units (and the optional oligomer/polymers if employed) can be arranged in any order within the obtained backbone; or selected from
(A1 ) a backbone consisting of a randomly arranged order of monomeric, oligomeric and/or polymeric (al)-sub-units and monomeric, oligomeric and/or polymeric (a2)-sub- units, with more than one sub-unit (a1) and/or more than one sub-unit (a2) being present;
(A2) a backbone consisting of oligo- or polymerized sub-units (a2) as an inner block and two outer blocks of oligomeric and/or polymeric (al)-sub-units, defined as “-[block of (a1)]-[block of (a2)]-[block of (a1 )]-“, and also possibly comprising higher block- polymers such as 5-, 7- and 9- etc. blocks where at the outside of the tri-block structure further blocks of (a1) and (a2) are connected, such as a penta-block “ [block of (a 1 )] - [block of (a2)] - [block of (a1)]-[block of (a2)] - [block of (a 1 )] - [block of (a2)] - [block of (a1)] “ and so on;
(A3) a backbone consisting of and inner block of oligomeric and/or polymeric (a1)-sub- units and two outer blocks of oligo- or polymeric sub-units (a2), in the form of at least an tri-block-polymer defined as “ - [block of (a2)]-[block of (a1 )] - [block of (a2)] and
(A4) a backbone consisting of a first block with
(i) on one end an end-cap - such end-cap being a C1 to C18-, preferably C1- C4-alkyl-group attached to said first block via an ether-function; and
(ii) an oligo- or polymeric sub-unit (a1); and a second block which is attached to said first block at the opposite end of said first block (“opposite” in relation to the end-cap on said first block) via an ether or ester-fu notion, said second block being composed of at least one sub-unit (a2) and optionally at least one sub-unit (a1), wherein the optional sub-unit(s) (a1) in said second block may be different to that/those in the first block or may be arranged in a different order compared to those in the first block, and the order of the sub-unit(s) (A1) and (a2) may be also in any order, including random structure, such di-block-structure having as an idealized structure in case of using only sub-unit(s) (a2) for the second block:
[end-cap]-[sub-unit(s) (a1)]-[sub-unit(s) (a2)] or in case of using sub-unit(s) (a1) and (a2) for the second block: [end-cap]-[sub-unit(s) (a1)]-[random-{sub-unit(s) (a2)-sub unit(s) (a1)}];
With the amounts for sub-units (a1) and (a2) being those as herein defined before; and wherein - optionally - at least one starter molecule is included in the backbone structure; and
(B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60 %, most preferably 20 to 50%, of polymeric sidechains (B) grafted onto the polymer backbone (A), wherein said polymeric sidechains (B) are obtainable by (co-)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), and optionally further monomer(s) (B3), and optionally further monomers, with the percentages as weight percent in relation to the total weight of the graft polymer; wherein the monomers are:
(B1) at least one vinyl ester, selected from vinyl acetate, vinyl propionate and/or vinyl laurate and any further vinylester known to a person skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and/or vinyl benzoate;
Optionally
(B2) at least one nitrogen-containing monomer being selected from the group consisting of vinyllactames, vinyl imidazoles, 1 -vinyltriazole, 4-vinylpyridine, 4-vinylpyridine-N- oxide, 2-vinylpyridine, 1-vinyloxazolidinone, N-vinylformamide, N-vinylacetamide, N- vinyl-N-methylacetamide, and acrylamides such as acrylamide, methacrylamide, N- alkyl-substituted acrylamides, N,N‘-di alkyl (meth) acrylamide; mono- and dialkylamino- alkyl-(meth)acrylates, being preferably a vinyllactame-monomer and/or a vinylimidazole- monomer, the vinyllactam being more preferably selected from N-vinyllactams, such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N- vinylpyrrolidone, N-vinylcaprolactam, and most preferably N-vinylpyrrolidone, and the vinylimidazole being preferably N-vinyl imidazole, 2-methyl-1 -imidazole, more preferably N-vinyl imidazole; optionally
(B3) at least one further monomer, such as any one or more of 1 -vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinyl pyridine-N-oxide, N-vinyl formamide and its amine if hydrolyzed after polymerization, N-vinyl acetamide, N-vinyl-N-methyl acetamide, alkyl esters of (meth)acrylic acid; and Optionally at least one further monomer, being different from those before, such other monomer being present only in an amount of less than 2% of the total amount of monomers employed for obtaining the polymeric sidechains (B), and are preferably present only as impurities but not deliberately added for polymerization; with the amount(s) preferably as follows:
- if (B2) is present -
(B) is from 10 to 60%, preferably up to 50%, more preferably up to 40%, and preferably from 20%;
(B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 9 to 55 %, preferably up to 50, more preferably up to 40, even more preferably up to 35, and even more preferably up to 30%;
(B2) (nitrogen-containing monomer) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 1 to 41 %, preferably up to 30, more preferably up to 25 such as 1 to 25 and more preferably 5 to 25, even more preferably up to 15 such as 1 to 15 and more preferably 5 to 15, and further such as up to 10 up to 40, 35, 20, 10, and every number in between 1 and 41 , wherein preferably the amount of (B2) is not higher than the amount of (B1 ) or
- if (B2) is not present -
(B) is from 5 to 60%, preferably up to 50%, and preferably from 20%;
(B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is the total amount of (B) minus the total amount of (B3),
(B2) (nitrogen-containing monomer) is 0%,
And further provided that in all cases before
(B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0, but in all cases at most 10% of the amount of (B1 ), and not more than the amount of (B2); wherein preferably at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 80, more preferably at least 90 weight percent, and most preferably essentially only vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B1 being employed), and optionally the vinyl ester is hydrolyzed after polymerization.
In one embodiment of the previous embodiment, the vinyl ester monomer is vinyl acetate as the only monomer (B 1 ), and more preferably vinylpyrrolidone is the only monomer (B2), and most preferably no other monomers (B3) and further monomers besides the previous ones are present.
In a preferred embodiment of the previous embodiment, the vinyl ester is hydrolyzed to about 20 to 50 mole percent, preferably about 30 to 45 mole %, most preferably about 40 mole%.
Inventive polymers have preferably at least one of the following additional properties, preferably two or more, to be more successfully employed in the various fields of applications targeted with this present invention: i) the polymer backbone (A) may bear as the end-groups two hydroxy-groups or may be capped on both ends with C1 to C22-alkyl groups, preferably C1 to C4 alkyl groups; ii) the graft polymer has a polydispersity (PDI) Mw/Mn of at most 10, preferably at most 5, more preferably at most 3, and most preferably in the range from 1 .0 to 2.6, and any number a as upper or lower limit and any range in between such as 1 ,3 to 2,6, 1 to 3 etc.(with Mw = weight average molecular weight and Mn = number average molecular weight [g/mol I g/mol]); iii) the biodegradability of the graft polymer is at least 35, more preferably at least 40, even more preferably at least 45, even further more preferably at least 50, such as 46, 47, 48, 49, 50, 55, 60, 65, 70, 75 etc. and any number in between and up to 100%, within 28 days, when tested under OECD 301 F..
Further, the graft polymer is preferably water-soluble to a certain extent, to be able to employ the polymers within the aqueous environment typically present in the fields of applications as generally targeted with this present invention. Preferably inventive polymers should exhibit a medium to good, more preferably a good solubility in the environment of an aqueous formulation as typically employed in such fields for the various kinds of formulations, e.g. dish washing, automatic dish-washing, hard surface cleaning, fabric cleaning, fabric care, cosmetic formulations etc.
Further, the graft polymer solution preferably has a viscosity that at reasonably high solid concentrations of the polymer as to be handled in and after production and to be provided to the user, which could be e.g. as a “pure” (then typically liquid) product, dissolved in a solvent, typically an aqueous solution containing water and organic solvents, only water or only organic solvents, the viscosity of such polymer or polymer solution being in a range that allows typical technical process steps such as pouring, pumping, dosing etc. Hence, the viscosities should be preferably in a range of about up to less than 4000 mPas, more preferably up to 3500 mPas, even more preferably up to 3000 mPas, such as up to 4500, 3750, 3250, 2750 or even 2600 or below such as 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150, or 100 mPas, at concentrations of the polymer (based on the total solid content of the polymer in solution, as defined by weight percent of the dry polymer within the total weight of the polymer solution) of preferably at least 10 wt.%, more preferably at least 20, and even more preferably at least 40 wt.%, and most preferably at least 50 wt.%, such as at least 60, 70, 80 or even 90 wt.%. The viscosity may be measured at either 25 °C or at elevated temperature, e.g. temperatures of 50 or even 60 °C. By this a suitable handling of the polymer solutions in commercial scales is possible. It is of course evident that depending on the amount of solvent being added the viscosity is lower when the amount of solvent increases and vice versa, thus allowing for adjustment in case desired. It is also evident that the viscosity being measured depends on the temperature at which it is being measured, e.g. the viscosity of a given polymer with a given solid content of e.g. 80 wt.% will be higher when measured at lower temperature and lower when measured at a higher temperature. In a preferred embodiment the solid content is in between 70 and 99 wt.%, more preferably in between 75 and 85 wt.%, with no additional solvent being added but the polymer as prepared. In a more preferred embodiment, the solid content is in between 70 and 99 wt.%, more preferably in between 75 and 95 wt.%, with no additional solvent being added but the polymer as prepared, and the viscosity is lower than 3000 mPas, more preferably 3250, or even below 2750, 2600, 2500, 2000, 1750, 1500, 1250, 1000, 750, 500 or even 250 mPas, when measured at 60 °C. The viscosity may be determined as generally known for such polymers, preferably as described below in the experimental part.
As further criteria, of course, the individual performance of a specific polymer needs to be evaluated and thus ranked for each individual formulation in a specific field of application. Due to the broad usefulness of the inventive polymers an exhaustive overview or detailed guidance for each area is not possible, but the present specification and examples give a guidance on how to prepare and select useful polymers of desired properties and how to tune the properties to the desired needs. One such criteria for the area of home care and especially fabric care of course it he performance upon washing, e.g. subjecting a certain material exhibiting stains of certain materials to a defined washing procedure.
The examples give some guidance for the application for washing of fabrics, i.e. the general area of fabric care.
Depending on the individual needs for a polymer exhibiting a defined degree of biodegradation, water solubility and viscosity (i.e. handling properties) the general and specific teachings herein - without being intended to be limited to the specific examples being given - will guide on how to obtain such polymer.
Process
The invention also encompasses a process for obtaining a graft polymer according to any of the previous embodiments as defined herein and specifically any embodiment in the previous section, but also in any of the examples disclosed herein, wherein at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), optionally further monomer(s) (B3) and optional further monomers (besides (B1), (B2) and (B3)) is/are polymerized in the presence of at least one polymer backbone (A) as defined herein, preferably selected from backbones (A1), (A2), (A3) and (A4) as defined herein, wherein the polymeric sidechains (B) are obtained by radical polymerization, preferably using radical forming compounds to initiate the radical polymerization, wherein each B1 , B2 and B3 (and further monomers besides (B1), (B2) and (B3)) and (A), (A1), (A2), (A3) and (A4) are as defined herein before, in any of the embodiments including the claims and including as exemplified in the examples below, with each of it preferably being selected from any of its grades of preferences, in as far as each can be selected individually form its preferences, but always confirming to the general requirements of compatibility of preferences, such as total sums not exceeding 100 % etc.
It has to be noted that the “grafting process” as such, wherein a polymeric backbone, such as the polymer backbone (A) described herein above, is grafted with polymeric sidechains, is known to a person skilled in the art. Any process known to the skilled person in this respect can in principle be employed within the present invention.
The radical polymerization as such is also known to a skilled person. That person also knows that the inventive process can be carried out in the presence of a radical-forming initiator (C) and/or at least one solvent (D).
The skilled person knows the respective components suitable as such.
The term “radical polymerization” as used within the context of the present invention comprises besides the free radical polymerization also variants thereof, such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, which are each known to the skilled person, including suitable control agents.
In a preferred embodiment, the process to produce a graft polymer of the invention and/or as detailed before comprises the polymerization of at least one vinyl ester monomer (B1) and optionally at least one nitrogen-containing monomer (B2), optionally at least one further monomer (B3) and optionally further monomer(s) - the latter being preferably present only as impurities, and more preferably are essentially not present -, in the presence of at least one polymer backbone (A), preferably selected from the backbones (A1), (A2), (A3) and (A4) as defined herein before, a free radical-forming initiator (C) and, if desired, up to 50% by weight, based on the sum of components (A), (B), and (C), of at least one solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomers (B1), optional (B2) and optional (B3) (the further monomers typically not being monitored as present only as impurity in low, thus neglectable amounts) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the copolymer backbone (A). In a preferred embodiment no monomer (B2) is employed. In a more preferred embodiment, no monomer (B2) nor monomer (B3) are employed. In an even more preferred embodiment only monomer(s) (B1) are employed. Generally, the amount of further monomer(s) besides (B1), (B2) and (B39 is minimized, preferably they are not present at all.
In a preferred embodiment of any of the embodiments of the process as detailed in the previous paragraph, at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent, and most preferably essentially only (i.e. about 100wt.% or even 100 wt.%) vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B1 being employed).
Generally, besides monomers (B1), (B2) and (B3), at least one further monomer, being different from those before, may be employed for the co-polymerization to yield the side chains (B), wherein such further monomer is present only in an amount of less than 2% of the total amount of monomers employed for obtaining the polymeric sidechains (B), and is preferably employed only as - in practical aspects non-avoidable - impurities but not deliberately added for polymerization, and most preferably is not present at all.
In a more preferred embodiment of the previous two paragraphs, the following additional provisions 1) (presence of (B2)) and 2) (absence of (B2)) apply for the amounts and ratios of monomers:
In case monomer (B2) is employed, the amounts of monomers are as follows, based on the total WEIGHT OF THE GRAFT POLYMER:
(B) is from 10 to 60%, preferably up to 50%, more preferably up to 40%, and preferably from 20%;
(B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 9 to 55 %, preferably up to 50, more preferably up to 40, even more preferably up to 35, and even more preferably up to 30%;
(B2) (nitrogen-containing monomer) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 1 to 41 %, preferably up to 30, more preferably up to 25 such as 1 to 25 and more preferably 5 to 25, even more preferably up to 15 such as 1 to 15 and more preferably 5 to 15, and further such as up to 10 up to 40, 35, 20, 10, and every number in between 1 and 41 , wherein preferably the amount of (B2) is not higher than the amount of (B1 );
(B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0, but in all cases at most 10% of the amount of (B1), and not more than the amount of (B2).
The amount of further monomer(s) besides (B1), (B2) and (B3) is as detailed before, and the monomers (B1), (B2) and (B3) are those as detailed herein before in any of the embodiments disclosed.
In case monomer (B2) is not employed, the amounts of monomers are as follows, based on the total WEIGHT OF THE GRAFT POLYMER:
B) is from 5 to 60%, preferably up to 50%, and preferably from 20%;
(B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is the total amount of (B) minus the total amount of (B3),
(B2) (nitrogen-containing monomer) is 0%; (B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0.
The amount of further monomer(s) besides (B1), (B2) and (B3) is as detailed before, and the monomers (B1), (B2) and (B3) are those as detailed herein before in any of the embodiments disclosed.
In a preferred embodiment, the amount of vinyl ester monomer (B1) employed is usually not smaller than 10% by weight (in relation to the sum of (B1) and (B2)).
Preferably, optional further monomers (B3) are present also only as impurities but not deliberately added for polymerization. More preferably, the amount is less than 1 , more preferably less than 0.5%, even more preferably less than 0.01% by weight based on total weight of monomers (B1), most preferably there is essentially no such monomers (B3), and most preferably even a total absence of any other monomer besides the monomers (B1 ) and optional monomers (B2). The same applies for the further monomers besides (B1), (B2) and (B3).
In specifically preferred embodiments, the amounts of monomers employed are as follows, based on the total WEIGHT OF THE GRAFT POLYMER:
(A) is from 40 to 90%, preferably from 50%, more preferably from 60%, and preferably at most 80%, of a polymer backbone as defined herein before, preferably at least one of (A1), (A2) and (A3), as a graft base,
(B) is from 10 to 60%, preferably up to 50%, more preferably up to 40%, and preferably from 20%;
(B1) (vinylester) is from 9 to 55 %, preferably up to 50, more preferably up to 40, even more preferably up to 35, and even more preferably up to 30%;
(B2) (at least one vinyllactam, preferably vinylpyrrolidone and/or vinylcaprolactam, more preferably vinylpyrrolidone) is from 1 to 25 %, preferably up to 20, more preferably up to 15, even more preferably up to 10, such as even only up to 5, wherein at most the amount of (B2) is not higher than the amount of (B1 );
(B3) (further monomer(s)) is from 0 to 2, preferably at most 1 , more preferably 0, but in all cases at most 10% of the amount of (B1 ), and not more than the amount of (B2);
More preferably the optional further monomers (B3) and the further monomers besides (B1 ), (B2) and (B3) are preferably present only as impurities but not deliberately added for polymerization; more preferably, the amount is less than 1 , more preferably less than 0.5%, even more preferably less than 0.01% by weight based on total weight of monomers (B1), most preferably there is essentially no such monomers (B3) nor further monomers, and most preferably even a total absence of any other monomer besides the monomers (B1 ) and (B2). The amount of vinyl ester monomer (B1) is usually not smaller than 10% by weight (in relation to the sum of (B1) and (B2)).
In alternatively specifically preferred embodiments, the amounts of monomers employed are as follows, based on the total WEIGHT OF THE GRAFT POLYMER: (A) is from 40 to 90%, preferably from 50%, more preferably from 80%, of a polymer backbone as defined herein before, preferably at least one of (A1), (A2) and (A3), as a graft base;
(B) is from 10 to 60%, preferably up to 50%, and preferably from 20%;
(B1) (vinylester) is the total amount of (B) minus the total amount of (B3);
(B2) is 0%;
(B3) (further monomer(s)) is from 0 to 2, preferably at most 1 , more preferably 0, but in all cases at most 10% of the amount of (B1 ), and not more than the amount of (B2); the amount of vinyl ester monomer (B1 ) is usually not smaller than 10% by weight (in relation to the sum of (B1) and (B2)); the optional further monomers (B3) and the further monomers beside (B1 ), (B2) and (B3) are preferably present only as impurities but not deliberately added for polymerization. More preferably, the amount is less than 1 , more preferably less than 0.5%, even more preferably less than 0.01 % by weight based on total weight of monomers (B1 ), most preferably there is essentially no such monomers (B3) nor further monomers, and most preferably even a total absence of any other monomer besides the monomers (B1 ).
The amount of ((free) radical-forming) initiator (C) is preferably from 0.1 to 5% by weight, in particular from 0.3 to 3.5% by weight, based in each case on the polymeric sidechains (B).
For the process according to the invention, it is preferred that the steady-state concentration of radicals present at the mean polymerization temperature is substantially constant and the graft monomers (B), and especially (B1), more preferably (B1) and (B2), even more preferably (B1), (B2) and (B3), are present in the reaction mixture constantly only in low concentration (for example of not more than 5% by weight in total). This allows the reaction to be controlled, and graft polymers can be prepared in a controlled manner with the desired low polydispersity.
To assure a safe temperature control although - especially when a polymerization is started at high solid concentrations or in bulk and/or with a large amount of monomers being present from the start on it is advisable, and thus preferred, to use an additional and efficient measure to control the temperature. This can be done by external and/or internal cooling; such cooling can be done by internal and/or external coolers such as heat exchangers, or using reflux condensers when working at the boiling temperature of the solvent or the solvent mixture at a given temperature/pressure-combination.
The same measure could of course be used for the preferred embodiment mentioned before wherein the monomers are added over a prolonged period of time, and thus the monomer concentration in the reaction volume being constantly low over time.
However, under such conditions, temperature control is usually not a crucial point, as the temperature is at least partially controlled also by the propagation of the polymerization reaction by controlling the radical concentration and the available amount of polymerizable monomers. Of course, depending on the scale of the polymerisation reaction, such additional cooling as described before may become necessary for both variants - batch reaction or bulk reactions with large amounts of monomer present from the start or semi-continuous or continuous polymerization reactions with typically constantly low monomer concentrations - when the scale gets large enough that the ratio from volume to surface of the polymerization mixture becomes very large.
This however is generally known to a person of skill in the art of commercial scale polymerisations, and thus can be adapted to the needs.
According to the invention, the initiator (C) and the graft monomers (B), and especially (B1) and/or (B2) and/or (B3), preferably twice “and”, are advantageously added in such a way that a low and substantially constant concentration of undecomposed initiator and graft monomers (B), and especially a constant but low amount of (B1) and especially even more (B2) (especially in case when vinylpyrrolidone is selected as (B2)), are present in the reaction mixture. The proportion of undecomposed initiator in the overall reaction mixture is preferably < 15% by weight, in particulars 10% by weight, based on the total amount of initiator metered in during the monomer addition.
In a more preferred embodiment, the process comprises the polymerization of at least one vinyl ester monomer (B1) and optionally at least one nitrogen-containing monomer (B2), optionally at least one other monomer (B3) and optionally at least one further monomer(s), more preferably only monomers (B1) and (B2), in the presence of at least one polymer backbone (A) as defined herein, preferably selected from (A1), (A2) and (A3), a free radicalforming initiator (C) and, if desired, up to 50% by weight, based on the sum of components (A), (B) and (C), of at least one solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomers (B) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the polymer backbone (A), wherein preferably at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent, and most preferably essentially only (i.e. about 100wt.% or even 100 wt.%) vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B1 being employed).
In an even more preferred embodiment of the preceding embodiment before, besides the monomer(s) (B1) essentially no monomer (B2) is employed, preferably (B1) comprises vinyl acetate, more preferably comprises essentially only vinyl acetate, all in the ranges and preferred ranges given in the section on the “graft polymers of this invention”.
