CN117730109A

CN117730109A - Artificial polymers with altered oligosaccharide or polysaccharide functionality or narrow oligosaccharide distribution, methods of making the same, compositions comprising the same, and methods of use thereof

Info

Publication number: CN117730109A
Application number: CN202280051108.6A
Authority: CN
Inventors: K·A·罗德里格斯; M·M·范德胡夫; S·班塔
Original assignee: Norion Chemicals International Ltd
Current assignee: Norion Chemicals International Ltd
Priority date: 2021-05-20
Filing date: 2022-05-20
Publication date: 2024-03-19

Abstract

The present invention relates to an artificial polymer comprising a synthetic component (a) covalently bonded to a natural component (B), wherein the natural component comprises an oligosaccharide or polysaccharide, and wherein the terminal groups of the oligosaccharide or polysaccharide are substantially free of aldehyde functionality when in open chain form. The present disclosure also relates to an artificial polymer comprising a synthetic component (a) covalently bonded to a natural component (B), wherein the natural component comprises a narrow oligosaccharide profile prepared by enzymatic degradation of a polysaccharide. The artificial polymers described herein are useful in a variety of end-use applications including cleaning, automatic dishwashing, detergents, minimizing scaling, water treatment, as adhesives, as superabsorbents, as rheology modifiers, and in personal care.

Description

Artificial polymers with altered oligosaccharide or polysaccharide functionality or narrow oligosaccharide distribution, methods of making the same, compositions comprising the same, and methods of use thereof

Priority claim

The present application claims priority from U.S. provisional application serial No. 63/191,