In an alternative embodiment to the one before, besides the monomer(s) (B1) essentially only monomer (B2) is employed, preferably (B1) comprises vinyl acetate, more preferably comprises essentially only vinyl acetate, and preferably (B2) comprises a vinyllactam, more preferably comprises vinylpyrrolidone, and even more preferably comprises essentially vinylpyrrolidone, all in the ranges and preferred ranges given in the section on the “graft polymers of this invention”. The mean polymerization temperature for the main polymerization and the postpolymerization is appropriately in the range from 50 to 140°C, preferably from 60 to 120°C and more preferably from 65 to 110°C. Typically, the temperature for the post-polymerization is higher by 5 to 40 °C compared to the polymerization.
The term “mean polymerization temperature” is intended to mean here that, although the process is substantially isothermal, there may, owing to the exothermicity of the reaction, be temperature variations which are preferably kept within the range of +/- 10°C, more preferably in the range of +/- 5°C.
According to the invention, the (radical-forming) initiator (C) at the mean polymerization temperature should have a decomposition half-life of from 40 to 500 min, preferably from 50 to 400 min and more preferably from 60 to 300 min.
Examples of suitable initiators (C) whose decomposition half-life in the temperature range from 50 to 140°C is from 20 to 500 min are:
O-C2-Ci2-acylated derivatives of tert-C4-Ci2-alkyl hydroperoxides and tert-(Cg-Ci2- aralkyl) hydroperoxides, such as tert-butyl peroxyacetate, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5- trimethylhexanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyneodecanoate, 1 ,1 ,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, tert-butyl peroxybenzoate, tertamyl peroxybenzoate and di-tert-butyl diperoxyphthalate; di-O-C4-Ci2-acylated derivatives of tert-Cs-C -alkylene bisperoxides, such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoyl- peroxy)hexane and 1 ,3-di(2-neodecanoylperoxyisopropyl)benzene; di(C2-Ci2-alkanoyl) and dibenzoyl peroxides, such as diacetyl peroxide, dipropionyl peroxide, disuccinyl peroxide, dicapryloyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, di(4- methylbenzoyl) peroxide, di(4-chlorobenzoyl) peroxide and di(2,4-dichlorobenzoyl) peroxide; tert-C4-Cs-alkyl peroxy(C4-Ci2-alkyl)carbonates, such as tert-amyl peroxy(2-ethyl- hexyl)carbonate; di(C2-Ci2-alkyl) peroxydicarbonates, such as di(n-butyl) peroxydicarbonate and di(2- ethylhexyl) peroxydicarbonate.
Depending on the mean polymerization temperature, examples of particularly suitable initiators (C) are: at a mean polymerization temperature of from 50 to 60°C: tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, 1 ,1 ,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1 ,3-di(2-neodecanoyl peroxyisopropyl)benzene, di(n-butyl) peroxydi carbon ate and di(2-ethylhexyl) peroxydicarbonate; at a mean polymerization temperature of from 60 to 70°C: tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate and di(2,4-dichlorobenzoyl) peroxide; at a mean polymerization temperature of from 70 to 80°C: tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(2,4-dichlorobenzoyl) peroxide and 2,5-dimethyl-2,5- di(2-ethylhexanoylperoxy)hexane; at a mean polymerization temperature of from 80 to 90°C: tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2- ethylhexanoate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dibenzoyl peroxide and di(4- methylbenzoyl) peroxide; at a mean polymerization temperature of from 90 to 100°C: tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide and di(4- methylbenzoyl) peroxide; at a mean polymerization temperature of from 100 to 110°C: tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate and tert-amyl peroxy(2-ethylhexyl)carbonate; at a mean polymerization temperature of from 110 to 120°C: tert-butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tertamyl peroxy(2-ethylhexyl)carbonate.
Preferred initiators (C) are O-C4-Ci2-acylated derivatives of tert-C4-C5-alkyl hydroperoxides, particular preference being given to tert-butyl peroxypivalate and tert-butyl peroxy-2- ethylhexanoate.
Particularly advantageous polymerization conditions can be established effortlessly by precise adjustment of initiator (C) and polymerization temperature. For instance, the preferred mean polymerization temperature in the case of use of tert-butyl peroxypivalate is from 60 to 80°C, and, in the case of tert-butyl peroxy-2-ethylhexanoate, from 80 to 100°C.
The inventive polymerization reaction can be carried out in the presence of, preferably small amounts of, a solvent (D). It is of course also possible to use mixtures of different solvents (D). Preference is given to using water-soluble or water-miscible organic solvents. However, water as only solvent is in principle also possible but not preferred.
When a solvent (D) is used as a diluent, generally from 1 to 40% by weight, preferably from 1 to 35% by weight, more preferably from 1 .5 to 30% by weight, most preferably from 2 to 25% by weight, based in each case on the sum of the components (A), (B1), optionally (B2), optionally (B3) and optional further monomers, and (C), are used. Examples of suitable solvents (D) include: monohydric alcohols, preferably aliphatic Ci-Ci6-alcohols, more preferably aliphatic C2-Ci2-alcohols, most preferably C2-C4-alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol; polyhydric alcohols, preferably C2-C -diols, more preferably C2-Ce-diols, most preferably C2-C4-alkylene glycols, such as ethylene glycol, 1 ,2-propylene glycol and 1 ,3-propylene glycol; alkylene glycol ethers, preferably alkylene glycol mono(Ci-Ci2-alkyl) ethers and alkylene glycol di(Ci-Ce-alkyl) ethers, more preferably alkylene glycol mono- and di(Ci- C2-alkyl) ethers, most preferably alkylene glycol mono(Ci-C2-alkyl) ethers, such as ethylene glycol monomethyl and -ethyl ether and propylene glycol monomethyl and - ethyl ether; polyalkylene glycols, preferably poly(C2-C4-alkylene) glycols having 2-20 C2-C4- alkylene glycol units, more preferably polyethylene glycols having 2-20 ethylene glycol units and polypropylene glycols having 2-10 propylene glycol units, most preferably polyethylene glycols having 2-15 ethylene glycol units and polypropylene glycols having 2-4 propylene glycol units, such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol; polyalkylene glycol monoethers, preferably poly(C2-C4-alkylene) glycol mono(Ci-C25- alkyl) ethers having 2-20 alkylene glycol units, more preferably poly(C2-C4-alkylene) glycol mono(Ci-C2o-alkyl) ethers having 2-20 alkylene glycol units, most preferably poly(C2-C3-alkylene) glycol mono(Ci-Ci6-alkyl) ethers having 3-20 alkylene glycol units; carboxylic esters, preferably C-i-Cs-alkyl esters of C-i-Ce-carboxylic acids, more preferably Ci-C4-alkyl esters of Ci-Cs-carboxylic acids, most preferably C2-C4-alkyl esters of C2-C3-carboxylic acids, such as ethyl acetate and ethyl propionate; aliphatic ketones which preferably have from 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone; cyclic ethers, in particular tetrahydrofuran.
The solvents (D) are advantageously those solvents, which are also used to formulate the inventive graft polymers for use (for example in washing and cleaning compositions) and can therefore remain in the polymerization product.
Preferred examples of these solvents are polyethylene glycols having 2-15 ethylene glycol units, polypropylene glycols having 2-6 propylene glycol units and in particular alkoxylation products of Ce-Cs-alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).
Particular preference is given here to alkoxylation products of Cs-Ci6-alcohols with a high degree of branching, which allow the formulation of polymer mixtures which are free-flowing at 40-70°C and have a very low polymer content at comparatively low viscosity. The branching may be present in the alkyl chain of the alcohol and/or in the polyalkoxylate moiety (copolymerization of at least one propylene oxide, butylene oxide or isobutylene oxide unit). Particularly suitable examples of these alkoxylation products are 2-ethylhexanol or 2- propylheptanol alkoxylated with 1-15 mol of ethylene oxide, C13/C15 OXO alcohol or Ci2/Ci4 or Cie/Cis fatty alcohol alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide, preference being given to 2-propylheptanol alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide.
In an alternative embodiment the polymerization is performed using a mixture of at least one organic solvent and water.
In a preferred embodiment, the amount of water during the polymerization is low, preferably at most 10 wt.%, more preferably at most 5wt% based on total solvent, more preferably at most 1 %.
In a further alternative embodiment the polymerization is performed using water as solvent (D). However, water as only solvent is not preferred.
The radical initiator (C) is preferably employed in the form of a concentrated solution in one of the solvents mentioned before. The concentration of course depends on the solubility of the radical initiator. It is preferred, that the concentration is as high as possible to allow to introduce as little as possible of the organic solvent into the polymerization reaction. In case the initiator is soluble in water, and thus water is used as solvent for introducing the initiator, the concentration is not critical from the viewpoint of residual levels of water.
Preferably, the amount of water during the polymerisation is at most 10 wt.%, preferably at most 5 wt.%, more preferably at most 1 wt.%, based on total weight of graft polymer (at the end of the polymerization) or based on total weight of (A) and (B) (at the start of the polymerization).
In the process according to the invention, polymer backbone (A), graft monomer(s) (B), initiator (C) and, if appropriate, solvent (D) are usually heated to the selected mean polymerization temperature in a reactor.
According to the invention, the polymerization is carried out in such a way that an excess of polymer (polymer backbone (A) and formed graft polymer) is constantly present in the reactor. The quantitative ratio of polymer to ungrafted monomer and initiator is generally > 10:1 , preferably > 15:1 and more preferably > 20:1.
The polymerization process according to the invention can in principle be carried out in various reactor types. Such reactor types are generally known, and includes any stirred-type reactor such as vessels, but also includes tube reactors, reactor cascades from vessels or various tubes etc.
The reactor used is preferably a stirred tank in which the polymer backbone (A), if appropriate together with portions, of generally up to 15% by weight of the particular total amount, of graft monomers (B), initiator (C) and solvent (D), are initially charged fully or partly and heated to the polymerization temperature, and the remaining amounts of (B), (C) and, if appropriate, (D) are metered in, preferably separately. The remaining amounts of (B), (C) and, if appropriate, (D) are metered in preferably over a period of > 2 h, more preferably of > 4 h and most preferably of > 5 h.
In the case of a particularly preferred, substantially solvent-free process variant, the entire amount of polymer backbone (A) is initially charged as a melt and the graft monomers (B1) and, if appropriate, (B2) and/or (B3), and also the initiator (C) present preferably in the form of a from 10 to 50% by weight solution in one of the solvents (D), are metered in, the temperature being controlled such that the selected polymerization temperature, on average during the polymerization, is maintained with a range of especially +/- 10°C, in particular +/- 5°C.
In a further particularly preferred, low-solvent process variant, the procedure is as described above, except that solvent (D) is metered in during the polymerization in order to limit the viscosity of the reaction mixture. It is also possible to commence with the metered addition of the solvent only at a later time with advanced polymerization, or to add it in portions.
The polymerization can be affected under standard pressure or at reduced or elevated pressure. When the boiling point of the monomers (B1) and/or (B2) (and if employed also monomer (B3)) and/or of any solvent (D) used is exceeded at the selected pressure, the polymerization is carried out with reflux cooling.
A post-polymerization process step may be added after the main polymerization reaction. For that a further amount of initiator (dissolved in the solvent(s)) can be added over a period of 0,5 hour and typically up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, (such duration however also depending on the scale of the reactor) with the radical initiator and the solvent(s) for the initiator typically - and preferred - being the same as the ones for the main polymerization reaction. Of course, a different radical initiator and/or different solvent(s) may be employed as well.
The temperature of the post-polymerisation process step may be the same as in the main polymerization reaction (which is preferred in this invention) or may be increased. In case increased, it may be typically higher by about 5 to 40°C, preferably 10 to 20°C.
In between the post-polymerisation and the main polymerization a certain period of time may be waited, where the main polymerization reaction is left to proceed, before the postpolymerisation reaction is started by starting the addition of further radical initiator.
For solvents having a boiling point of approximately less than 110-120 °C at atmospheric pressure, such solvents may - as a purification step - be removed partially or essentially complete by thermal or vacuum distillation or stripping with a gas such as steam or nitrogen, such as stripping with steam made from water, all at ambient or reduced pressure, preferably vacuum distillation, whereas higher boiling solvents will usually stay in the polymer products obtained.
When mercaptoethanol is employed as chain transfer regulator, steam distillation is the preferred step of purification. Hence, higher boiling solvents like 1-methoxy-2-propanol, 1 ,2- propandiol and tripropylene glycol will stay in the polymer product, and thus their amounts should be minimized as far as possible by using as high as possible concentrations of the radical initiator when such solvents are used only for introducing the initiator, unless such solvents form also part of the formulation the graft polymer will be used within.
The graft polymers of the invention prepared using the process as defined herein may contain a certain amount of ungrafted polymers (“ungrafted side chains”) made of vinyl ester(s), e.g. poly vinyl acetate in case only vinyl acetate is employed, and/or - when further monomers are employed - homo- and copolymers of vinyl ester(s) with the other monomers. The amount of such ungrafted vinyl ester-homo- and copolymers may be high or low, depending on the reaction conditions, but is preferably to be lowered and thus low. By this lowering, the amount of grafted side chains is preferably increased. Such lowering can be achieved by suitable reaction conditions, such as dosing of vinyl ester and radical initiator and their relative amounts and also in relation to the amount of backbone being present. Such reaction controlling and the necessary process steps is generally known to a person of skill in the present field, specific guidance being given herein.
This adjustment of the degree of grafting and this amount of ungrafted polymers can be used to optimize the performance in areas of specific interest, e.g. certain (e.g. detergent-) formulations, application areas or desired cleaning etc. performance.
It is believed that the conditions considered favorable herein promote a - suspected - higher degree of grafting; such higher degree of grafting is associated with a better performance. This suspected higher degree of grafting however does not compromise the biodegradation - which is attributed to the ester linkage in the backbone, which can “compensate” the lower biodegradation of a graft polymer having a higher degree of grafting - which is seen in the “conventional graft polymers” based on polyalkylene oxides as backbone.
A drawback is that it is extremely difficult if not even impossible to actually verify such degree of grafting on a polymer, especially with increasing molecular weights of the polymers, as the total amount of grafting sites in a polymer is generally very low compared to the molecular weight; thus, the signal-to-noise-ratio is unfavorable for polymers in view of current analytical tools.
In another - alternative - embodiment of the present invention, the polymeric sidechains (B) of the graft polymer according to the present invention are fully or partially hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mole%, and preferably from 20mole%, more preferably 20 to 50, even more preferably 30 to 45, such as about 40 mole %, based on the total moles of (B1) employed, after the polymerization reaction and thus after the graft polymer as such is obtained. This means that the full or at least partial hydrolyzation of the polymeric sidechains (B) of the graft polymer is carried out in a further process step after the polymerization process (including after the optional postpolymerisation step if employed) of the polymeric sidechains (B) is finished.
In another alternative embodiment, no hydrolysis is performed on the graft polymer after the polymerization process of the polymeric sidechains (B) is finished. Due to this full or at least partial hydrolyzation of the polymeric sidechains (B) of the graft polymers according to the present invention, the respective sidechain units originating from the at least one vinyl ester monomer (B1) are changed from the respective ester function into the alcohol function within the polymeric sidechain (B). It has to be noted that the corresponding vinyl alcohol is not suitable to be employed as monomer within the polymerization process of the polymeric sidechains (B) due to stability aspects of the “vinylalcohol”-monomer. In order to obtain an alcohol function (hydroxy substituent) within the polymeric sidechains (B) of the graft polymers according to the present invention, the alcohol function is typically introduced by hydrolyzing the ester function of the sidechains.
From a theoretical point of view, each ester function of the polymeric sidechain (B) may be partially or completely replaced by an alcohol function (hydroxy group). In such a case, the polymeric sidechain is fully hydrolyzed (“saponified”).
The hydrolysis can be carried out by any method known to a person skilled in the art. For example, the hydrolysis can be induced by addition of a suitable base, such as sodium hydroxide or potassium hydroxide. Such hydrolysis processes are known from prior art.
In a preferred embodiment of the embodiments before, vinyl acetate is employed as monomer (B1 ) and vinylpyrrolidone as monomer (B2) and no other monomers are employed besides (B1) and (B2), and the polymer moiety stemming from vinyl acetate is partially hydrolyzed after polymerisation, preferably in an amount of from 20 to 50 mole, more preferably 30 to 45, such as - most preferably - about 40 mole %based on the total moles of (B1) employed.
The graft polymer of this invention, i.e. the polymer solution obtained from the process, may be also subjected to a means of concentration and/or drying.
The graft polymer solution obtained may be concentrated by subjecting the polymer solutions to means for removing part of the volatiles and especially solvent(s) to increase the solid polymer concentration. This may be achieved by distillation processes such as thermal or vacuum distillation, or by stripping using gases such as steam or inert gases such as nitrogen or argon, which is performed until the desired solid content is achieved. Such process can be combined with the purification step as disclosed before wherein the graft polymer solution obtained is purified by removing part orall of the volatile components such as volatile solvents and/or unreacted, volatile monomers, by removing the desired amount of solvent.
The graft polymer solution may be also after the main and/or the optional post-polymerization step and the optional purification step further concentrated or dried by subjecting the graft polymer solution to means of removing the volatiles partially or fully, such as - for concentration - distillation processes such as thermal or vacuum distillation, or by stripping using gases such as steam or inert gases such as nitrogen or argon, which is performed until the desired solid content is achieved, and/or drying such as roller-drum drying, spray-drying, vacuum drying or freeze-drying, preferably - mainly for cost-reasons - spray-drying. Such drying process may be also combined with an agglomeration or granulation process such as spray-agglomeration, granulation or drying in a fluidized-bed dryer. Hence, the process of the invention encompasses preferably at least one further process step selected from i) to iv), with i) post-polymerisation; ii) purification; iii) concentration; and iv) drying.
More preferably, the process as detailed herein in any of the embodiments defined, comprises at least one further process step selected from: i) a post-polymerization process step that is performed after the main polymerization reaction, wherein preferably a further amount of initiator (optionally dissolved in the solvent(s)) is added over a period of 0,5 hour and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, with the radical initiator and the solvent(s) for the initiator typically - and preferred - being the same as the ones for the main polymerization reaction; and wherein after the polymerization reaction and before the post-polymerisation reaction preferably a period is waited when the main polymerization reaction is left to proceed, before the post-polymerisation reaction is started by starting the addition of further radical initiator, such period being preferably from 10 minutes and up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, and most preferably up to 30 minutes; and wherein the temperature of the post-polymerisation process step is - preferably - the same as in the main polymerization reaction, or is increased, such increase being preferably higher by about 5 to 40°C, preferably 10 to 20°C compared to the temperature of the main polymerisation reaction; ii) a step of subjecting the graft polymer as obtained from the main polymerization or - if performed, the post-polymerisation process - to a means of purification, concentration and/or drying to remove part of or almost all of the remaining solvent(s) (as far as they are removable due to their boiling points) and/or volatiles such as residual monomers, wherein a. the concentration is performed by removing part of the solvent(s) and optionally also volatiles - by this this step additionally serves as means for purification - to increase the solid polymer concentration - and optionally as well for purification - , by preferably applying a distillation process such as thermal or vacuum distillation, preferably vacuum distillation, and/or applying stripping with gas such as steam or an inert gas such as nitrogen, preferably using steam from water, which is performed until the desired solid content and optionally also purity is achieved, preferably is performed until the desired part or all of the volatile components such as volatile solvents and/or unreacted, volatile monomers, are removed; b. the drying is performed by subjecting the graft polymer containing at least residual amounts of volatiles such as remaining solvent and/or unreacted monomers etc. to a means of removing the volatiles, such as drying using a roller-drum, a spray-dryer, vacuum drying or freeze-drying, preferably - mainly for cost-reasons - spray-drying; and optionally combining such drying process step with a means of agglomeration or granulation to obtain agglomerated or granulated graft polymer particles, such process being preferably selected from spray-agglomeration, granulation or drying in a fluidized-bed dryer, spray-granulation device and the like. Uses
In principle the graft polymers of this invention can be employed in any application to replace conventional graft polymers of the same or very similar composition (in terms of relative amounts of polymer backbone and grafted monomers especially when the type and amounts of grafted monomers is similar or comparable. Such applications are for example: redeposition of soils and removing of stains, avoiding or reducing re-soiling or greying or depositioning of solids, dispersion of actives in formulations of agrochemicals, pigments, colours, inorganic salts etc., inhibiting crystal growth including for inhibiting gas hydrate formation and/or reducing sedimentation and/or agglomeration, improve pigment dispersion stability, hydrophobisation of surfaces, reduction of growth of microbes on surfaces, and/or odor control etc., all compared to corresponding polymers or graft polymers according to the prior art.
Typical applications are:
Technical applications: Such compositions and formulations include glues of any kind, nonwater and - preferably - water-based liquid formulations or solid formulations, the use as dispersant in dispersions of any kind, such as in oilfield applications, automotive applications, typically where a solid or a liquid is to be dispersed within another liquid or solid.
Lacquer, paints and colorants formulations: Such compositions and formulations include non-water- and - preferably - water-based lacquer and colourants, paints, finishings.
Agricultural Formulations: Such compositions and formulations include formulations and compositions containing agrochemical actives within a liquid, semi-solid, mixed-liquid-solid or solid environment.
Aroma Chemical-formulations: Such compositions and formulations include formulations which dissolve or disperse aroma chemicals in liquid or solid compositions, to evenly disperse and/or retain their stability, so as to retain their aroma profile over extended periods of time; encompassed are also compositions that show a release of aroma chemicals over time, such as extended release or retarded release formulations.
The inventive graft polymers as defined herein, obtainable by a process as defined herein or obtained by the process as defined herein, can improve the overall bio-degradation ratio of such formulation, compositions and products by replacing non-biodegradable polymers of similar structures or properties. They may thus be advantageously used - partly also depending on the monomer(s) B employed for grafting and thus adjusted in their performance to the specific needs of the specific applications; such monomer substitution pattern as possibly also derivable from the prior art of analogous graft polymers based on simple PEGs and polyalkylene glycols.
Specifically, and beyond the performance in a certain type of application, the graft polymers according to the present invention lead to an improved biodegradability when being employed within such compositions or products, compared to the previously known graft polymers.
Hence, another subject matter of the present invention is the use of the graft polymers of the invention and/or obtained by or obtainable by a process of the invention and/or as detailed before, in cleaning compositions, fabric and home care products, in particular cleaning compositions for improved oily and fatty stain removal, removal of solid dirt such as clay, prevention of greying of fabric surfaces, and/or anti-scale agents, wherein the cleaning composition is preferably a laundry detergent formulation and/or a dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.
Hence, another subject matter of the present invention is the use of the graft polymers of the invention and/or obtained by or obtainable by a process of the invention and/or as detailed before in any of in this chapter before-mentioned applications, such as fabric care and home care products, in cosmetic and personal care formulations, as crude oil emulsion breaker, in technical applications including in pigment dispersions for ink jet inks, in formulations for electro plating, in cementitious compositions, in agrochemical formulations as e.g. dispersants, crystal growth inhibitor and/or solubilizer, in lacquer and colorants formulations, textile and leather treatment products for use during or after production, formulations containing inorganic salts such as especially silver salts, mining, metal production and treatment including metal refining and metal quenching, purification of liquids such as waste water from industry, production or consumers, preferably in agrochemical compositions and cleaning compositions and in fabric and home care products, in particular cleaning compositions for improved oily and fatty stain removal, removal of solid dirt such as clay, prevention of greying of fabric surfaces, and/or anti-scale agents and most preferably - for inhibiting the transfer of dyes, wherein the cleaning composition is preferably a laundry detergent formulation, more preferably a liquid laundry detergent formulation.
Another subject-matter of the present invention is, therefore, also a cleaning composition, fabric care and home care product, industrial and institutional cleaning product, agrochemical formulations, ora formulation or product for any of the previously mentioned applications and application fields, preferably in laundry detergents, in cleaning compositions and/or in fabric and home care products, each comprising at least one graft polymer as defined above or obtained by or obtainable by a process of the invention and/or as detailed herein.
Hence, a preferred subject matter of this invention is also the use of at least one inventive graft polymer and/or at least one graft polymer obtained or obtainable by the inventive process in fabric care and home care products, industrial and institutional cleaning product, agrochemical formulations, or a formulation or product for any of the previously mentioned applications and application fields, preferably in cleaning compositions and in laundry treatment, laundry care products and laundry washing products, more preferably a laundry detergent formulation, even more preferably a liquid laundry detergent formulation. In particular, the inventive graft polymer is employed in such composition/product/formulation for improved dye transfer inhibition.
Such inventive uses and inventive compositions/products encompass the use of the graft polymer as detailed herein and/or as obtainable from or obtained from the inventive process, such graft polymer resembling that as detailed above describing the polymer structure in any of its embodiments disclosed herein before, including any variations mentioned, and more specifically any of the preferred, more preferred etc. embodiments. Laundry detergents, cleaning compositions and/or fabric and home care products as such are known to a person skilled in the art. Any composition etc. known to a person skilled in the art, in connection with the respective use, can be employed within the context of the present invention.
In a preferred embodiment, it is a cleaning composition and/or fabric and home care product and/or industrial and institutional cleaning product, comprising at least one graft polymer as defined above. In particular, it is a cleaning composition for improved cleaning performance, and/or- (preferably “and”) - improved anti redeposition for example in respect of redeposition of soils and removing of stains, preferably a laundry detergent formulation and/or a manual dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.
The graft polymers support the removal of various hydrophobic and hydrophilic soils, such as body soils, food and grease soil, particulate soil such clay or carbon black, grass soil, make-up, motor oil etc. from textile or hard surfaces by the surfactants and thus improve the washing and cleaning performances of the formulations.
Moreover, the graft polymers also bring about better dispersion of the removed soil in the washing or cleaning liquor and prevent its redeposition onto the surfaces of the washed or cleaned materials. Herein, the removed soil include all typical soil that exist in the laundry process, for example, body soil, food and grease soil, particulate soil such clay or carbon black, grass soil, make-up, motor oil etc. Such anti-redeposion effect can be observed on various fabric types, including cotton, polycotton, polyester, copolymer of poly ether I poly urea (Spandex™), etc. In addition, such anti-redeposition effect is also effective on fabrics that have a fabric enhancer history, or when the fabric wash is carried out in the presence of fabric enhancer or other laundry additives such as freshness beads or bleach.
In one embodiment it is also preferred in the present invention that the cleaning composition comprises (besides at least one graft polymer as described above) additionally at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme being selected from lipases.
Another subject-matter of the present invention is, therefore, a cleaning composition such as a fabric and home care product and an industrial and institutional (l&l) cleaning product, comprising at least one graft polymer as defined above, and in particular a cleaning composition for improved primary cleaning, improved whiteness, or both, preferably both (such actions as detailed before). At least one graft polymer as described herein is present in said inventive cleaning compositions in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1 % to about 10%, and most preferably from about 0.5% to about 5%, in relation to the total weight of such composition or product in relation to the total weight of such composition or product; such cleaning composition may - and preferably does - further comprise a from about 1% to about 70% by weight of a surfactant system.
Preferably, such inventive cleaning composition is a fabric and home care product or an industrial and institutional (l&l) cleaning product, preferably a fabric and home care product, more preferably a laundry detergent or manual dish washing detergent, comprising at least one inventive graft polymer, and optionally further comprising at least one surfactant or a surfactant system, providing improved removal, dispersion and/or emulsification of soils and I or modification of treated surfaces and I or whiteness maintenance of treated surfaces.
Even more preferably, the cleaning compositions of the present invention comprising at least one inventive graft polymer, and optionally further comprising at least one surfactant or a surfactant system - as detailed before - are those for cleaning and anti redeposition performance within laundry and manual dish wash applications, even more specifically, for improved cleaning and anti redeposition performance (such actions as detailed before) such as those on fabrics and dishware, and may additionally comprise at least one enzyme selected from the list consisting of optionally further comprising at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably at least one enzyme being selected from lipases.
In one embodiment of the present invention, the inventive graft polymer may be used for improved cleaning and anti redeposition performance (such action as detailed before) for instance primary washing and/or soil removal of particulate stains and/or oily and fatty stains, and/or additionally for whiteness maintenance, preferably in laundry care. In another preferred embodiment the inventive graft polymer may be used for reducing the greying of fabric (anti-greying), preferably more than one of the before mentioned actions as present, i.e. more than one of improved cleaning, anti redeposition, primary washing, soil removal of particulate stains and/or oily and fatty stains, whiteness maintenance and/or anti-greying being exhibited by the graft polymers of the invention.
In another embodiment, the inventive graft polymer may be used for improved dye transfer inhibition, i.e. to prevent the transfer of dyes from one piece of fabric to another piece of fabric, either by direct contact or via the washing liquor. For such application it is preferred that the graft polymer contains at least one monomer (B2) as herein defined for such cases. More preferably, (B2) is at least one vinyllactam, even more preferably at least one vinylpyrrolidone and/or caprolactam, most preferably vinylpyrrolidone. Such graft polymers comprising such (B2) are being defined herein with suitable compositions and processes to obtain such graft polymers.
In one preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.
In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (e.g. powder or tab/unit dose) detergent composition for manual or automatic dish wash, preferably a liquid manual dish wash detergent composition. Such compositions are known to a person of skill in the art.
In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that may be used for cleaning various surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass.
In one embodiment, the inventive graft polymers may be utilized in cleaning compositions comprising a surfactant system comprising C10-C15 alkyl benzene sulfonates (LAS) as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.
In a further embodiment, the inventive graft polymers may be utilized in cleaning compositions, such as laundry detergents of any kind, and the like, comprising C8-C18 linear or branched alkyl ethersulfates with 1-5 ethoxy-units as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.
In a further embodiment the inventive graft polymers may be utilized in cleaning compositions, such as laundry detergents of any kind, and the like, comprising C12-C18 alkyl ethoxylate surfactants with 5-10 ethoxy-units as the primary surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non- ionic surfactants, or mixtures thereof.
In one embodiment of the present invention, the graft polymer is a component of a cleaning composition, such as preferably a laundry or a dish wash formulation, more preferably a liquid laundry or manual dish wash formulation, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant.
Within such inventive laundry detergent, cleaning composition or fabric and home care product as detailed in any of the embodiments of this invention and specifically any of the previous most preferred embodiments, at least one graft polymer - when solely employed as dye transfer inhibitor and thus - preferably - containing (B2)-monomers in amounts of more than 5 wt.% based on total monomers (B)- as detailed in any such of the embodiments disclosed herein including specifically any of the previous most preferred embodiments in this chapter disclosing such graft polymer - is present at a concentration of from about 0.05% to about 10%, preferably from about 0.1% to 8%, more preferably from about 0.2% to about 6%, and even more preferably from about 0.2% to about 4%, and most preferably in amounts of up to 2%, each in weight % in relation to the total weight of such composition or product, an all numbers in between, and including all ranges resulting from selecting any of the lower limits and combing with any of the upper limits, each in weight % in relation to the total weight of such composition or product, and optionally further at least one enzyme, preferably selected from one or more lipases, selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, cutinases, DNases, xylanases, mannanases, dispersins, ocidoreductases, lactases and peroxidases, and combinations of at least two of the foregoing types, is comprised, and further optionally an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition, more preferably comprising 0.1 to 2% of phenoxyethanol, is comprised, and optionally further 4, 4’-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition is comprised, and further a surfactant system is comprised from about 1 % to about 70% by weight of such detergent, composition or product.
Within such inventive laundry detergent, cleaning composition or fabric and home care product as detailed in any of the embodiments of this invention and specifically any of the previous most preferred embodiments, at least one graft polymer - when not employed as dye transfer inhibitor and thus - preferably - not containing (B2)-monomers or only amounts of (B2)-monomers below 10, preferably below 5 wt.% based on total monomers (B) - as detailed in any such of the embodiments disclosed herein including specifically any of the previous most preferred embodiments in this chapter disclosing such graft polymer - is present at a concentration of from about 0.05% to about 10%, preferably from about 0.1 % to 8%, more preferably from about 0.2% to about 6%, and even more preferably from about 0.2% to about 4%, and most preferably in amounts of up to 2%, each in weight % in relation to the total weight of such composition or product, an all numbers in between, and including all ranges resulting from selecting any of the lower limits and combing with any of the upper limits, each in weight % in relation to the total weight of such composition or product, and optionally further at least one enzyme, preferably selected from one or more lipases, selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, cutinases, DNases, xylanases, mannanases, dispersins, ocidoreductases, lactases and peroxidases, and combinations of at least two of the foregoing types, is comprised, and further optionally an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition, more preferably comprising 0.1 to 2% of phenoxyethanol, is comprised, and optionally further 4,4’-dichoro 2- hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition is comprised, and further a surfactant system is comprised from about 1 % to about 70% by weight of such detergent, composition or product. In a further embodiment, this invention also encompasses a composition comprising a graft polymer as described herein before, further comprises an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.
In a further embodiment, this invention also encompasses a method of preserving an aqueous composition against microbial contamination or growth, such composition comprising a graft polymer as described herein before, such composition being preferably a detergent composition, such method comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents as disclosed hereinafter, such antimicrobial agent preferably being 2-phenoxyethanol.
In a further embodiment, this invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising a graft polymer as described herein before, such composition further comprising 4,4’-dichoro 2- hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition.
In a further embodiment, this invention also encompasses a method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising a graft polymer as described herein before, such composition further comprising 4,4’-dichoro 2- hydroxydiphenylether.
The selection of the additional surfactants in these embodiments may be dependent upon the application and the desired benefit.
The graft polymers according to the present invention may be used, for example, within cleaning compositions and/or fabric and home care products. They lead to an at least comparable and preferably even improved performance within such compositions or products, where the inventive graft polymers can replace similar graft polymers which however are not biodegradable or such ones exhibiting a much lower biodegradation.
Definitions
As used herein, the articles “a” and “an” when used in a claim or an embodiment, are understood to mean one or more of what is claimed or described. As used herein, the terms “include(s)” and “including” are meant to be non-limiting, and thus encompass more than the specific item mentioned after those words. The term “about” as used herein encompasses the exact number “X” mentioned as e.g. “about X%” etc., and small variations of X, including from minus 5 to plus 5 % deviation from X (with X for this calculation set to 100%), preferably from minus 2 to plus 2 %, more preferably from minus 1 to plus 1 %, even more preferably from minus 0,5 to plus 0,5 % and smaller variations. Of course, if the value X given itself is already “100%” (such as for purity etc.) then the term “about” clearly can and thus does only mean deviations thereof which are smaller than “100”.
Similarly, the dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, also encompassed are - besides the strict numerical values - also a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.
The term "free of water" means that the composition contains no more than 5 wt.-% of water based on the total amount of solvent, in another embodiment no more than 1 wt.-% of water based on the total amount of solvent, in a further embodiment the solvent contains no water at all.
The compositions of the present disclosure can “comprise” (i.e. contain other ingredients), “consist essentially of’ (comprise mainly or almost only the mentioned ingredients and other ingredients in only very minor amounts, mainly only as impurities), or “consist of’ (i.e. contain only the mentioned ingredients and in addition may contain only impurities not avoidable in an technical environment, preferably only the ingredients) the components of the present disclosure.
Similarly, the terms “substantially free of....” or“ substantially free from...” or “(containing/comprising) essentially no....” may be used herein; this means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1 %, or even less than 0.1 %, or even more less than 0.01 %, or even 0%, by weight of the composition.
Generally, as used herein, the term “obtainable by” means that corresponding products do not necessarily have to be produced (i.e. obtained) by the corresponding method or process de-scribed in the respective specific context, but also products are comprised which exhibit all features of a product produced (obtained) by said corresponding method or process, wherein said products were actually not produced (obtained) by such method or process. However, the term “obtainable by” also comprises the more limiting term “obtained by”, i.e. products which were actually produced (obtained) by a method or process described in the respective specific context.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions. All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. Unless otherwise specified, all measurements herein are conducted at 20°C and under the atmospheric pressure. In all embodiments of the present disclosure, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise.
Throughout this description, the term “inventive compound” may be used instead of the “inventive (graft) polymer(s)” and “(graft) polymer(s) of this (present) invention”, meaning those compounds being disclosed herein as invention, defined by their structure and/or their process to produce or obtainable by the process defined herein.
The definitions and their preferences given within the “Definition”-section are included as part of this invention as described herein.
The specific embodiments as described throughout this disclosure are encompassed by the present invention as part of this invention; the various further options being disclosed in this present specification as “optional”, “preferred”, “more preferred”, “even more preferred” or “most preferred” (or “preferably” etc.) options of a specific embodiment may be individually and independently (unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded) selected and then combined within any of the other embodiments (where other such options and preferences can be also selected individually and independently unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded), with each and any and all such possible combinations being included as part of this invention as individual embodiments.
Description of cleaning compositions, formulations and their ingredients
The phrase "cleaning composition" as used herein includes compositions and formulations designed for cleaning soiled material. Such compositions and formulations include those designed for cleaning soiled material or surfaces of any kind.
Compositions for “industrial and institutional cleaning” includes such cleaning compositions being designed for use in industrial and institutional cleaning, such as those for use of cleaning soiled material or surfaces of any kind, such as hard surface cleaners for surfaces of any kind, including tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, lacquered surfaces.
The phrase “fabric care composition” is meant to include compositions and formulations designed for treating fabric. Such compositions include but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein and detailed herein below when describing the compositions. Such compositions may be used as a pre-laundering treatment, a post- laundering treatment, or may be added during the rinse or wash cycle of the laundering operation, and as further detailed herein below when describing the use and application of the inventive graft polymers and compositions comprising such graft polymers.
“Compositions for Fabric and Home Care” include cleaning compositions including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, light duty liquid detergents compositions, heavy duty liquid detergent compositions, detergent gels commonly used for laundry, bleaching compositions, laundry additives, fabric enhancer compositions, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein. Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse orwash cycle of the laundering operation, preferably during the wash cycle of the laundering or dish washing operation. More preferably, such Composition for Fabric and Home Care is a laundry cleaning composition, a laundry care product or laundry washing product, most preferably a liquid laundry detergent formulation or liquid laundry detergent product.
The cleaning compositions of the invention may be in any form, namely, in the form of a “liquid” composition including liquid-containing composition types such as paste, gel, emulsion, foam and mousse; a solid composition such as powder, granules, micro-capsules, beads, noodles, pearlised balls, agglomerates, tablets, granular compositions, sheets, pastilles, beads, fibrous articles, bars, flakes; or a mixture thereof; ;types delivered in single- , udal- or multi-compartment pouches or containers; single-phase or multi-phase unit dose; a spray orfoam detergent; premoistened wipes (i.e. , the cleaning composition in combination with a nonwoven material such as that discussed in US 6,121 ,165, Mackey, et al.); dry wipes (i.e., the cleaning composition in combination with a nonwoven materials, such as that discussed in US 5,980,931 , Fowler, et al.) activated with water by a user or consumer; and other homogeneous, non-homogeneous or single-phase or multiphase cleaning product forms.
The composition can be encapsulated in a single or multi-compartment pouch. A multicompartment pouch may have at least two, at least three, or at least four compartments. A multi-compartmented pouch may include compartments that are side-by-side and/or superposed. The composition contained in the pouch or compartments thereof may be liquid, solid (such as powders), or combinations thereof.
Non- limiting examples of “liquids”/”liquid compositions” include light duty and heavy duty liquid detergent compositions, fabric enhancers, detergent gels commonly used for laundry, bleach and laundry additives. Gases, e.g., suspended bubbles, or solids, e.g. particles, may be included within the liquids.
The liquid cleaning compositions of the present invention preferably have a viscosity of from 50 to 10000 mPa*s; liquid manual dish wash cleaning compositions (also liquid manual “dish wash compositions”) have a viscosity of preferably from 100 to 10000 mPa*s, more preferably from 200 to 5000 mPa*s and most preferably from 500 to 3000 mPa*s at 20 11s and 20 °C; liquid laundry cleaning compositions have a viscosity of preferably from 50 to 3000 mPa*s, more preferably from 100 to 1500 mPa*s and most preferably from 200 to 1000 mPa*s at 20 11s and 20 °C.
The liquid cleaning compositions of the present invention may have any suitable pH-value. Preferably the pH of the composition is adjusted to between 4 and 14. More preferably the composition has a pH of from 6 to 13, even more preferably from 6 to 10, most preferably from 7 to 9. The pH of the composition can be adjusted using pH modifying ingredients known in the art and is measured as a 10% product concentration in demineralized water at 25 °C. For example, NaOH may be used and the actual weight% of NaOH may be varied and trimmed up to the desired pH such as pH 8.0. In one embodiment of the present invention, a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.
Cleaning compositions such as fabric and home care products and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, are known to a person skilled in the art. Any composition etc. known to a person skilled in the art, in connection with the respective use, can be employed within the context of the present invention by including at least one inventive polymer, preferably at least one polymer in amounts suitable for expressing a certain property within such a composition, especially when such a composition is used in its area of use.
One aspect of the present invention is also the use of the inventive polymers as additives for detergent formulations, particularly for liquid detergent formulations, preferably concentrated liquid detergent formulations, or single mono doses for laundry.
All such cleaning compositions, their ingredients including (adjunct) cleaning additives, their general compositions and more specific compositions are known, as for example illustrated in the publications 800542 and 800500 as published by Protegas, Liechtenstein, and also from WO 2022/136409 and WO 2022/136408, wherein in any of the before prior art documents the graft polymer within the general compositions and also each individualized specific cleaning composition disclosed in the beforementioned publications may be replaced partially or completely by the graft polymer of this present invention having the same function. In those beforementioned documents, also various types of formulations for cleaning compositions are disclosed; all such composition types - the general compositions and also each individualized specific cleaning composition - can be equally applied also to those cleaning compositions contemplated herein. Hence, the present invention also encompasses any and all of such disclosed compositions of the before-mentioned prior art-disclosures but further comprising at least one of the inventive graft polymer in addition to or as a replacement for any already ins such prior artcomposition contained polymer or any such compound, which can be replaced by such inventive graft polymer - such replacements known to a person of skill in the art - , with the content of the inventive graft polymer being present in said formulations at a concentration of generally from 0,05 to 20 wt.%, preferably up to 15 wt. %, more preferably up to 10 wt.%, even more preferably up to 5 wt.%, and more preferably from 0,1 , and even further more preferably from 0,5 wt.%, such as preferably 0.1 to 5 weight%, and in case of a dye transfer inhibition activity as main activity preferably at a concentration of 0.5 to 2 weight%.
Cleaning additives
The cleaning compositions of the invention may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as “adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before.
Suitable adjunct cleaning additives include builders, cobuilders, a surfactant system, fatty acids and/or salts thereof, structurants, thickeners and rheology modifiers, clay/soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, amphiphilic copolymers (including those that are free of vinyl pyrrolidone), chelating agents, enzymes, enzyme stabilizing systems, encapsulated benefit agents such as encapsulated perfume, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, catalytic materials, brighteners, malodor control agents, pigments, dyes, opacifiers, pearlescent agents, hueing agents, dye transfer inhibiting agents, fabric softeners, carriers, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial and anti-microbial agents, preservatives, anti-oxidants, softeners, carriers, fillers, solvents, processing aids, pro-perfumes, and perfumes.
The adjunct(s) may be present in the composition at levels suitable for the intended use of the composition. Typical usage levels range from as low as 0.001 % by weight of composition for adjuncts such as optical brighteners to 50% by weight of composition for builders.
Liquid cleaning compositions additionally may comprise besides a surfactant system and graft polymer - and preferably do comprise at least one of - rheology control/modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.
Solid compositions additionally may comprise - and preferably do comprise at least one of - fillers, bleaches, bleach activators and catalytic materials.
Suitable examples of such cleaning adjuncts and levels of use are found in WO 99/05242, U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1. Those of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
Hence, the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above and below in more detail. The surfactant system may be composed from one surfactant or from a combination of surfactants selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
The cleaning compositions of the invention preferably comprise a surfactant system in an amount sufficient to provide desired cleaning properties. In some embodiments, the cleaning composition comprises, by weight of the composition, from about 1% to about 70% of a surfactant system. In other embodiments, the liquid cleaning composition comprises, by weight of the composition, from about 2% to about 60% of the surfactant system. In further embodiments, the cleaning composition comprises, by weight of the composition, from about 5% to about 30% of the surfactant system. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
Laundry compositions
In laundry formulations, anionic surfactants contribute usually by far the largest share of surfactants within such formulation. Hence, preferably, the inventive cleaning compositions for use in laundry comprise at least one anionic surfactant and optionally further surfactants selected from any of the surfactants classes described herein, preferably from non-ionic surfactants and/or amphoteric surfactants and/or zwitterionic surfactants and/or cationic surfactants.
Nonlimiting examples of anionic surfactants - which may be employed also in combinations of more than one surfactant - useful herein include C9-C20 linear alkylbenzenesulfonates (LAS), C10-C20 primary, branched chain and random alkyl sulfates (AS); C10-C18 secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) wherein x is from 1 to 30; C10-C18 alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES); and alpha-olefin sulfonate (AOS).
Preferred examples of suitable anionic surfactants are alkali metal and ammonium salts of C8-Ci2-alkyl sulfates, of Ci2-Cis-fatty alcohol ether sulfates, of Ci2-Cis-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-Ci2-alkylphenols (ethoxylation: 3 to 50 mol of ethylene oxide/mol), of Ci2-Ci8-alkylsulfonic acids, of C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, of Cw-Cis-alkylarylsulfonic acids, preferably of n-C -Cis-alkylbenzene sulfonic acids, of C10-C18 alkyl alkoxy carboxylates and of soaps such as for example Cs-C24-carboxylic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.
In one embodiment of the present invention, anionic surfactants are selected from n-C -Cis- alkylbenzene sulfonic acids and from fatty alcohol polyether sulfates, which, within the context of the present invention, are in particular sulfuric acid half-esters of ethoxylated C12- Cis-alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), preferably of n-Ci2-Cis- alkanols.
In one embodiment of the present invention, also alcohol polyether sulfates derived from branched (i.e. synthetic) Cn-Ci8-alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol) may be employed.
Preferably, the alkoxylation group of both types of alkoxylated alkyl sulfates, based on C12- Cis-fatty alcohols or based on branched (i.e. synthetic) Cn-Ci8-alcohols, is an ethoxylation group and an average ethoxylation degree of any of the alkoxylated alkyl sulfates is 1 to 5, preferably 1 to 3.
Preferably, the laundry detergent formulation of the present invention comprises from at least 1 wt% to 50 wt%, preferably in the range from greater than or equal to about 2 wt% to equal to or less than about 30 wt%, more preferably in the range from greater than or equal to 3 wt% to less than or equal to 25 wt%, and most preferably in the range from greater than or equal to 5 wt% to less than or equal to 25 wt% of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.
In a preferred embodiment of the present invention, anionic surfactants are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10-C18 alkylsulfates.
Non-limiting examples of non-ionic surfactants - which may be employed also in combinations of more than one other surfactant - include: C8-C18 alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF; C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as discussed in U.S. 4,565,647 Llenado, issued January 26, 1986; specifically alkylpolyglycosides as discussed in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides as discussed in US 5,332,528; and ether capped poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO 01/42408.
Preferred examples of non-ionic surfactants are in particular alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides). Examples of (additional) amphoteric surfactants are so-called amine oxides.
Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (A)
Figure imgf000056_0001
[ formula (A)] in which the variables are defined as follows:
R1 is selected from linear C1 -C10-alkyl, preferably ethyl and particularly preferably methyl,
R2 is selected from C8-C22-alkyl, for example n-C8H17, n-C10H21 , n-C12H25, n- C14H29, n-C16H33 or n-C18H37,
R3 is selected from C1-C10-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl or isodecyl, m and n are in the range from zero to 300, where the sum of n and m is at least one.
Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.
Here, compounds of the general formula (A) may be block copolymers or random copolymers, preference being given to block copolymers.
Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (B)
Figure imgf000056_0002
[formula (B)] in which the variables are defined as follows:
R1 is identical or different and selected from linear Ci-C4-alkyl, preferably identical in each case and ethyl and particularly preferably methyl,
R4 is selected from Ce-C2o-alkyl, in particular n-CsHn, n-C H2i, n-Ci2H25, n-Ci4H29, n-CieHss, n-CisH37, a is a number in the range from zero to 6, preferably 1 to 6, b is a number in the range from zero to 20, preferably 4 to 20, d is a number in the range from 4 to 25.
Preferably, at least one of a and b is greater than zero.
Here, compounds of the general formula (B) may be block copolymers or random copolymers, preference being given to block copolymers.
Further suitable non-ionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable non-ionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. An overview of suitable further non-ionic surfactants can be found in EP-A 0 851 023 and in DE- A 198 19 187.
Mixtures of two or more different non-ionic surfactants may of course also be present. In a preferred embodiment of the present invention, non-ionic surfactants are selected from C12/14 and C16/18 fatty alkoholalkoxylates, C13/15 oxoalkoholalkoxylates, C13- alkoholalkoxylates, and 2-propylheptylalkoholalkoxylates, each of them with 3 - 15 ethoxy units, preferably 5-10 ethoxy units, or with 1-3 propoxy- and 2-15 ethoxy units.
Non-limiting examples of amphoteric surfactants - which may be employed also in combinations of more than one other surfactant - include: water-soluble amine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. See WO 01/32816, US 4,681 ,704, and US 4,133,779. Suitable surfactants include thus so-called amine oxides, such as lauryl dimethyl amine oxide (“lauramine oxide”).
Preferred examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amido propyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides and especially coco dimethyl amino oxides. Amine oxides may have a linear or mid-branched alkyl moiety. Typical linear amine oxides include water-soluble amine oxides containing one R1 = C8-18 alkyl moiety and two R2 and R3 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide is characterized by the formula
R1-N(R2)(R3)-O wherein R1 is a C8-18 alkyl and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferred amine oxides include linear C , linear C10-C12, and linear C12-C14 alkyl dimethyl amine oxides. As used herein "mid-branched" means that the amine oxide has one alkyl moiety having n1 carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching for the amine oxide is also known in the art as an internal amine oxide. The total sum of n1 and n2 is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16. The number of carbon atoms for the one alkyl moiety (n1) should be approximately the same number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric. As used herein "symmetric" means that (n1-n2) is less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt%, more preferably at least 75 wt% to 100 wt% of the mid-branched amine oxides for use herein. The amine oxide further comprises two moieties, independently selected from a C1-C3 alkyl, a C1-C3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups. Preferably the two moieties are selected from a C1-C3 alkyl, more preferably both are selected as a C1 alkyl.
In a preferred embodiment of the present invention, amphoteric surfactants are selected from C8-C18 alkyl-dimethyl aminoxides and C8-C18 alkyl-di(hydroxyethyl)aminoxide. Cleaning compositions may also contain zwitterionic surfactants - which may be employed also in combinations of more than one other surfactant.
Suitable zwitterionic surfactants include betaines, such as alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as the phosphobetaines. Examples of suitable betaines and sulfobetaines are the following (designated in accordance with INCI): Almond amidopropyl of betaines, Apricotamidopropyl betaines, Avocadamidopropyl of betaines, Babassuamidopropyl of betaines, Behenamidopropyl betaines, Behenyl of betaines, Canol amidopropyl betaines, Capryl/Capramidopropyl betaines, Carnitine, Cetyl of betaines, Cocamidoethyl of betaines, Cocamidopropyl betaines, Cocamidopropyl Hydroxysultaine, Coco betaines, Coco Hydroxysultaine, Coco/Oleam idopropyl betaines, Coco Sultaine, Decyl of betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl of PG-betaines, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow of betaines, Isostearamidopropyl betaines, Lauramidopropyl betaines, Lauryl of betaines, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl betaines, Minkamidopropyl of betaines, Myristamidopropyl betaines, Myristyl of betaines, Oleamidopropyl betaines, Oleamidopropyl Hydroxysultaine, Oleyl of betaines, Olivamidopropyl of betaines, Palmamidopropyl betaines, Palmitamidopropyl betaines, Palmitoyl Carnitine, Palm Kernelamidopropyl betaines, Polytetrafluoroethylene Acetoxypropyl of betaines, Ricinoleam idopropyl betaines, Sesamidopropyl betaines, Soyamidopropyl betaines, Stearamidopropyl betaines, Stearyl of betaines, Tallowamidopropyl betaines, Tallowamidopropyl Hydroxysultaine, Tallow of betaines, Tallow Dihydroxyethyl of betaines, Undecylenamidopropyl betaines and Wheat Germamidopropyl betaines.
Preferred betaines are, for example, Ci2-Ci8-alkylbetaines and sulfobetaines. The zwitterionic surfactant preferably is a betaine surfactant, more preferable a Cocoamidopropylbetaine surfactant.
Non-limiting examples of cationic surfactants - which may be employed also in combinations of more than one other surfactant - include: the quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as discussed in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as discussed in US patents Nos. 4,228,042, 4,239,6604,260,529 and US 6,022,844; and amino surfactants as discussed in US 6,221 ,825 and WO 00/47708, specifically amido propyldimethyl amine (APA).
Compositions according to the invention may comprise at least one builder. In the context of the present invention, no distinction will be made between builders and such components elsewhere called “co-builders”. Examples of builders are complexing agents, hereinafter also referred to as complexing agents, ion exchange compounds, dispersing agents, scale inhibiting agents and precipitating agents. Builders are selected from citrate, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarboxylates. In the context of the present invention, the term citrate includes the mono- and the dialkali metal salts and in particular the mono- and preferably the trisodium salt of citric acid, ammonium or substituted ammonium salts of citric acid as well as citric acid. Citrate can be used as the anhydrous compound or as the hydrate, for example as sodium citrate dihydrate. Quantities of citrate are calculated referring to anhydrous trisodium citrate.
The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate. Preferably, however, the composition according to the invention is free from phosphates and polyphosphates, with hydrogenphosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate (“phosphate-free”). In connection with phosphates and polyphosphates, “free from” should be understood within the context of the present invention as meaning that the content of phosphate and polyphosphate is in total in the range from 10 ppm to 0.2% by weight of the respective composition, determined by gravimetry.
The term carbonates include alkali metal carbonates and alkali metal hydrogen carbonates, preferred are the sodium salts. Particularly preferred is Na2COa.
Examples of phosphonates are hydroxyalkanephosphonates and aminoalkane- phosphonates. Among the hydroxyalkanephosphonates, the 1-hydroxyethane-1 ,1- diphosphonate (HEDP) is of particular importance as builder. It is preferably used as sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Suitable aminoalkanephosphonates are preferably ethylene diaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and also their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salts of DTPMP.
Examples of amino carboxylates and polycarboxylates are nitrilotriacetates, ethylene diamine tetraacetate, diethylene triamine pentaacetate, triethylene tetraamine hexaacetate, propylene diamines tetraacetic acid, ethanol-diglycines, methylglycine diacetate, and glutamine diacetate. The term amino carboxylates and polycarboxylates also include their respective non-substituted or substituted ammonium salts and the alkali metal salts such as the sodium salts, in particular of the respective fully neutralized compound.
Silicates in the context of the present invention include in particular sodium disilicate and sodium metasilicate, alumosilicates such as for example zeolites and sheet silicates, in particular those of the formula a-Na2Si20s, P-Na2Si20s, and 5-Na2Si20s.
Compositions according to the invention may contain one or more builder selected from materials not being mentioned above. Examples of builders are a-hydroxypropionic acid and oxidized starch.
In one embodiment of the present invention, builder is selected from polycarboxylates. The term “polycarboxylates” includes non-polymeric polycarboxylates such as succinic acid, C2- Ci6-alkyl disuccinates, C2-Ci6-alkenyl disuccinates, ethylene diamine N,N’-disuccinic acid, tartaric acid diacetate, alkali metal malonates, tartaric acid monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid. Oligomeric or polymeric polycarboxylates are for example polyaspartic acid and its alkali metal salts, in particular its sodium salt, (meth)acrylic acid homopolymers and (meth)acrylic acid copolymers and their alkali metal salts, in particular their sodium salts. Suitable co-monomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has a weight-average molecular weight Mw in the range from 2000 to 40 000 g/mol, preferably 2000 to 10 000 g/mol, in particular 3000 to 8000 g/mol. Further suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid or or anhydrides thereof such as maleic anhydride. Suitable copolymers are in particular copolymers of acrylic acid and maleic acid of a weight average molecular weight Mw in the range of 2000 to 100000, preferably 3000 to 80000.
The preferred weight-average molecular weight Mw of the polyaspartic acid lies in the range between 1000 g/mol and 20 000 g/mol, preferably between 1500 and 15 000 g/mol and particularly preferably between 2000 and 10 000 g/mol.
It is also possible to use copolymers of at least one monomer from the group consisting of monoethylenically unsaturated Ca-C -mono- or C4-C -dicarboxylic acids or anhydrides thereof, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilically or hydrophobically modified co-monomer as listed below.
Suitable hydrophobic co-monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with ten or more carbon atoms or mixtures thereof, such as, for example, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene, C22-a-olefin, a mixture of C20- C24-a-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule. Suitable hydrophilic co-monomers are monomers with sulfonate or phosphonate groups, and also non-ionic monomers with hydroxyl function or alkylene oxide groups. Byway of example, mention may be made of: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. Polyalkylene glycols here can comprise 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
Particularly preferred sulfonic-acid-group-containing monomers here are 1-acrylamido-1- propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3- methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2- propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1 -sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of said acids, such as sodium, potassium or ammonium salts thereof.
Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.
Further suitable oligomeric or polymeric polycarboxylates comprise graft polymers of (meth)acrylic acid or maleic acid onto polysaccharides such as degraded starch, carboxymethylated polysaccharides such as carboxymethylated cellulose, carboxymethylated inulin or carboxymethylated starch or polyepoxysuccinic acid and their alkali metal salts,, in particular their sodium salts.
Moreover, amphoteric polymers can also be used as builders.
Compositions according to the invention can comprise, for example, in the range from in total 0.1 to 90 % by weight, preferably 5 to 80% by weight, preferably up to 70% by weight, of builder(s), especially in the case of solid formulations. Liquid formulations according to the invention preferably comprise in the range of from 0.1 to 20 % by weight of builder, such as up to 85, 75, 65, 60, 55, 50, 45, 40, 35, 30, 35, 15, or 10 % by weight.
Formulations according to the invention can comprise one or more alkali carriers. Alkali carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired. Of suitability are, for example, the alkali metal carbonates, the alkali metal hydrogen carbonates, and alkali metal metasilicates mentioned above, and, additionally, alkali metal hydroxides. A preferred alkali metal is in each case potassium, particular preference being given to sodium. In one embodiment of the present invention, a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.
In one embodiment of the present invention, the laundry formulation according to the invention comprises additionally at least one enzyme.
Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types.
Such enzyme(s) can be incorporated at levels sufficient to provide an effective amount for cleaning. The preferred amount is in the range from 0.001 % to 5 % of active enzyme by weight in the detergent composition according to the invention. Together with enzymes also enzyme stabilizing systems may be used such as for example calcium ions, boric acid, boronic acid, propylene glycol and short chain carboxylic acids. In the context of the present invention, short chain carboxylic acids are selected from monocarboxylic acids with 1 to 3 carbon atoms per molecule and from dicarboxylic acids with 2 to 6 carbon atoms per molecule. Preferred examples are formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, HOOC(CH2)3COOH, adipic acid and mixtures from at least two of the foregoing, as well as the respective sodium and potassium salts.
Preferably, the at least one enzyme is a detergent enzyme.
In one embodiment, the enzyme is classified as an oxidoreductase (EC 1), a transferase (EC
2), a hydrolase (EC 3), a lyase (EC 4), an isomerase (EC 5), or a ligase (EC 6). The EC- numbering is according to Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology including its supplements published 1993-1999. Preferably, the enzyme is a hydrolase (EC
3).
In a preferred embodiment, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, DNase, phosphodiesterases, phytases, carbohydrases, galactanases, xanthanases, xyloglucanases, oxidoreductase, perhydrolases, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, alpha-galactosidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase, and dispersins, and combinations of at least two of the foregoing types. More preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the foregoing types. Most preferably, the enzyme is a protease, preferably, a serine protease, more preferably, a subtilisin protease.
Preferably, the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101 E (according to BPN’ numbering). Preferably, the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881 A1.
The composition of the present invention can comprise one type of enzyme or more than one enzyme of different types, e.g., an amylase and a protease, or more than one enzyme of the same type, e.g., two or more different proteases, or mixtures thereof, e.g., an amylase and two different proteases.
The enzyme(s) can be incorporated into the composition at levels sufficient to provide an effective amount for achieving a beneficial effect, preferably for primary washing effects and/or secondary washing effects, like anti-greying or antipilling effects (e.g., in case of cellulases). Preferably, the enzyme is present in the composition at levels from about 0.00001% to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001% to about 1 %, or even more preferably from about 0.001% to about 0.5% enzyme protein by weight of the composition.
Preferably, the enzyme-containing composition further comprises an enzyme stabilizing system.
Preferably, the enzyme-containing composition described herein comprises from about 0.001 % to about 10%, from about 0.005% to about 8%, or from about 0.01 % to about 6%, by weight of the composition, of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme.
Preferably, the enzyme stabilizing system comprises at least one compound selected from the group consisting of polyols (preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2- propanediol, or sorbitol), inorganic salts (preferably, CaCI2, MgCI2, or NaCI), short chain (preferably, C1-C3) carboxylic acids or salts thereof (preferably, formic acid, formate (preferably, sodium formate), acetic acid, acetate, or lactate), borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. Preferably, the enzyme stabilizing system comprises a combination of at least two of the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids and preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. In particular, if proteases are present in the composition, protease inhibitors may be added, preferably selected from borate, boric acid, boronic acids (preferably, 4-FPBA), peptide aldehydes (preferably, peptide aldehydes like Z- VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde hydrosulfite adducts..
Compositions according to the invention may comprise one or more bleaching agent (bleaches).
Preferred bleaches are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term “persulfate” in each case includes the salt of the peracid H2SO5 and also the peroxodisulfate.
In this connection, the alkali metal salts can in each case also be alkali metal hydrogen carbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulfate. However, the dialkali metal salts are preferred in each case.
Formulations according to the invention can comprise one or more bleach catalysts. Bleach catalysts can be selected from oxaziridinium-based bleach catalysts, bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron- , cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.
Formulations according to the invention can comprise one or more bleach activators, for example tetraacetyl ethylene diamine, tetraacetylmethylene diamine, tetraacetylglycoluril, tetraacetylhexylene diamine, acylated phenolsulfonates such as for example n-nonanoyl- or isononanoyloxybenzene sulfonates, N-methylmorpholinium-acetonitrile salts (“MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N- nonanoylsuccinimide, 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
Formulations according to the invention can comprise one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds which inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
In one embodiment of the present invention, formulations according to the invention comprise in total in the range from 0.1 to 1 .5% by weight of corrosion inhibitor.
Formulations according to the invention may also comprise further cleaning polymers and/or soil release polymers and/or anti-graying polymers. The further cleaning polymers may include, without limitation, “multifunctional polyethylene imines” (for example BASF’s Sokalan® HP20) and/or “multifunctional diamines” (for example BASF’s Sokalan® HP96). Such multifunctional polyethylene imines are typically ethoxylated polyethylene imines with a weight-average molecular weight Mw in the range from 3000 to 250000, preferably 5000 to 200000, more preferably 8000 to 100000, more preferably 8000 to 50000, more preferably 10000 to 30000, and most preferably 10000 to 20000 g/mol. Suitable multifunctional polyethylene imines have 80 wt% to 99 wt%, preferably 85 wt% to 99 wt%, more preferably 90 wt% to 98 wt%, most preferably 93 wt% to 97 wt% or 94 wt% to 96 wt% ethylene oxide side chains, based on the total weight of the materials. Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell. Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight Mw in the range of 500 to 5000 g/mol. Preferably employed is a molecular weight from 500 to 1000 g/mol, even more preferred is a Mw of 600 to 800 g/mol. The ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.
Suitable multifunctional diamines are typically ethoxylated C2 to C12 alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated. Typical multifunctional diamines have a weight-average molecular weight Mw in the range from 2000 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g/mol. In a preferred embodiment of the invention, ethoxylated hexamethylene diamine, furthermore quaternized and sulfated, may be employed, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.
Suitable further multifunctional polyethylene imines, multifunctional di- and oligoamines include those as claimed in WO2021/254828, WO2022/136408A1 , WO2022/136409A1 , WO2021/165468, W02023/021103, W02023/021104, W02023/021105 and
WO2023/117494.
In a preferred embodiment of the present invention, the cleaning compositions may contain at least one multifunctional polyethylene imine and/or at least one multifunctional di- and/or oligoamine, specifically any of the claimed polymers from WO2021/254828, WO2022/136408A1 , WO2022/136409A1 , WO2021/165468, W02023/021103,
W02023/021104, W02023/021105 and/or WO2023/117494, to improve the cleaning performance, such as preferably improve the stain removal ability, especially the primary detergency of particulate stains on polyester fabrics of laundry detergents. The multifunctional polyethylene imines or multifunctional di- or oligomines or mixtures thereof according to the descriptions above may be added to the laundry detergents and cleaning compositions in amounts of generally from 0.05 to 15 wt%, preferably from 0.1 to 10 wt% and more preferably from 0.25 to 5 wt% and even as low as up to 2 wt.%, based on the particular overall composition, including other components and water and/or solvents.
Thus, one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one inventive polymer and (ii) at least one compound selected from multifunctional polyethylene imines and multifunctional di-and oligoamines and mixtures thereof. In one embodiment of the present invention, the ratio of the at least one inventive polymer and (ii) the at least one compound selected from multifunctional polyethylene imines and multifunctional di- and oligoamines and mixtures thereof, is from 10:1 to 1 :10, preferably from 5:1 to 1 :5 and more preferably from 3:1 to 1 :3.
Suitable anti-graying polymers comprise copolymers of acrylic or maleic acid and styrene, graft polymers of acrylic acid onto maltodextrin or carboxymethylated cellulose and their alkali metal salts,, in particular their sodium salts.
Laundry formulations comprising the inventive polymer may also comprise at least one complexing agent.
Preferred complexing agents are methylglycinediacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and salts thereof. Particularly preferred complexing agents are methylglycinediacetic acid and salts thereof. According to the invention, preference is given to 1 to 50% (wiirde ich reduzieren auf 20 Gew.%) by weight of complexing agents.
MGDA and GLDA can be present as racemate or as enantiomerically pure compound. GLDA is preferably selected from L-GLDA or enantiomerically enriched mixtures of L-GLDA in which at least 80 mol%, preferably at least 90 mol%, of L-GLDA is present.
In one embodiment of the present invention, complexing agent is racemic MGDA. In another embodiment of the present invention, complexing agent is selected from L-MGDA and from enantiomer mixtures of L- and D-MGDA in which L-MGDA predominates and in which the L/D molar ratio is in the range from 55:45 to 95:5, preferably 60:40 to 85:15. The L/D molar ratio can be determined for example by polarimetry or by chromatographic means, preferably by HPLC with a chiral column, for example with cyclodextrin as stationary phase or with an optically active ammonium salt immobilized on the column. For example, it is possible to use an immobilized D-penicillamine salt.
MGDA or GLDA is preferably used as the salt. Preferred salts are ammonium salts and alkali metal salts, particularly preferably the potassium and in particular the sodium salts. These can for example have the general formula (CA I) or (CA II):
[CH3-CH(COO)-N(CH2-COO)2]Na3-x-y KxHy (CA I) x in the range from 0.0 to 0.5, preferably up to 0.25, y in the range from 0.0 to 0.5, preferably up to 0.25,
[OOC-(CH2)2-CH(COO)-N(CH2-COO)2]Na4-x-yKxHy (CA II) x in the range from 0.0 to 0.5, preferably up to 0.25, y in the range from 0.0 to 0.5, preferably up to 0.25.
Very particular preference is given to the trisodium salt of MGDA and the tetrasodium salt of GLDA.
Laundry formulations comprising the inventive polymer may also comprise at least one antimicrobial agent. An antimicrobial agent is a chemical compound that kills microorganisms or inhibits their growth or reproduction. Microorganisms can be bacteria, yeasts or molds. A preservative is an antimicrobial agent which may be added to aqueous products and compositions to maintain the original performance, characteristics and integrity of the products and compositions by killing contaminating microorganisms or inhibiting their growth.
The composition/formulation may contain one or more antimicrobial agents and/or preservatives as listed in patent WO2021/115912 A1 (“Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes”) on pages 35 to 39. Especially of interest for the cleaning compositions and fabric and home care products and specifically in the laundry formulations are any of the following antimicrobial agents and/or preservatives:
4,4’-dichloro 2-hydroxydiphenyl ether (further names: 5-chloro-2-(4-chlorophenoxy) phenol, Diclosan, DCPP), Tinosan® HP 100 (30wt.% of DCPP in in 1 ,2-propylene glycol); 2- Phenoxyethanol (further names: Phenoxyethanol, Methylphenylglycol, Phenoxetol, ethylene glycol phenyl ether, Ethylene glycol monophenyl ether, 2-(phenoxy) ethanol, 2-phenoxy-1- ethanol); 2-bromo-2-nitropropane-1 ,3-diol (further names: 2-bromo-2-nitro-1 ,3-propanediol, Bronopol); Glutaraldehyde (further names: 1-5-pentandial, pentane-1 , 5-dial, glutaral, glutardialdehyde); Glyoxal (further names: ethandial, oxylaldehyde, 1 ,2-ethandial); 5-bromo- 5-nitro-1 ,3-dioxane (further names: 5-bromo-5-nitro-m-dioxane, Bronidox ®);Phenoxypropanol (further names: propylene glycol phenyl ether, phenoxyisopropanol 1- phenoxy-2-propanol, 2-phenoxy-1 -propanol); Glucoprotamine (chemical description: reaction product of glutamic acid and alkylpropylenediamine, further names: Glucoprotamine 50); Cyclohexyl hydroxyl diazenium-1 -oxide, potassium salt (further names: N-cyclohexyl- diazenium dioxide, Potassium HDO, Xyligene,);Formic acid (further names: methanoic acid, Protectol® FM, Protectol® FM 75, Protectol® FM 85, Protectol® FM 99, Lutensol® FM) and its salts, e.g. sodium formiate);Tetrahydro-3,5-dimethyl-1 ,3,5-thiadia-zine-2-thione (further names: 3,5-dimethyl-1 ,3-5-thiadiazinane-2-thione, Dazomet; 2,4-dichlorobenzyl alcohol (, further names: dichlorobenzyl alcohol, 2,4-dichloro-benzenemethanol, (2,4-dichloro-phenyl)- methanol, DCBA); 1 -propanol (further names: n-propanol, propan-1 -ol, n-propyl alcohol; 1 ,3,5-Tris-(2-hydroxyethyl)-hexahydro-1 ,3,5-triazin (further names: Hexyhydrotriazine, Tris(hydroethyl)-hexyhydrotriazin, hexyhydro-1 ,3-5-tris(2-hydroxyethyl)-s-triazine, 2, 2', 2"- (hexahydro-1 ,3,5-triazine-1 ,3,5- triyl)triethanol; 2-butyl-benzo[d]isothiazol-3-one (“BBIT”); 2- methyl-2H-isothiazol-3-one (“MIT””); 2-octyl-2H-isothiazol-3-one (“OIT”); 5-Chloro-2-methyl- 2H-isothiazol-3-one (“CIT” or “CMIT”); Mixture of 5-chloro-2-methyl-2H- isothiazol-3-one (“CMIT”) and 2-methyl-2H-isothiazol-3-one (“MIT”) (Mixture of CMIT/MIT); 1 ,2- benzisothiazol-3(2H)-one (“BIT”); Hexa-2,4-dienoic acid (trivial name “sorbic acid”) and its salts, e.g., calcium sorbate, sodium sorbate; potassium (E,E)-hexa-2,4-dienoate (Potassium Sorbate); Lactic acid and its salts; L-(+)-lactic acid; especially sodium lactate; Benzoic acid and salts of benzoic acid, e.g., sodium benzoate, ammonium benzo-ate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate; Salicylic acid and its salts, e.g., calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate; Benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate; Didecyldimethylammonium chloride (“DDAC”); N-(3-aminopropyl)-N- dodecylpropane-1 ,3-diamine ("Diamine"); Peracetic acid; Hydrogen peroxide. At least one antimicrobial agent or preservative may be added to the inventive composition in a concentration of 0.001 to 10% relative to the total weight of the composition.
Preferably, the composition contains 2-phenoxyethanol in a concentration of 0.1 to 2% or 4,4’-dichloro 2-hydroxydiphenyl ether (DCPP) in a concentration of 0.005 to 0.6%
The inventive laundry formulation may comprise at least one antimicrobial agent from the above list and/or a combination thereof, and/or a combination with at least one further antimicrobial agent not listed here.
Formulations according to the invention may also comprise water and/or additional organic solvents, e.g. ethanol or propylene glycol, and/or fillers such as sodium sulfate.
Further optional ingredients may be but are not limited to viscosity modifiers, cationic surfactants, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, and dye transfer inhibiting agents.
Dish wash compositions
Another aspect of the present invention is also a dish wash composition, comprising at least one inventive polymer as described above.
Thus, an aspect of the present invention is also the use of the inventive polymer as described above, in dish wash applications, such as manual or automated dish wash applications.
Dish wash compositions according to the invention can be in the form of a liquid, semi-liquid, cream, lotion, gel, or solid composition, solid embodiments encompassing, for example, powders and tablets. Liquid compositions are typically preferred for manual dish wash applications, whereas solid formulations and pouch formulations (where the pouches may contain also solids in addition to liquid ingredients) are typically preferred for automated dish washing compositions; however, in some areas of the world also liquid automated dish wash compositions are used and are thus of course also encompassed by the term “dish wash composition”.
The dish wash compositions are intended for direct or indirect application onto dishware and metal and glass surfaces, such as drinking and other glasses, beakers, dish and cooking ware like pots and pans, and cutlery such as forks, spoons, knives and the like.
The inventive method of cleaning dishware, metal and/or glass surfaces comprises the step of applying the dish wash cleaning composition, preferably in liquid form, onto the surface, either directly or by means of a cleaning implement, i.e., in neat form. The composition is applied directly onto the surface to be treated and/or onto a cleaning device or implement such as a dish cloth, a sponge or a dish brush and the like without undergoing major dilution (immediately) prior to the application. The cleaning device or implement is preferably wet before or after the composition is delivered to it. In the method of the invention, the composition can also be applied in diluted form. Both neat and dilute application give rise to superior cleaning performance, i.e. the formulations of the invention containing at least one inventive polymer exhibit excellent degreasing properties. The effort of removing fat and/or oily soils from the dishware, metal and/or glass surfaces is decreased due to the presence of the inventive polymer, even when the level of surfactant used is lower than in conventional compositions.
Preferably the composition is formulated to provide superior grease cleaning (degreasing) properties, long-lasting suds and/or improved viscosity control at decreased temperature exposures; preferably at least two, more preferably all three properties are present in the inventive dish wash composition. Optional - preferably present - further benefits of the inventive manual dish wash composition include soil removal, shine, and/or hand care; more preferably at least two and most preferably all three further benefits are present in the inventive dish wash composition.
In one embodiment of the present invention, the inventive polymer is one component of a manual dish wash formulation that additionally comprises at least one surfactant, preferably at least one anionic surfactant.
In another embodiment of the present invention, the inventive polymer is one component of a manual dish wash formulation that additionally comprises at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric surfactants and/or zwitterionic surfactants. In a preferred embodiment of the present invention, the manual dish wash formulations contain at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or mixtures thereof, to aid in the foaming, detergency, and/or mildness of the detergent composition.
Examples of suitable anionic surfactants are already mentioned above for laundry compositions.
Preferred anionic surfactants for dish wash compositions are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10-C18 alkylsulfates.
Preferably, the manual dish wash detergent formulation of the present invention comprises from at least 1 wt% to 50 wt%, preferably in the range from greater than or equal to about 3 wt% to equal to or less than about 35 wt%, more preferably in the range from greater than or equal to 5 wt% to less than or equal to 30 wt%, and most preferably in the range from greater than or equal to 5 wt% to less than or equal to 20 wt% of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.
Dish wash compositions according to the invention may comprise at least one amphoteric surfactant.
Examples of suitable amphoteric surfactants for dish wash compositions are already mentioned above for laundry compositions.
Preferred amphoteric surfactants for dish wash compositions are selected from C8-C18 alkyldimethyl aminoxides and C8-C18 alkyl-di(hydroxyethyl)aminoxide. The manual dish wash detergent composition of the invention preferably comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of an amphoteric surfactant, preferably an amine oxide surfactant. Preferably the composition of the invention comprises a mixture of the anionic surfactants and alkyl dimethyl amine oxides in a weight ratio of less than about 10:1 , more preferably less than about 8:1 , more preferably from about 5:1 to about 2:1 .
Addition of the amphoteric surfactant provides good foaming properties in the dish wash composition.
Dish wash compositions according to the invention may comprise at least one zwitterionic surfactant.
Examples of suitable zwitterionic surfactants for dish wash compositions are already mentioned above for laundry compositions.
Preferred zwitterionic surfactants for dish wash compositions are selected from betaine surfactants, more preferable from Cocoamidopropylbetaine surfactants.
In a preferred embodiment of the present invention, the zwitterionic surfactant is Cocamidopropylbetaine.
The manual dish wash detergent composition of the invention optionally comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of a zwitterionic surfactant, preferably a betaine surfactant.
Dish wash compositions according to the invention may comprise at least one cationic surfactant.
Examples of suitable cationic surfactants for dish wash compositions are already mentioned above for laundry compositions.
Cationic surfactants, when present in the composition, are present in an effective amount, more preferably from 0.1 wt% to 5 wt%, preferably 0.2 wt% to 2 wt% of the composition.
Dish wash compositions according to the invention may comprise at least one non-ionic surfactant.
Examples of suitable non-ionic surfactants for dish wash compositions are already mentioned above for laundry compositions.
Preferred non-ionic surfactants are the condensation products of Guerbet alcohols with from 2 to 18 moles, preferably 2 to 15, more preferably 5-12 of ethylene oxide per mole of alcohol. Other preferred non-ionic surfactants for use herein include fatty alcohol polyglycol ethers, alkylpolyglucosides and fatty acid glucamides.
The manual hand dish detergent composition of the present invention may comprise from 0.1 wt% to 10 wt%, preferably from 0.3 wt% to 5 wt%, more preferably from 0.4 wt% to 2 wt% of the composition, of a linear or branched C10 alkoxylated non-ionic surfactant having an average degree of alkoxylation of from 2 to 6, preferably from 3 to 5. Preferably, the linear or branched C10 alkoxylated non-ionic surfactant is a branched C10 ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 2 to 6, preferably of from 3 to 5. Preferably, the composition comprises from 60 wt% to 100 wt%, preferably from 80 wt% to 100 wt%, more preferably 100 wt% of the total linear or branched C10 alkoxylated non-ionic surfactant of the branched C10 ethoxylated non-ionic surfactant. The linear or branched C10 alkoxylated non-ionic surfactant preferably is a 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5. A suitable 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of 4 is Lutensol® XP40, commercially available from BASF SE, Ludwigshafen, Germany. The use of a 2- propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5 leads to improved foam levels and long-lasting suds.
Thus, one aspect of the present invention is a manual dish wash detergent composition, in particular a liquid manual dish wash detergent composition, comprising (i) at least one inventive polymer, and (ii) at least one further 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5.
Dish wash compositions according to the invention may comprise at least one hydrotrope in an effective amount, to ensure the compatibility of the liquid manual dish wash detergent compositions with water.
Suitable hydrotropes for use herein include anionic hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium, potassium, and ammonium cumene sulfonate, and mixtures thereof, and related compounds, as disclosed in U.S. Patent 3,915,903.
The liquid manual dish wash detergent compositions of the present invention typically comprise from 0.1 wt% to 15 wt% of the total liquid detergent composition of a hydrotrope, or mixtures thereof, preferably from 1 wt% to 10 wt%, most preferably from 2 wt% to 5 wt% of the total liquid manual dish wash composition.
Dish wash compositions according to the invention may comprise at least one organic solvent.
Examples of organic solvents are C4-C14 ethers and diethers, glycols, alkoxylated glycols, C6-C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
When present, the liquid dish wash compositions will contain from 0.01 wt% to 20 wt%, preferably from 0.5 wt% to 15 wt%, more preferably from 1 wt% to 10 wt%, most preferably from 1 wt% to 5 wt% of the liquid detergent composition of a solvent. These solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present. At higher solvent systems, the absolute values of the viscosity may drop but there is a local maximum point in the viscosity profile.
The dish wash compositions herein may further comprise from 30 wt% to 90 wt% of an aqueous liquid carrier, comprising water, in which the other essential and optional ingredients are dissolved, dispersed or suspended. More preferably the compositions of the present invention comprise from 45 wt% to 85 wt%, even more preferably from 60 wt% to 80 wt% of the aqueous liquid carrier. The aqueous liquid carrier, however, may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature (25 °C) and which may also serve some other function besides that of an inert filler. Dish wash compositions according to the invention may comprise at least one electrolyte. Suitable electrolytes are preferably selected from inorganic salts, even more preferably selected from monovalent salts, most preferably sodium chloride.
The liquid manual dish wash compositions according to the invention may comprise from 0.1 wt% to 5 wt%, preferably from 0.2 wt% to 2 wt% of the composition of an electrolyte.
Manual dish wash formulations comprising the inventive polymer may also comprise at least one antimicrobial agent.
Examples of suitable antimicrobial agents for dish wash compositions are already mentioned above for laundry compositions.
The antimicrobial agent may be added to the inventive hand dish wash compositon in a concentration of 0.0001 wt% to 10 wt% relative to the total weight of composition. Preferably, the formulation contains 2-phenoxyethanol in a concentration of 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt% and/or 4, 4’-dichloro 2-hydroxydiphenyl ether in a concentration of 0.001 wt% to 1 wt%, more preferably 0.002 wt% to 0.6 wt% (in all cases relative to the total weight of the composition).
Further additional ingredients are such as but not limited to conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, emollients, humectants, skin rejuvenating actives, carboxylic acids, scrubbing particles, bleach and bleach activators, perfumes, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, antibacterial agents, pH adjusters including NaOH and alkanolamines such as mono-ethanolamines and buffering means.
General cleaning compositions and formulations
As the polymers of the invention are biodegradable, and especially the cleaning formulations typically have a pH of about 7 or higher, and additionally often contain also enzymes - which are included into such cleaning formulations to degrade biodegradable stuff such as grease, proteins, polysaccharides etc which are present in the stains and dirt which shall be removed by the cleaning compositions - some consideration is needed to be taken to formulate those bio-degradable polymers of the invention. Such formulations suitable are in principle known, and include the formulation in solids - where he enzymes and the polymers can be separated by coatings or adding them in separate particles which are mixed - and liquids and semiliquids, where the polymers and the enzymes can be separated by formulating them in different compartments, such as different compartments of multi-chamber-pouches or bottles having different chambers, from which the liquids are poured out at the same time in a predefined amount to assure the application of the right amount per individual point of use of each component from each chamber. Such multi-compartment-pouches and bottles etc are known to a person of skill as well.
The liquid formulations disclosed in this chapter may comprise 0 to 2 % 2-phenoxyethanol, preferably about 1 %, in addition to all other mentioned ingredients. The above and below disclosed liquid formulations may comprise 0-0,2% 4,4’-dichoro 2- hydroxydiphenylethe, preferably about 0,15 %, in addition to all other mentioned ingredients. The bleach-free solid laundry compositions may comprise 0-0,2% 4,4’-dichoro 2- hydroxydiphenylethe, preferably about 0,15 %, in addition to all other mentioned ingredients.
The formulations disclosed in this chapter may - in addition to all other mentioned ingredients -comprise one or more enzymes selected from those disclosed herein above, more preferably a protease and/or an amylase, wherein even more preferably the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101 E (according to BPN’ numbering) and wherein the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881A1 , such enzyme(s) preferably being present in the formulations at levels from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, or even more preferably from about 0.001% to about 0.5% enzyme protein by weight of the composition.
The following compositions shown below including those in the tables disclose general cleaning compositions of certain types, which correspond to typical compositions correlating with typical washing conditions as typically employed in various regions and countries of the world. The at least one inventive polymer may be added to such formulation (s) in suitable amounts as outlined herein.
When the shown composition does not comprise an inventive graft polymer, such composition is a comparative composition. When it comprises an inventive graft polymer, especially in the amounts that are described herein as preferred, more preferred etc ranges, such compositions are considered to fall within the scope of the present invention.
In a preferred embodiment the graft polymer according to the present invention is used in a laundry detergent.
Liquid laundry detergents according to the present invention are composed of:
0,05 - 20 % of at least one inventive polymer
1 - 50% of surfactants
0,1 - 40 % of builders, cobuilders and/or chelating agents
0,1 - 50 % other adjuncts water to add up 100 %.
Preferred liquid laundry detergents according to the present invention are composed of:
0,5 - 15 % of at least one inventive polymer 5 - 40 % of anionic surfactants selected from C10-C15- LAS and C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units
1 ,5 - 10 % of nonioic surfactants selected from C10-C18-alkyl ethoxylates containing 3 - 10 ethoxy-units
2 - 20 % of soluble organic builders/ cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxy-di- and hydroxytricaboxylic acids, aminopolycarboxylates and polycarboxylic acids 0,05 - 5 % of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system
0,5 - 20 % of mono- or diols selected from ethanol, isopropanol, ethylenglycol, or propylenglyclol
0,1 - 20 % other adjuncts water to add up to 100%.
Solid laundry detergents (like e.g. powders, granules or tablets) according to the present invention are composed of:
0,2 - 20 % of at least one inventive polymer
1 - 50% of surfactants
0,1 - 90 % of builders, cobuilders and/or chelating agents
0-50% of fillers
0 - 40% of bleach actives
0,1 - 30 % of other adjuncts and/or water wherein the sum of the ingredients adds up 100 %.
Preferred solid laundry detergents according to the present invention are composed of: 0,5 - 10 % of at least one inventive polymer
5 - 30 % of anionic surfactants selected from C10-C15- LAS, C10-C18 alkylsulfates and C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units
1 ,5 - 7,5 % of non-ionic surfactants selected from C10-C18-alkyl ethoxylates containing 3 - 10 ethoxy-units
20 - 80 % of inorganic builders and fillers selected from sodium carbonate, sodium bicarbonate, zeolites, soluble silicates, sodium sulfate
0,5 - 15 % of cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, aminopolycarboxylates and polycarboxylic acids
0,1 - 5 % of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system
0,5 - 30 % of bleach actives
0,1 - 20 % other adjuncts water to ad up to 100%
In a preferred embodiment the polymer according to the present invention is used in a manual dish wash detergent.
Liquid manual dish wash detergents according to the present invention are composed of: 0,05 - 10 % of at least one inventive polymer 1 - 50% of surfactants 0,1 - 50 % of other adjuncts water to add up 100 %.
Preferred liquid manual dish wash detergents according to the present invention are composed of: 0,2 - 5 % of at least one inventive polymer 5 - 40 % of anionic surfactants selected from C10-C15- LAS, C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units, and C10-C18 alkylsulfate
2 10 % of Cocamidopropylbetaine 0 - 10 % of Lauramine oxide
0 - 2 % of a non-ionic surfactant, preferably a C10-Guerbet alcohol alkoxylate
0 - 5 % of an enzyme, preferably Amylase, and preferably also an enzyme stabilizing system
0,5 - 20 % of mono- or diols selected from ethanol, isopropanol, ethylenglycol, or propylenglyclol
0,1 - 20 % other adjuncts water to add up to 100% General formula for laundry detergent compositions according to the invention: (numbers: wt.%)
Figure imgf000074_0001
Liquid laundry frame formulations according to the invention:
Figure imgf000075_0001
Liquid laundry frame formulations according to the invention - continued:
Figure imgf000076_0001
Laundry powder frame formulations according to the invention:
Figure imgf000077_0001
Laundry powder frame formulations according to the invention - continued:
Figure imgf000078_0001
Further typical liquid detergent formulations LD1 , LD2 and LD3 are shown in the following three tables: (numbers: wt.% active) Liquid detergent 1- LD1 “excellent” detergent;
Figure imgf000079_0001
Liquid detergent 2- LD2 “medium” performance detergent
Figure imgf000079_0002
Liquid detergent 3- LD3 “medium” performance “biobased” detergent
Figure imgf000079_0003
All previous three tables on LD1 , LD2, LD3: *”graft polymer” = (poly ethylene glycol of Mn 6000 g/mol as graft base, grafted with 40 weigth % vinyl acetate (based on total polymer weight; produced following general disclosure of W02007138054A1).
Liquid manual dish wash frame formulations according to the invention:
Figure imgf000080_0001
It is preferred, that within the respective laundry detergent, cleaning composition and/or fabric and home care product, the at least one graft polymer is present at a concentration of from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1 % to about 10%, and most preferably from about 0.5% to about 5%, in relation to the total weight of such composition or product in relation to the total weight of such composition or product, each in weight % in relation to the total weight of such composition or product, and all numbers in between, and including all ranges resulting from selecting any of the lower limits mentioned and including further 0.2, 0.3, 0.4, 1 , 1 ,5, 2, 2.5, 3, 3.5 and 4, and combing with any of the upper limits mentioned and including 19, 18, 17, 16, 14, 13, 12, 11 , 9, 8, 7, and 6.
When the inventive graft polymer is used as solely as a dye transfer inhibiting agent within the cleaning formulations and more specifically in the laundry detergents, more preferably the liquid laundry detergents, then the amounts employed are different to the ones shown in the general formulas and the specific formulas shown in this chapter, and are as follows: At least one graft polymer as described herein and/or the at least one graft polymer obtained or obtainable by the inventive process as detailed before is present - when acting solely as dye transfer inhibiting agent - in said inventive compositions and products at a concentration of from about 0.05% to about 20%, preferably 0,05 to 10%, more preferably from about 0,1 % to 8%, even more preferably from about 0.2% to about 6%, and further more preferably from about 0,2% to about 4%, and most preferably in amounts of up to 2%, each in weight % in relation to the total weight of such composition or product, and further including all ranges resulting from selecting any of the lower limits and any of the upper limits and all numbers in between those mentioned.
The specific embodiments as described throughout this disclosure are encompassed by the present invention as part of this invention; the various further options being disclosed in this present specification as “optional”, “preferred”, “more preferred”, “even more preferred” or “most preferred” options of a specific embodiment may be individually and independently (unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded) selected and then combined within any of the other embodiments (where other such options and preferences can be also selected individually and independently), with each and any and all such possible combinations being included as part of this invention as individual embodiments.
The following examples shall further illustrate the present invention without restricting the scope of the invention.
Example Section
The number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity Mw/Mn of the inventive graft polymers can be determined by gel permeation chromatography in dimethylacetamide. The mobile phase (eluent) to be used is dimethylacetamide comprising 0.5 wt% LiBr. The concentration of graft polymer in tetrahydrofuran is 4.0 mg per mL. After filtration (pore size 0.2 pm), 100 pL of this solution are to be injected into the GPC system. Four columns (heated to 60°C) may be used for separation (PLgel precolumn, 3 PLgel MIXED-E column). The GPC system is operated at a flow rate of 1 mL per min. A DRI Agilent 1100 may be used as the detection system. Polyethylene glycol) (PEG) standards (PL) having a molecular weight Mn from 106 to 1 378 000 g/mol may be used for the calibration.
The molecular weights given in the tables are calculated weights unless “Mw” or “Mn” is stated, based on the total molar amounts of ingredients employed for the preparation reaction. As those reactions proceed basically to completeness, this is an acceptable way of calculation the molecular weights
The following backbone are prepared as backbone for inventive graft polymers; their abbreviations of the structures are:
Figure imgf000082_0001
General synthesis concept of backbones A, C, H, I, and J:
Caprolactone is oligomerized before alkylene oxide polymerization yielding mixed random/block structures, and backbones are obtained by alkoxylation of polycaprolactones. A starter molecule can be used (such as in case of backbone I and J: neopentylglycol, “NPG”).
Figure imgf000082_0002
General Synthesis concept of backbones B, D, E, F, G:
Caprolactone is added after alkylene oxide polymerization yielding block structures polycaprolactone- polyalkylene oxide -polycaprolactone
Figure imgf000083_0001
General Synthesis concept of backbone K:
Suitable starters are reacted with a premixed combination of alkylene oxides and caprolactone.
Figure imgf000083_0002
Synthesis of inventive graft polymer 1-21 :
Inventive graft polymers 1-21 are synthesized based on backbone A-J.
Figure imgf000084_0001
Note:
VAc = Vinyl acetate; VL = Vinyl laurate; VP = Vinyl pyrrolidone; ‘partially hydrolyzed: 40 mol% hydrolysis based on the total amount of VAc.
(Note: In case of deviations between the backbone description in the tables and the synthesis descriptions hereinafter, the following descriptions prevail.) Example 1 (Inv. 1)
Example 1 a: polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone
In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 240.0 g polyethylene glycol (molecular weight 400 g/mol) and 0.75 g tin(ll)ethylhexanoate were placed and heated to 100°C.
415.0 g epsilon-caprolactone was added within 15 minutes. The reaction mixture was heated to 160°C and stirred for 14 hours at 160°C under nitrogen. After cooling to room temperature, 645.0 g of an orange oil was obtained. 1H-NMR in MeOD indicated 99.5% conversion of caprolactone. Example 1 b (Backbone A): polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone and ethoxylated with 70 moles ethylene oxide
In a 2 I autoclave 271.2 g polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone (example 1 a) and 2.1 g potassium tert, butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. 770.9 g ethylene oxide was added within 14 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. After filtration 1041.0 g of a light brown solid was obtained. 1 H-NMR in CDCI3 confirmed the expected structure.
Example 1 c (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone A (455.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (2.81 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (245.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 9,20 g/h and 00:10 h to 06:10 h: 4.34 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 40.8 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (1.79 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 745 g of a polymer solution.
Example 2 (Inv. 2)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone A (450.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (10.08 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 36.89 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (450.50 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 15,7 g/h and 00:10 h to 06:10 h: 7.39 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 75.0 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (3.19 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 11.66 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 961 g of a polymer solution.
Example 3 (Inv. 3)
Example 3 a (Backbone C): polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone and ethoxylated with 102.2 moles ethylene oxide
In a 2 I autoclave 192.9 g polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone (example 1 a) and 2.0 g potassium tert, butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. 801.8 g ethylene oxide was added within 14 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. After filtration 990.0 g of a light brown solid was obtained. 1 H-NMR in CDCI3 confirmed the expected structure.
Example 3 b (graft polymer):
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone C (455.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (2.81 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (245.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 9,20 g/h and 00:10 h to 06:10 h: 4.34 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 40.8 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (1.79 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 745 g of a polymer solution.
Example 4 (Inv. 4)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone C (400.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (7.24 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 31.90 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (600.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 13,1 g/h and 00:10 h to 06:10 h: 5.13 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 83.4 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (4.80 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 21.12 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 1065 g of a polymer solution.
Example 5 (Inv. 5)
Example 5 a: polyethylene glycol (molecular weight 1500 g/mol), ethoxylated with 44 moles ethylene oxide
In a 2 I autoclave 599.9 g polyethylene glycol (molecular weight 1500 g/mol) and 2.7 g potassium tert, butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. 754.2 g ethylene oxide was added within 14 hours. To complete the reaction, the mixture was allowed to postreact for additional 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. After filtration 1350.0 g of a light brown solid was obtained. 1 H-NMR in CDCI3 confirmed the expected structure.
Example 5 b (Backbone D): polyethylene glycol (molecular weight 1500 g/mol), ethoxylated with 44 moles ethylene oxide and modified with 6 moles caprolactone
In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 1044.1 g polyethylene glycol (molecular weight 1500 g/mol), ethoxylated with 44 moles ethylene oxide (example 5a) and 1 .25 g tin(ll)ethylhexanoate were placed and heated to 90°C.
205.5 g epsilon-caprolactone was added within 15 minutes. The reaction mixture was heated to 160°C and stirred for 10 hours at 160°C under nitrogen. After cooling to room temperature, 1236.0 g of an orange oil was obtained. 1H-NMR in CDCI3 indicated 98.8% conversion of caprolactone.
Example 5 c (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone D (455.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (2.81 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (245.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 9,20 g/h and 00:10 h to 06:10 h: 4.34 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 40.8 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (1.79 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 745 g of a polymer solution.
Example 6 (Inv. 6)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone D (679.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (10.87 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 39.76 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (a mixture of 242.50 g of vinyl acetate and 48.50 g of vinyl laurate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 16,9 g/h and 00:10 h to 06:10 h: 7.97 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 48.5 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (3.43 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 12.56 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 1036 g of a polymer solution.
Example 7 (Inv. 7)
Example 7 a (Backbone E): polyethylene glycol (molecular weight 1500 g/mol), modified with 3 moles caprolactone
In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 480.0 g polyethylene glycol (molecular weight 1500 g/mol), and 0.6 g tin(ll)ethylhexanoate were placed and heated to 80°C.
109.6 g epsilon-caprolactone was added within 5 minutes. The reaction mixture was heated to 160°C and stirred for 10 hours at 160°C under nitrogen. After cooling to room temperature, 580.0 g of an orange oil was obtained. 1H-NMR in CDCI3 indicated 96.7% conversion of caprolactone Example 7 b (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone E (540.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (7.56 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 27.67 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (135.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 11 ,8 g/h and 00:10 h to 06:10 h: 5.55 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 22.5 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (2.39 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 8.74 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 721 g of a polymer solution.
Example 8 (Inv. 8)
Example 8 a: polyethylene glycol (molecular weight 600 g/mol), ethoxylated with 47.2 moles ethylene oxide
In a 2 I autoclave 222.5 g polyethylene glycol (molecular weight 600 g/mol) and 2.0 g potassium tert, butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 130°C. 770.0 g ethylene oxide was added within 10 hours. To complete the reaction, the mixture was allowed to postreact for additional 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. After filtration 990.0 g of a light brown solid was obtained (hydroxy value. 45.8 mgKOH/g).
Example 8 b (Backbone F): polyethylene glycol (molecular weight 600 g/mol), ethoxylated with 47.2 moles ethylene oxide and modified with 10 moles caprolactone
In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 617.9 g polyethylene glycol (molecular weight 600 g/mol), ethoxylated with 47.2 moles ethylene oxide (example 8a) and 0.9 g tin(ll)ethylhexanoate were placed and heated to 80°C. 288.8 g epsilon-caprolactone was added within 15 minutes. The reaction mixture was heated to 160°C and stirred for 12 hours at 160°C under nitrogen. After cooling to room temperature, 900.0 g of an orange oil was obtained. 1H-NMR in CDCI3 indicated 99.0% conversion of caprolactone.
Example 8 c (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone F (397.29 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (3.16 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 35.56 g of propane-1 ,2-diol) and 10 min upon the start of Feed 1 , Feed 2 (238.37 g of vinyl acetate) and Feed 3 (158.92 g of N- Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 12,9 g/h and 00:10 h to 06:10 h: 6.09 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 39.7 g/h) and Feed 3 (00:10 h to 06:10 h: 26.5 g/h). Upon completion of Feed 1 , Feed 2 and Feed 3, Feed 4 (2.03 g of tert-Butyl peroxy- 2-ethylhexanoate dissolved in 22.80 g of propane-1 , 2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 721 g of a polymer solution.
Example 9 (Inv. 9)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone F (50.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (1.12 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 4.10 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (50.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 1 ,74 g/h and 00:10 h to 06:10 h: 0.82 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 8.33 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (0.35 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 1 .30 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 107 g of a polymer solution
Example 10 (Inv. 10)
Example 10 a: polyethylene glycol (molecular weight 600 g/mol), ethoxylated with 47.2 moles ethylene oxide and modified with 3 moles caprolactone) (Backbone G)ln a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 669.8 g polyethylene glycol (molecular weight 600 g/mol), ethoxylated with 47.2 moles ethylene oxide (example 8a) and 0.8 g tin(ll)ethylhexanoate were placed and heated to 80°C.
85.6 g epsilon-caprolactone was added within 15 minutes. The reaction mixture was heated to 160°C and stirred for 12 hours at 160°C under nitrogen. After cooling to room temperature, 746.0 g of an orange solid was obtained. 1H-NMR in CDCI3 indicated 98.0% conversion of caprolactone.
Example 10 b (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone G (75.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (1.68 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 6.15 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (75.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 2.61 g/h and 00:10 h to 06:10 h: 1 .23 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 12.50 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (0.53 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 1 .94 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 160 g of a polymer solution
Example 11 (Inv. 11)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone G (97.50 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (0.60 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 6.92 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1 , Feed 2 (30.00 g of vinyl acetate) and Feed 3 (22.50 g of N- Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 2.51 g/h and 00:10 h to 06:10 h: 3.75 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 5.00 g/h) and Feed 3 (00:10 h to 06:10 h: 3.75 g/h). Upon completion of Feed 1 , Feed 2 and Feed 3, Feed 4 (0.38 g of tert-Butyl peroxy- 2-ethylhexanoate dissolved in 4.44 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 162 g of polymer a solution.
Example 12 (Inv. 12)
Example 12 a: Neopentylglycol, modified with 8 moles caprolactone
In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 104.1 g neopentyl glycol and 1.0 g tin(ll)ethylhexanoate were placed and heated to 140°C. 913.0 g epsilon-caprolactone was added within 15 minutes. The reaction mixture was heated to 160°C to 205°C and stirred for 4 hours at 160°C under nitrogen. After cooling to room temperature, 971 .0 g of an light yellow oil was obtained. 1H-NMR in CDCI3 indicated 99.0% conversion of caprolactone.
Example 12 b: Neopentylglycol, modified with 8 moles caprolactone and ethoxylated with 46 moles ethylene oxide) (Backbone H)
In a 2 I autoclave 356.1 g neopentylglycol, modified with 8 moles caprolactone (example 12 a) and 2.01 g potassium tert, butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. 709.2 g ethylene oxide was added within 14 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. 1.1 g acetic acid was added. After filtrationl 060.0 g of a light brown solid was obtained. 1 H-NMR in CDCI3 confirmed the expected structure.
Example 12 c (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone H (79.80 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (1.49 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 13.17 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (53.20 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.89 g/h and 00:10 h to 06:10 h: 0.23 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 8.87 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (0.34 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 2.99 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 150 g of a polymer solution Example 13 (Inv. 13)
Example 13 a: Neopentylglycol, modified with 8 moles caprolactone and alkoxylated with a mixture of 40 moles ethylene oxide and 4 moles propylene oxide (Backbone I)
In a 2 I autoclave 300.0 g neopentylglycol, modified with 8 moles caprolactone (example 12 a) and 1.8 g potassium tert, butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. A mixture of 519.6 g ethylene oxide and 68.5 g propylene oxide was added within 14 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. 0.9 g acetic acid was added. After filtration 880.0 g of a light brown oil was obtained. 1 H-NMR in CDCI3 confirmed the expected structure.
Example 13 b (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone I (78.00 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (1.35 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 11.88 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (42.00 g of vinyl acetate) were started and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.41 g/h and 00:10 h to 06:10 h: 0.23 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 7.09 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (0.31 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 2.70 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 136 g of a polymer solution
Example 14 (Inv. 14)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone I (97.50 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (1.22 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1 , Feed 2 (45.00 g of vinyl acetate) and Feed 3 (7.50 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.49 g/h and 00:10 h to 06:10 h: 1.25 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 7.50 g/h) and Feed 3 (00:10 h to 06:10 h: 1.25 g/h). Upon completion of Feed 1 , Feed 2 and Feed 3, Feed 4 (0.38 g of tert-Butyl peroxy-2- ethylhexanoate dissolved in 3.80 g of propane-1 , 2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 165 g of a polymer solution.
Example 15 (Inv. 15)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone 1(97.50 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (1.22 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1 , Feed 2 (37.50 g of vinyl acetate) and Feed 3 (15.00 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.49 g/h and 00:10 h to 06:10 h: 2.12 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 6.25 g/h) and Feed 3 (00:10 h to 06:10 h: 2.50 g/h). Upon completion of Feed 1 , Feed 2 and Feed 3, Feed 4 (0.38 g of tert-Butyl peroxy-2- ethylhexanoate dissolved in 3.80 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 167 g of a polymer solution.
Example 16 (Inv. 16)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone I (97.50 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (1.22 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1 , Feed 2 (30.00 g of vinyl acetate) and Feed 3 (22.50 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.49 g/h and 00:10 h to 06:10 h: 2.12 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 5.00 g/h) and Feed 3 (00:10 h to 06:10 h: 3.75 g/h). Upon completion of Feed 1 , Feed 2 and Feed 3, Feed 4 (0.38 g of tert-Butyl peroxy-2- ethylhexanoate dissolved in 3.80 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 165 g of a polymer solution.
Example 17 (Inv. 17)
Example 17 a: Neopentylglycol, modified with 2 moles caprolactone
In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 156.2 g neopentyl glycol and 0.5 g tin(ll)ethylhexanoate were placed and heated to 140°C. 342.4 g epsilon-caprolactone was added within 15 minutes. The reaction mixture was heated to 160°C and stirred for 2 hours at 160°C under nitrogen. After cooling to room temperature, 477.0 g of a light yellow oil was obtained. 1H-NMR in CDCI3 indicated 99.0% conversion of caprolactone.
Example 17 b: Neopentylglycol, modified with 2 moles caprolactone and ethoxylated with 40 moles ethylene oxide (Backbone J)
In a 2 I autoclave 149.6 g neopentylglycol, modified with 2 moles caprolactone (example 17 a) and 1.9 g potassium tert, butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. 792.0 g ethylene oxide was added within 14 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. 1 .0 g acetic acid was added. After filtration 940.0 g of a light brown oil was obtained. 1 H-NMR in CDCI3 confirmed the expected structure.
Example 17 c (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone J(97.50 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (1 .68 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 6.15 g of tripropylene glycol) and 10 min upon the start of Feed 1 , Feed 2 (37.50 g of vinyl acetate) and Feed 3 (15.00 g of Vinyl laurate) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 2.61 g/h and 00:10 h to 06:10 h: 1.23 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 6.25 g/h) and Feed 3 (00:10 h to 06:10 h: 2.50 g/h). Upon completion of Feed 1 , Feed 2 and Feed 3, Feed 4 (0.54 g of tert-Butyl peroxy-2- ethylhexanoate dissolved in 1.96 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 :00 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 159 g of a polymer solution.
Example 18 (Inv. 18) (Hydrolysation)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Example 8 b (110.00 g) under nitrogen atmosphere and heated to 80°C. Water (49.86 g) was added and Feed 1 (aqueous sodium hydroxide, 50%, 11.50 g) was started with a constant feed rate within 1 :00 h. After the addition was completed, the mixture was stirred at 80°C for 1 h to yield 250 g of a polymer solution.
Example 19 (Inv. 19)
Example 19 a: polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone and 70 moles ethylene oxide (Backbone B):
In a 2 I autoclave 150 g polyethylene glycol (molecular weight 400 g/mol), and 2.7 g potassium tert, butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. A mixture of 977.5 g ethylene oxide and 217.1 g caprolactone was added within 15 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. After filtration 1340.0 g of a light brown solid was obtained. 1 H-NMR in CDCI3 confirmed the expected structure.
Example 19 b (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone B (480.0 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (2.97 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 26.1 g of propane-1 , 2-diol) and 10 min upon the start of Feed 1 , Feed 2 (258.5 g of vinyl acetate) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 9.70 g/h and 00:10 h to 06:10 h: 4.58 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 43.08 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (1 .88 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 16.6 g of propane-1 , 2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 781 g of a polymer solution. Example 20 (Inv. 20)
Example 20 a: polyethylene glycol (molecular weight 400 g/mol), modified with 6 moles caprolactone and 70 moles ethylene oxide (Backbone K):
In a 2 I autoclave 150 g polyethylene glycol (molecular weight 400 g/mol), and 2.7 g potassium tert, butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. A mixture of 977.5 g ethylene oxide and 217.1 g caprolactone was added within 15 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. After filtration 1340.0 g of a light brown solid was obtained. 1 H-NMR in CDCI3 confirmed the expected structure.
Example 20 b (graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone K (350.0 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (4.02 g of tert- Butyl peroxy-2-ethylhexanoate dissolved in 33.0 g of propane-1 ,2-diol) and 10 min upon the start of Feed 1 , Feed 2 (650.0 g of vinyl acetate) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 12.4 g/h and 00:10 h h to 06:10 h: 5.83 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 108.3 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (2.55 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 21.0 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 1059 g of a polymer solution.
Example 21 (Inv. 21 - graft polymer)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone K (550.0 g) under nitrogen atmosphere and heated to 90°C. Feed 1 (3.40 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 30.0 g of propane-1 ,2-diol) and 10 min upon the start of Feed 1 , Feed 2 (296.2 g of vinyl acetate) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 11.1 g/h and 00:10 h h to 06:10 h: 5.25 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 49.4 g/h). Upon completion of Feed 1 and Feed 2, Feed 3 (2.55 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 21.0 g of propane-1 ,2-diol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was stirred for 1 h at 90°C upon complete addition of the feed. The polymerization mixture was heated to 95°C and a vacuum of 500 mbarwas applied to remove the volatiles. The yield was 899 g of a polymer solution.
Synthesis of comparative graft polymer 1 : (based on un-published patent application PCT/EP2022/065983, i.e. now published as WO 2022/263354)
Comparative graft polymer 1 based on PEG ester backbone was synthesized via the following steps 1.3: Step 1 : Oxidation of PAG
Polyalkylene oxides (PAG) with two primary OH end groups (called "diol") were oxidized to mixtures containing at least a polyalkylene oxide with two COOH end groups (called "diacid") and a polyalkylene oxide with one primary OH and one COOH end group (called "monoacid"), and, optionally, also remaining polyalkylene oxide with two primary OH end groups. The mixtures were prepared as follows.
Platinum on charcoal (5.0 wt.-% Pt on C, water content: 59.7 wt.-%, 283 g, 29.2 mmol Pt) was suspended in a mixture of polyalkylene oxide comprising two primary OH end groups and water (details see Table 1), heated to 52°C and stirred at 800 rpm. Oxygen was passed through the stirred mixture (20 nL/h) via a glass tube, equipped with a glass frit and the temperature was allowed to rise to 60°C. Oxygen dosage and temperature were maintained for the period mentioned in table 1 , the oxygen dosage was then stopped and the mixture was allowed to cool down to room temperature. Solids were separated from the liquid phase by filtration and the filter cake was washed with 500 mL of warm water. The washing water was mixed with the filtrate. Water was removed from the liquid mixture by distillation over a wiped film evaporator (overall height: 87.2 cm, diameter: 3.54 cm, wiped height: 43 cm, feed: 4.0 mL/min, 44°C, 1.8 kPa abs, 600 rpm).
Polymer backbone-Table 1 - Oxidation of PEG
Figure imgf000095_0001
#1 EO = polyethylene oxide
#2 Calculated on basis of acid number of the reaction solution
Step 2: Esterification
A mixture of oxidized polyalkylene oxides (see Table 2) obtained by the oxidation of the diol (see Table 1) and the esterification catalyst (see Table 2) were mixed and heated for a period of time mentioned in Table 2 under vacuum at a pressure of 1 kPa abs at a temperature of 135°C. Table 2 - Esterification to PEG-Ester
Figure imgf000096_0001
Annotation to Polymer backbone-Table 2:
#1 cat = Zn-octanoate
#2 K-value measures the relative viscosity of dilute polymer solutions and is a relative measure of the average molecular weight. As the average molecular weight of the polymer increases for a particular polymer, the K-value tends to also increase. The K-value is determined in a 3% by weight NaCI solution at 23°C and a polymer concentration of 1 % polymer according to the method of H. Fikentscher in “Cellulosechemie”, 1932, 13, 58.
Step 3: Synthesis of comparative graft polymer 1
The polymer backbone B1 (350.0 g) is dosed in a vessel equipped with a stainless-steel anchor stirrer (and 2 other necks) and heated to 95°C. 1.00 g of a 14wt% solution of t- butylperoxy-2-ethylhexanoate in tripropylene glycol was added within 1 min. Afterwards, the dosage of vinyl-acetate (350.0 g) was started and continued over 7.5 h with constant feed rate. At the same time the Initiator solution (50.0 g) t-butylperoxy-2-ethylhexanoate was dosed as a 14wt% solution in tripropylene glycol with a constant feed rate within 8.5 h. For completion of the reaction, the mixture is stirred for another 180 minutes. Finally, volatile components were stripped for 90 minutes at 120°C with nitrogen at a feed rate of 6 L N2/h.
Synthesis procedures for comparative polymers Comp Ex.2 - Comp Ex.5
The procedure follows published process descriptions to produce polymers already known and used in the state of the art-documents.
Comp. Ex. 2: Graft polymerization of vinyl acetate (40 wt.%) on PEG (Mn 6000 g/mol; 60 wt.%)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 660 g of PEG (Mn 6000 g/mol) under nitrogen atmosphere and melted at 90 °C. Feed 1 containing 4.42 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 35.09 g of 1 ,2-propanediol, was dosed to the stirred vessel in 6:10 h, at 90 °C. 5.56 wt.-% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1 , Feed 2 (440 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90 °C. Upon completion of the Feeds 1 and 2, the temperature was increased to 95 °C and Feed 3 consisting of 2.81 g of tertbutyl peroxy-2-ethy I hexanoate, dissolved in 23.21 g of 1 ,2-propanediol, were dosed within 56 min with constant flow rate at 95 °C. The mixture was stirred for one hour at 95 °C upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95 °C and 500 mbar.
Comp. Ex. 3: Graft polymerization of vinyl acetate (30 wt.%) on PEG (Mn 6000 g/mol; 70 wt.%)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 700 g of PEG (Mn 6000 g/mol) under nitrogen atmosphere and melted at 90 °C. Feed 1 containing 12.24 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 50.30 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90 °C. 5.56 wt.-% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1 , Feed 2 (300 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90 °C. Upon completion of the Feeds 1 and 2, the temperature was increased to 95 °C and Feed 3 consisting of 4.80 g of tertbutyl peroxy-2-ethylhexanoate, dissolved in 19.70 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 95 °C. The mixture was stirred for one hour at 95 °C upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95 °C and 500 mbar.
Comp. Ex. 4: Graft polymerization of vinyl acetate (40 wt.%) on PEG (Mn 4000 g/mol; 60 wt.%)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 600 g of PEG (Mn 4000 g/mol) under nitrogen atmosphere and melted at 90 °C. Feed 1 containing 3.57 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 29.90 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90 °C. 5.56 wt.-% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1 , Feed 2 (400 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90 °C. Upon completion of the Feeds 1 and 2, the temperature was increased to 95 °C and Feed 3 consisting of 4.90 g of tertbutyl peroxy-2-ethylhexanoate, dissolved in 41.00 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 95 °C. The mixture was stirred for one hour at 95 °C upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95 °C and 500 mbar.
Comp. Ex. 5: Graft polymerization of vinyl acetate (60 wt.%) on PEG (Mn 6000 g/mol; 40 wt.%)
A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 400 g of PEG (Mn 6000 g/mol) under nitrogen atmosphere and melted at 90 °C. Feed 1 containing 4.8 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 23.6 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90 °C. 5.56 wt.-% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1 , Feed 2 (600 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90 °C. Upon completion of the Feeds 1 and 2, the temperature was increased to 95 °C and Feed 3 consisting of 3.16 g of tertbutyl peroxy-2-ethylhexanoate, dissolved in 15.70 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 95 °C. The mixture was stirred for one hour at 95 °C upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95 °C and 500 mbar.
Figure imgf000098_0001
Annotations: VAc: vinyl acetate
Polymer biodegradability
Polymer Biodegradation in wastewater was tested in triplicate using the OECD 301 F manometric respirometry method. 30 mg/mL test substance is inoculated into wastewater taken from Mannheim Wastewater Treatment Plant and incubated in a closed flask at 25°C for 28 days. The consumption of oxygen during this time is measured as the change in pressure inside the flask using an OxiTop C (WTW). Evolved CO2 is absorbed using an NaOH solution. The amount of oxygen consumed by the microbial population during biodegradation of the test substance, after correction using a blank, is expressed as a % of the ThOD (Theoretical Oxygen Demand).
The biodegradation data of comparative and inventive polymers at 28 day of the OECD 301 F test is summarized in the table before the synthesis descriptions.
As shown in the table, the inventive graft polymers typically show a higher percentage of biodegradation at 28 day of the OECD 301 F test.
Stability of inventive graft polymer 5 (Inv. 5) vs comparative graft polymer 1
Aqueous solutions of the inventive graft polymer 5 (Inv. 5) and comparative polymer 1 (9 wt%) were prepared and the mixtures were stored at 54 °C for two weeks.
A brown precipitate was formed during storage of the comparative graft polymer 1 . Recorded 1H NMR (298 K, D2O, 400 MHz) spectra of the precipitate and the solution showed no differences. The comparison of the 1H NMR spectra of the fresh and the stored sample of comparative graft polymer showed significant rearrangements of the 1H NMR shifts in the regions of 4.0 to 4.35 ppm (typical for PEG-Ester bonds) and 1 .8 to 2.2 ppm (typical for bound I non bound acetate) as shown in Figure 1 .
The comparison of 1H NMR spectra (298 K, D2O, 400 MHz) of the fresh and the stored samples of inventive graft polymer (Inv. 5) showed no significant rearrangements in the spectra as shown in Figure 2.
The results clearly demonstrate better hydrolysis instability from inventive polymers.
Method for evaluating suds mileage of hand dish composition
The objective of the Suds Mileage Index test is to compare the evolution over time of suds volume generated for different test formulations at specified water hardness, solution temperatures and formulation concentrations, while under the influence of periodic soil injections. Data are compared and expressed versus a reference composition as a suds mileage index (reference composition has suds mileage index of 100). The steps of the method are as follows:
1) A defined amount of a test composition, depending on the targeted composition concentration (0.12 wt%), is dispensed through a plastic pipette at a flow rate of 0.67 mL/ sec at a height of 37 cm above the bottom surface of a sink (dimension: 300 mm diameter and 288 mm height) into a water stream (water hardness: 15 gpg, water temperature:35°C) that is filling up the sink to 4 L with a constant pressure of 4 bar.
2) An initial suds volume generated (measured as average foam height X sink surface area and expressed in cm3) is recorded immediately after end of filling.
3) A fixed amount (6 mL) of soil is immediately injected into the middle of the sink.
4) The resultant solution is mixed with a metal blade (10 cm x 5 cm) positioned in the middle of the sink at the air liquid interface under an angle of 45 degrees rotating at 85 RPM for 20 revolutions.
5) Another measurement of the total suds volume is recorded immediately after end of blade rotation.
6) Steps 3-5 are repeated until the measured total suds volume reaches a minimum level of 400 cm3. The amount of added soil that is needed to get to the 400 cm3 level is considered as the suds mileage for the test composition.
7) Each test composition is tested 4 times per testing condition (i.e., water temperature, composition concentration, water hardness, soil type).
8) The average suds mileage is calculated as the average of the 4 replicates foreach sample.
9) Calculate a Suds Mileage Index by comparing the average mileage of a test composition sample versus a reference composition sample. The calculation is as follows:
Average number of soil additions of test composition
Suds Mileage Index = - - - - — - — — - - — - x 100
Average number of soil additions of reference composition
Soil composition is produced through standard mixing of the components described in Table 3.
Table 3: Greasy Soil
Figure imgf000099_0001
Method for evaluating whiteness benefit of polymers in laundry detergent
Whiteness maintenance, also referred to as whiteness preservation, is the ability of a detergent to keep white items from whiteness loss when they are washed in the presence of soil. White garments can become dirty/dingy looking overtime when soils are removed from dirty clothes and suspended in the wash water, then these soils can re-deposit onto clothing, making the clothing less white each time they are washed.
The whiteness benefit of polymers of the present disclosure is evaluated using automatic Tergotometer with 10 pots for laundry formulation testing.
SBL2004 test soil strips supplied by WFK T estgewebe GmbH are used to simulate consumer soil levels (mix of body soil, food, dirt etc.). On average, every 1 SBL2004 strip is loaded with 8g soil. The SBL2004 test soil strips were cut into 5x5 cm squares for use in the test.
White Fabric swatches of Table 4 below purchased from WFK Testgewebe GmbH are used as whiteness tracers. Before the wash test, L, a, b values of all whiteness tracers are measured using Konica Minolta CM-3610D spectrophotometer.
Table 4
Figure imgf000100_0001
Additional ballast (background fabric swatches) are also used to simulate a fabric load and provide mechanical energy during the real laundry process. Ballast loads are comprised of cotton and polycotton knit swatches at 5x5 cm size.
4 cycles of wash are needed to complete the test:
Cycle 1 : Desired amount of detergent is fully dissolved by mixing with 1 L water (at defined hardness) in each tergotometer port. 60 grams of fabrics, including whiteness tracers (4 types, each with 4 replicates), 21 pieces 5x5 cm SBL2004, and ballast are washed and rinsed in the tergotometer pot under defined conditions.
In the test of water-soluble unit dose composition, wash concentration is 2000ppm. Additional 47 ppm PVOH film is also added to the tergotometer pot. The wash temperature is 30°C, water hardness is 20gpg.
Cycle 2: The whiteness tracers and ballast from each pot are then washed and rinsed again together with a new set of SBL2004 (5x5cm, 21 pieces) follow the process of cycle 1. All other conditions remain the same as cycle 1 .
Cycle 3: The whiteness tracers and ballast from each pot are then washed and rinsed again together with a new set of SBL2004 (5x5cm, 21 pieces) follow the process of cycle 1. All other conditions remain the same as cycle 1 . Cycle 4: The whiteness tracers and ballast from each port are then washed and rinsed again together with a new set of SBL2004 (5x5cm, 21 pieces) follow the process of cycle 1. All other conditions remain the same as cycle 1 .
After Cycle 4, all whiteness tracers & ballast are tumbled dried between 60-65°C until dry, the tracers are then measured again using Konica Minolta CM-3610D spectrophotometer. The changes in Whiteness Index (AWI(CIE)) are calculated based on L, a, b measure before and after wash.
AWI(CIE)= WI(CIE)(afterwash) - WI(CIE)(before wash).
Method for evaluating stain removal benefit of polymers in laundry detergent
Cleaning benefit of polymers are evaluated using tergotometer. Some examples test stains suitable for this test are:
Standard Grass ex CFT
Standard Clay ex CFT
ASTM Dust Sebum ex CFT
Highly Discriminating Sebum on polycotton ex CFT
Burnt Bacon on Knitted cotton (prepared using burnt bacon ex Equest)
Dyed Bacon on Knitted Cotton (prepared using dyed bacon ex Equest)
The stains are analysed using Image Analysis System for Laundry stain removal testing before and after the wash.
SBL2004 test soil strips supplied by WFK T estgewebe GmbH are used to simulate consumer soil levels (mix of body soil, food, dirt etc.). On average, every 1 SBL2004 strip is loaded with 8g soil. The SBL2004 test soil strips were cut into 5x5 cm squares for use in the test.
Additional ballast (background fabric swatches) are also used to simulate a fabric load and provide mechanical energy during the real laundry process. Ballast loads are comprised of knitted cotton swatches at 5x5 cm size. 4 cycles of the wash are performed:
Desired amount of detergent is fully dissolved by mixing with 1 L water (at defined hardness) in each tergotometer port. 60 grams of fabrics, stains (2 internal replicates of each stain in each pot), 13 pieces 5x5 cm SBL2004, and ballast are washed and rinsed in the tergotometer pot under defined conditions. In the test of water-soluble unit dose composition, wash concentration is 2000ppm. Additional 47 ppm PVOH film is also added to the tergotometer pot. The wash temperature is 30°C, water hardness is 7gpg. The test has four external replicates.
All stains are tumbled dried between 60-65°C until dry, then stains are measured again using Image Analysis System for Laundry stain removal testing.
Stain Removal Index (SRI) are automatically calculated from the L, a, b values using the formula shown below. The higher the SRI, the better the stain removal.
SRI = 100*((AEb - AEa)/ AEb)
AEb = ((LC-Lb)2 + (ac-ab)2 + (bc-bb)2)
AEa = ((LC-La)2 + (ac-aa)2 + (bc-ba)2)
Subscript ‘b’ denotes data for the stain before washing Subscript ‘a’ denotes data for the stain after washing
Subscript ‘c’ denotes data for the unstained fabric
Polymer Performance in hand dish detergent Hand dish detergent compositions below are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. The impact of inventive polymers on suds mileage are evaluated by comparing the suds mileage of formulation A (Reference) and B (Reference with inventive polymers) in Table 5. The suds mileage performance is evaluated using the method for evaluating suds mileage of hand dish compositions described herein, and Suds Mileage Index is reported in Table 6.
Table 5
Figure imgf000102_0001
‘amphiphilic alkoxylated polyethyleneimine (total MW: about 28000 g/mol) with a polyethyleneimine backbone of MW 600 and alkoxylation chains each chain comprising 24 internal EO units and 16 terminal PO units.
As indicated in Table 6, inventive polymers can deliver strong suds mileage benefit. Table 6
Figure imgf000103_0001
Method for Dye Re-deposition in a Laundry Detergent
Preparation of a concentrated dye solution extracted from a test fabric.
A concentrated dye solution is extracted from dyed test fabrics and used to determine the ability of a polymer to prevent dye re-deposition onto white test fabrics. Dyed knit test fabrics are prepared at 3% dye loading as a percentage of the weight of the fiber using a 20: 1 liquor ratio (70 g/L sodium sulfate salt and 15 g/L soda ash) with identical auxiliary chemicals, time, temperature, and post-dye scour. Knit fabrics are cut into 3” x 3” swatches (7.6 cm x 7.6 cm), and 4 fabric squares are layered on top of each other and fold in half and transferred into a 40 mL glass scintillation vial (Qorpak VWR supplier part #18087-086) using forceps. Deionized water (38 mL) is added to the vial, and vials are placed in heating blocks (Multi Temperature Zone Reaction Blocks, KEM Scientific, SN: 26197) on top of an orbital Shaker (VWR Standard Analog Shaker, Model: 3500, SN: 191011001 , NA CAT No: 89032-092) and heated at set temperature of 50 °C, and speed setting of 2 for a minimum 24h to extract available dye. Vials are removed from heat and extracted dye solution and fabrics are transferred into a syringe with the depressor removed fitted with a glass fiber filter (Nalgene glass fiber syringe filters, 25 mm diameter, 1.1 micron, Thermo Scientific, Cat#722-2000, Lot 1705032503). The depressor is re-inserted and depress contents into new scintillation vial. UV-VIS Spectrum is measured and absorbance at Imax is recorded. Concentrated extracts are diluted to 0.25 absorbance units (AU) at Imax. To 20 ml Scintillation vials with urea cap PE cone (Duran Wheaton Kimble 986546, 66021-533), is added 2.8 mL of filtered dye solution, 0.1 mL of 500 gpg hardness solution made from a 3:1 Ca/Mg ratio of CaCh/2 H2O, and MgCl2/6H2O, 0.1 mL of Detergent G diluted to 8.27%. For the no polymer reference, DI water is added to reach a volume of 3.5 mL (0.495 mL). For all other samples, 0.175 mL of a 0.1 % by weight polymer solution is added followed by 0.32 mL to reach a total volume of 3.5 mL. The vial is swirled by hand.
White Acceptor Fabrics (2 x 2.75 cm, 100% cotton knit, WFK CK-19502) that have been measured for L*ab using a spectrophotometer such as a Konica Minolta are added to each solution making sure fabrics are submersed in solution. Vials are shaken on a mechanical shakerat room temperature for 30 min wash time. Vials are removed from the shaker, fabrics are removed using forceps, and liquid is removed using a countertop spin dryer after spinning for 1 .5 min. Fabrics are rinsed by placing fabrics into new 20 mL vials containing 3.5 mL, 15 gpg water and shaken on mechanical wrist shaker for 15 min at room temperature. Fabrics are removed from each vial using forceps, and liquid removed using a countertop spin dryer after 1 .5 min of spinning. After spinning, fabrics are dried on racks in the food dehydrator at 52 °C for 1 hour. Washed and dried fabrics are measured for L*ab and the color change difference between unwashed and washed is recorded as dE2000 (G. Sharma, W. Wu, E.N. Dalal, "THE CIEDE2000 COLOUR-DIFFERENCE FORMULA: Implementation Notes, Supplementary Test Data, and Mathematical Observations," submitted to COLOR
RESEARCH AND APPLICATION, Jan 2004).
Polymer Whiteness Performance in Liquid Detergent
Water soluble unit dose detergent composition E and F, and heavy-duty liquid detergent composition G, H below are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients (Table 7 / Table 8).
Table 7
Figure imgf000104_0001
The whiteness maintenance of the inventive and comparative polymers is evaluated according to the method for evaluating whiteness performance of polymers by directly comparing the whiteness performance of reference composition E and test composition F. AWI(CIE) of composition F vs composition E is reported in Table 9 as an indication of polymer whiteness performance benefit. As shown in Table 9, the inventive polymer delivers significant whiteness benefit.
Table 8
Figure imgf000105_0001
Chelant = DETA + GLDA
Table 9
Figure imgf000105_0002
* is a different test, so data maybe not comparable. Typically, +1-5 is noticeable difference to human eye.
The stain removal performance of the inventive and comparative polymers is evaluated according to the method for evaluating whiteness performance of polymers by directly comparing the whiteness performance of reference composition E and test composition F. ASRI of composition F vs composition E is reported in Table 10 as an indication of polymer whiteness performance benefit. As shown in Table 10, the inventive polymer delivers significant stain removal benefit on sebum stains and black todd clay. The inventive graft polymers contain VP (especially when VP is more than 5%) show particular strong black todd clay stain removal benefit.
The dye re-deposition performance of the inventive polymers is evaluated according to the dye re-deposition method by comparing performance of reference composition G having no polymer to test compositions H. The color change before and after washing is reported as dE2000 in Table 11 / Table 12 as an indication of polymer dye re-deposition benefit.
Table 10
Figure imgf000106_0001
As shown in Table 11 , the inventive polymer delivers significant dye transfer benefit as shown by the decrease in dye re-deposition with a lower dE2000 on Reactive Red 120 and Reactive Red 239 compared to the same detergent without any polymer. Without wishing to be bound by theory, for grafting type I, as the vinyl pyrrolidone weight % increases, the dye transfer benefit increases and biodegradability is maintained above 60%. Inventive 16 has a 4.3 units less Reactive Red 120 transfer and 1 .5 unit less dye transfer on Reactive Red 239.
Table 11
Figure imgf000106_0002
Table 12 shows that the inventive polymer based on grafting type F also delivers a significant and noticeable dye transfer benefit relative to the reference detergent with no polymer. Inventive 8 and Inventive 18 delivers significant dye transfer benefit as shown by the decrease in dye re-deposition with a lower dE2000 on Reactive Red 120 and Reactive Red 239 and Reactive Blue 171. The Inventive polymer 18 has even less dye transfer than inventive 8 since the vinyl acetate is 40% hydrolyzed making it more hydrophilic. Table 12
Figure imgf000107_0001
Vinyl acetate is 40% hydrolyzed.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.

Claims

Claims
1 . A graft polymer characterized by:
(A) 20 to 95%, preferably 30 to 90%, more preferably 40 to 85%, most preferably 50 to 80% of a polymer backbone as a graft base, which comprises at least one sub-unit (a1) and at least one sub-unit (a2), wherein (a1) is a unit comprising, preferably essentially consisting of, moieties derived from at least one alkylene oxide monomer and/or at least one polyalkylene oxidepolymer having two hydroxy-end-groups, the alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,
(a2) is a unit comprising, preferably consisting of, moieties derived from at least one lactone and/or at least one hydroxy acid, such sub-unit (a2) being a moiety derived from a single lactone and/or hydroxy-acid or being oligo-or-polymeric units consisting of at least one type of lactone and/or at least one type of hydroxy acid, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e. cyclic esters, starting with a-lactone (three ring atoms) followed by p-lactone (four ring atoms), y-lactone (five ring atoms) and so on; such lactones preferably being p-propiolactone, g-butyrolactone, 6- valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g- decalactone, e-decalactone; preferably caprolactone; and ii) hydroxy acid(s), which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, specifically an a-, p- or y-hydroxy acid derived from the corresponding lactone by hydrolyzation, and lactic acid, glycolic acid, 4-hydroxybutanoic acid, 6-hydroxy hexanoic acid, 12-hydroxy stearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone, wherein the polymer backbone is a) obtained
(A1) by co-polymerization of at least one sub-unit (a1) and at least one sub-unit (a2), wherein optionally at least one oligomer or polymer made from at least one subunit (a1) or at least one sub-unit (a2) can be employed within the copolymerization of at least one sub-unit (a1) and at least one sub-unit (a2) as well;
(A2) by first oligo-/polymerizing sub-unit(s) (a2) and then polymerizing the product with sub-unit(s) (a1);
(A3) By first oligo-Zpolymerizing sub-unit(s) (a1 ) and then co-polymerizing the product with sub-unit(s) (a2);or
(A4) by first providing an oligo- or polymeric sub-unit (a1) which is bears an end-cap on one side, preferably is etherified with alcohols, more preferably short-chain alcohols C1 to C4, which - as starter-block - is thereafter reacted with at least one sub-unit (a2) and optionally at least one sub-unit (a1 ) - wherein the sub-unit (a1) may be different to that/those in the starter block or may be arranged in a different order compared to those in the starter block - to attach to the non-end capped side of the starter block a new block comprising moieties from the subunits employed forthe (co-)polymerization, thereby obtaining a di-block-structure of [end-cap]-[sub-unit(s) (a1)]-[sub-unit(s) (a2)], or [end-cap]-[sub-unit(s) (a1)]- [random-{sub-unit(s) (a2)-sub unit(s) (a1)}]; wherein in case more than one sub-unit (a1) and/or more than one sub-unit (a2) are present already in an employed oligomer or polymer, those sub-units can be arranged in any order within such employed oligomer or polymer, and wherein in case more than one sub-unit (a1) and/or more than one sub-unit (a2) are present for the polymerization, those sub-units (and the optional oligomer/polymers if employed) can be arranged in any order within the obtained backbone; and wherein in case of (A1 ), (A2) and (A3) the use of a starter molecule is optional; or b) selected from
(A1) a backbone consisting of a randomly arranged order of monomeric, oligomeric and/or polymeric (al)-sub-units and monomeric, oligomeric and/or polymeric (a2)-sub-units, with more than one sub-unit (a1 ) and/or more than one sub-unit (a2) being present;
(A2) a backbone consisting of oligo- or polymerized sub-units (a2) as an inner block and two outer blocks of oligomeric and/or polymeric (a1 )-sub-units, defined as “-[block of (a1)]-[block of (a2)]-[block of (a1 )]-“, and also possibly comprising higher block-polymers such as 5-, 7- and 9- etc. blocks where at the outside of the tri-block structure further blocks of (a1) and (a2) are connected, such as a penta-block “ [block of (a1)] - [block of (a2)] - [block of (a1)]-[block of (a2)] - [block of (a1)] - [block of (a2)] - [block of (a1)] “ and so on;
(A3) a backbone consisting of and inner block of oligomeric and/or polymeric (a1)- sub-units and two outer blocks of oligo- or polymeric sub-units (a2), in the form of at least an tri-block-polymer defined as “ - [block of (a2)]-[block of (a1)] - [block of (a2)] and
(A4) a backbone consisting of a first block with
(i) on one end an end-cap - such end-cap being a C1 to C18-, preferably C1- C4-alkyl-group attached to said first block via an ether-function; and
(ii) an oligo- or polymeric sub-unit (a1); and a second block which is attached to said first block at the opposite end of said first block (“opposite” in relation to the end-cap on said first block) via an ether or ester-fu notion, said second block being composed of at least one sub-unit (a2) and optionally at least one sub-unit (a1), wherein the optional sub-unit(s) (a1) in said second block may be different to that/those in the first block or may be arranged in a different order compared to those in the first block, and the order of the sub-unit(s) (A1) and (a2) may be also in any order, including random structure, such di-block-structure having as an idealized structure in case of using only sub-unit(s) (a2) for the second block: [end-cap]-[sub-unit(s) (a1)]-[sub-unit(s) or in case of using sub-unit(s) (a1) and (a2) for the second block: [end-cap]-[sub-unit(s) (a1)]-[random-{sub-unit(s) (a2)-sub unit(s) (a1)}]; and wherein in case of (A1), (A2) and (A3) the use of a starter molecule is optional; and
(B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60 %, most preferably 20 to 50%, of polymeric sidechains (B) grafted onto the polymer backbone (A), wherein said polymeric sidechains (B) are obtainable by (co-)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), and optionally further monomer(s) (B3), and optionally further monomers, with all percentages as weight percent in relation to the total weight of the graft polymer.
2. The graft polymer according to claim 1 , wherein at least two different alkylene oxides are employed for the preparation of the backbone I are present in the backbone.
3. The graft polymer according to claim 1 to 2, wherein the monomers are:
(B1) at least one vinyl ester, selected from vinyl acetate, vinyl propionate and/or vinyl laurate and any further vinylester known to a person skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and/or vinyl benzoate;
Optionally
(B2) at least one nitrogen-containing monomer being selected from the group consisting of vinyllactames, vinyl imidazoles, 1 -vinyltriazole, 4-vinylpyridine, 4-vinylpyridine-N- oxide, 2-vinylpyridine, 1-vinyloxazolidinone, N-vinylformamide, N-vinylacetamide, N- vinyl-N-methylacetamide, and acrylamides such as acrylamide, methacrylamide, N- alkyl-substituted acrylamides, N,N‘-di alkyl (meth) acrylamide; mono- and dialkylamino- alkyl-(meth)acrylates, being preferably a vinyllactame-monomer and/or a vinylimidazole- monomer, the vinyllactam being more preferably selected from N-vinyllactams, such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N- vinylpyrrolidone, N-vinylcaprolactam, and most preferably N-vinylpyrrolidone, and the vinylimidazole being preferably N-vinyl imidazole, 2-methyl-1 -imidazole, more preferably N-vinyl imidazole; optionally
(B3) at least one further monomer, such as any one or more of 1 -vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinyl pyridine-N-oxide, N-vinyl formamide and its amine if hydrolyzed after polymerization, N-vinyl acetamide, N-vinyl-N-methyl acetamide, alkyl esters of (meth)acrylic acid; and Optionally at least one further monomer, being different from those before, such other monomer being present only in an amount of less than 2% of the total amount of monomers employed for obtaining the polymeric sidechains (B), and are preferably present only as impurities but not deliberately added for polymerization.
4. Graft polymer according to any of claims 1 to 3, wherein the amount of
- if (B2) is present -
(B) is from 10 to 60%, preferably up to 50%, more preferably up to 40%, and preferably from 20%; (B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 9 to 55 %, preferably up to 50, more preferably up to 40, even more preferably up to 35, and even more preferably up to 30%;
(B2) (nitrogen-containing monomer) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is from 1 to 41 %, preferably up to 30, more preferably up to 25 such as 1 to 25 and more preferably 5 to 25, even more preferably up to 15 such as 1 to 15 and more preferably 5 to 15, and further such as up to 10 up to 40, 35, 20, 10, and every number in between 1 and 41 , wherein preferably the amount of (B2) is not higher than the amount of (B1 ) or
- if (B2) is not present -
(B) is from 5 to 60%, preferably up to 50%, and preferably from 20%;
(B1) (vinylester) in weight percent being based on the total WEIGHT OF THE GRAFT POLYMER is the total amount of (B) minus the total amount of (B3),
(B2) (nitrogen-containing monomer) is 0%,
And further provided that in all cases before
(B3) (further monomer) is from 0 to 10, preferably at most 2, more preferably at most 1 , even more preferably about 0, but in all cases at most 10% of the amount of (B1), and not more than the amount of (B2). Graft polymer according to any of claims 1 to 4, wherein at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 80, more preferably at least 90 weight percent, and most preferably essentially only vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B1 being employed). Graft polymer according to any of claims 1 to 5, wherein
(A) the polyalkoxylate-ester backbone comprises moieties derived from
(i) alkylene oxides (AO) comprising at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably at least one of EO and PO, with the AO in an amount of from 40 to 99, preferably up to 90, and preferably from 50, more preferably from 60, and even more preferably from 70wt%, and any number and range in between, each based on the total weight of the backbone, the amount of EO being of from 0 to 100wt.%, preferably from 10, more preferably from 20, even more preferably from 30, even more preferably from 40, such as from 50, 60, 70, 80 or even from 90wt%, based on total AO, the PO and/or BO, in an total amount of each from 0 to 100 wt.%, preferably up to 90, more preferably up to 80, even more preferably up to 70, even more preferably up to 60, and most preferably up to 50, and any number in between such as up to 5, 10, 15, 25, 30, 35, 40, 45, 55, 65, 75, 85 or up to 95, and more preferably from 10, even more preferably from 20, even further more preferably from 30, such as from 40, 50, 60, 70, 80 or even from 90wt%, each based on the total weight of AO, with the total amount of PO and BO adding up to 100wt.% for the sum of PO and BO, with the total amount of AO adding up to 100wt.%;
(ii) lactone /hydroxy acid monomer in an amount of from 1 and up to 60, preferably up to 50, more preferably up to 40, most preferably up to 30 wt. %, and preferably from 2, more preferably from 3, even more preferably from 4 and most preferably from 5 wt.%, each based on the total weight of the backbone, preferably only caprolactone;
With the total weight of the sum of sub-units (a1) and sub-units(a2) in the backbone (A) adding up to 100 wt%.
7. Graft polymer according to claim 6, wherein
(i) alkylene oxides (AO) is selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably only EO and PO, with the AO in an amount of from 40 to 99, preferably up to 90, and preferably from 50, more preferably from 60, and even more preferably from 70wt%, and any number and range in between, each based on the total weight of the backbone, the amount of EO being of from 10 to 90, preferably 20 to 80, more preferably 30 to 70, and most preferably 40 to 60wt%, based on total AO, the total amount of PO and BO being from 10 to 90, preferably 20 to 80, more preferably 30 to 70, and most preferably 40 to 60wt%, each based on the total weight of AO, with the total amount of PO and BO adding up to 100wt.% for the sum of PO and BO, and with the total amount of AO adding up to 100wt.%;
(ii) lactone /hydroxy acid monomer in an amount of from 1 and up to 60, preferably up to 40, more preferably up to 30, even more preferably up to 25, even further more preferably up to 20, and most preferably up to 15 wt. %, and preferably from 2, more preferably from 3, even more preferably from 4 and most preferably from 5 wt.%, each based on the total weight of the backbone, preferably only caprolactone;
With the total weight of the sum of sub-units (a1) and sub-units(a2) in the backbone (A) adding up to 100 wt%.
8. Graft polymer according to claim 6, wherein
(i) alkylene oxides (AO) is selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably only EO and PO, more preferably only EO the amount of EO being of from 20 to 100 wt%, based on total AO, the total amount of PO and BO being from 0 to 80 wt.%, preferably up to 50, more preferably up to 30, even more preferably up to 20, and even further preferably up to 10, and most preferably zero, such as 45, 45, 45, 25, 15, 7 and 5, and any number in between, each based on the total weight of AO, with the total amount of PO and BO adding up to 100wt.% for the sum of PO and BO, with the total amount of AO adding up to 100wt.%; (ii) lactone /hydroxy acid monomer in an amount of from 5 and up to 50, preferably up to 40, more preferably up to 35, and even more preferably up to 30, and as lower limit preferably from 7, more preferably from 10, even more preferably from 12 wt%, and most preferably from 15, such as 6,8, 9, 11 , 12, 13, 14 and 15 and any number in between as lower limit and such as 30, 33, 37, 45 and any number in between as upper limit, based on the total weight of the backbone, preferably only caprolactone;
With the total weight of the sum of sub-units (a1) and sub-units(a2) in the backbone (A) adding up to 100 wt%.
9. Graft polymer according to any of claims 1 to 8, wherein
(B) the monomers are:
(B1) at least one vinyl ester, selected from vinyl acetate, vinyl propionate and/or vinyl laurate, in amounts of from 70 to 100% by weight of the total weight of monomers that are grafted onto the backbone (A), preferably only vinyl acetate, and
(B2) optionally at least one nitrogen-containing monomer in amounts of from 0 to 30% by weight of the total amount of monomers that are grafted onto the backbone (A), being preferably a N-vinyllactam, such as N-vinylpyrrolidone, N-vinylpiperidone, N- vinylcaprolactam, even more preferably N-vinylpyrrolidone and/or N- vinylcaprolactam, and most preferably N-vinylpyrrolidone, with the vinyl ester monomer(s) (B1) optionally being partially or fully hydrolyzed after polymerization.
10. Graft polymer according to any of claims 1 to 9, wherein essentially no other monomers (B2) nor (B3) are employed.
11. Graft polymer according to any of claims 1 to 10, wherein monomer (B1) and (B2) are present and no other monomers are employed.
12. Graft polymer according to any of claims 1 to 11 , wherein the at least one vinyl estermonomer (Bl)-derived moiety is partially or fully hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mole%, and preferably from 20mole%, more preferably 20 to 50, even more preferably 30 to 45, such as about 40 mole %based on the total moles of (B1) employed, after the polymerization reaction.
13. Graft polymer according to any of claims 1 to 12, wherein wherein at least one of i), ii) and iii) is fulfilled: i) the polymer backbones (A1), (A2) and (A3) may bear as the end-groups two hydroxy-groups or may be capped with C1 to C22-alkyl groups, preferably C1 to C4 alkyl groups; such end-group being attached using standard means after final preparation of the backbone whereas for (A4) such end-cap is done on the oligo- /polymeric sub-unit (a1) prior to the polycondensation employing sub-unit(s) (a2); ii) the graft polymer has a polydispersity (PDI) Mw/Mn of at most 10, preferably at most 5, more preferably at most 3, and most preferably in the range from 1 .0 to 2.6, and any number a as upper or lower limit and any range in between such as 1 ,3 to 2,6, 1 to 3 etc. (with Mw = weight average molecular weight and Mn = number average molecular weight [g/mol I g/mol]); iii) the biodegradability of the graft polymer is at least 35, more preferably at least 40, even more preferably at least 45, even further more preferably at least 50, such as 46, 47, 48, 49, 50, 55, 60, 65, 70, 75 etc. and any number in between and up to 100%, within 28 days, when tested under OECD 301 F. A process for obtaining a graft polymer according to one of claims 1 to 13, comprising the step of polymerizing at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), and optionally further monomer(s) (B3) and further optionally including further monomer(s) as impurities within (B1), (B2) and/or (B3) is/are polymerized in the presence of at least one polymer backbone (A), wherein the polymeric sidechains (B) are obtained by radical polymerization, preferably using radical forming compounds to initiate the radical polymerization. The process according to claim 14, comprising the polymerization of at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), optionally further monomer(s) (B3), in the presence of at least one polymer backbone
(A), preferably selected from backbones (A1), (A2), (A3) and (A4), a free radical-forming initiator (C) and, optionally, up to 50% by weight, based on the sum of components (A),
(B), and (C), of at least one solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomers (B1), optional (B2) and optional (B3) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the polymer backbone (A), wherein preferably at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent, and most preferably essentially only (i.e. about 100wt.% or even 100 wt.%) vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B1 being employed), and - preferably - the amounts of monomers are those as of any of the claims before listing such amounts. Process according to any of claims 14 or 15, wherein essentially no other monomer (B3) is employed. Process according to any of claims 14 to 16, wherein essentially no other monomers (B2) nor (B3) are employed. Process according to any of claims 14 to 17, wherein the at least one vinyl estermonomer (Bl)-derived moiety, preferably stemming from employing only vinyl acetate as (B1), is partially or fully hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mole%, and preferably from 20mole%, more preferably 20 to 50, even more preferably 30 to 45, such as about 40 mole %, based on the total moles of (B1) employed, after the polymerization reaction, and preferably no other monomer (B3) is employed, more preferably as (B2) a N-vinyllactame, preferably N-vinylpyrrolidone, is employed.
19. Process according to any of claims 14 to 18, wherein the process comprises at least one further process step selected from i) to iv): i) Post-polymerisation; ii) Purification; iii) Concentration; and iv) Drying.
20. Process according to any of claims 14 to 19, wherein the process comprises at least one further process step selected from: i) a post-polymerization process step that is performed after the main polymerization reaction, wherein preferably a further amount of initiator (optionally dissolved in the solvent(s)) is added over a period of 0,5 hour and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, with the radical initiator and the solvent(s) for the initiator typically - and preferred - being the same as the ones for the main polymerization reaction; and wherein after the polymerization reaction and before the postpolymerisation reaction preferably a period is waited when the main polymerization reaction is left to proceed, before the post-polymerisation reaction is started by starting the addition of further radical initiator, such period being preferably from 10 minutes and up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, and most preferably up to 30 minutes; and wherein the temperature of the post-polymerisation process step is - preferably - the same as in the main polymerization reaction, or is increased, such increase being preferably higher by about 5 to 40°C, preferably 10 to 20°C compared to the temperature of the main polymerisation reaction; ii) a step of subjecting the graft polymer as obtained from the main polymerization or - if performed, the post-polymerisation process - to a means of purification, concentration and/or drying to remove part of or almost all of the remaining solvent(s) (as far as they are removable due to their boiling points) and/or volatiles such as residual monomers, wherein a. the concentration is performed by removing part of the solvent(s) and optionally also volatiles - by this this step additionally serves as means for purification - to increase the solid polymer concentration - and optionally as well for purification - , by preferably applying a distillation process such as thermal or vacuum distillation, preferably vacuum distillation, and/or applying stripping with gas such as steam or an inert gas such as nitrogen, preferably using steam from water, which is performed until the desired solid content and optionally also purity is achieved, preferably is performed until the desired part or all of the volatile components such as volatile solvents and/or unreacted, volatile monomers, are removed; b. the drying is performed by subjecting the graft polymer containing at least residual amounts of volatiles such as remaining solvent and/or unreacted monomers etc. to a means of removing the volatiles, such as drying using a roller-drum, a spray-dryer, vacuum drying or freeze-drying, preferably - mainly for cost-reasons - spray-drying; and optionally combining such drying process step with a means of agglomeration or granulation to obtain agglomerated or granulated graft polymer particles, such process being preferably selected from spray-agglomeration, granulation or drying in a fluidized-bed dryer, spray-granulation device and the like. Process according to any of claims 14 to 20, wherein the amount of water during the polymerisation is at most 10 wt.%, preferably at most 5 wt.%, more preferably at most 1 wt.%, based on total weight of graft polymer (at the end of the polymerization) or based on total weight of (A) and (B) (at the start of the polymerization). Use of at least one graft polymer according to any of claims 1 to 13 or obtained by or obtainable by the process according to any of claims 14 to 21 in a composition, that is a fabric and home care product, cleaning composition, industrial and institutional cleaning product. The use according to claim 22 in cleaning compositions and/or in fabric and home care products, preferably in cleaning compositions for in fabric and home care, the cleaning composition preferably being a laundry detergent formulation or a dish wash detergent formulation, optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme being selected from lipases, hydrolases, amylases, proteases, cellulases, wherein the at least one graft polymer is present in an amount ranging from about 0.01 % to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1 % to about 10%, and most preferably from about 0.5% to about 5%, in relation to the total weight of such composition or product in relation to the total weight of such composition or product, and such product or composition further comprising from about 1% to about 70% by weight of a surfactant system. A composition that is a fabric and home care product, cleaning composition, industrial and institutional cleaning product, preferably a laundry detergent, a dish wash composition, a cleaning composition and/or a fabric and home care product, each containing at least one graft polymer according to any of claims 1 to 13 or obtained by or obtainable by the process according to any of claims 14 to 21 , the cleaning composition preferably being a laundry detergent formulation or a dish wash detergent formulation, optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme being selected from lipases, hydrolases, amylases, proteases, cellulases, wherein the at least one graft polymer is present in an amount ranging from about 0.01 % to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, in relation to the total weight of such composition or product in relation to the total weight of such composition or product, and such product or composition further comprising from about 1% to about 70% by weight of a surfactant system.
25. The composition according to claim 24 further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol.
26. The composition according to claim 24 or 25 comprising 4,4’-dichloro 2- hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.
27. A method of preserving a composition according to claim 25 against microbial contamination or growth, which method comprises addition of an antimicrobial agent selected from the group consisting of 2-phenoxyethanol to the composition which is an aqueous composition comprising water as solvent.
28. A method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a composition according to claim 24 or 25, wherein the composition comprises 4,4’-dichloro 2-hydroxydiphenylether, preferably comprising 4,4’-dichloro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition.
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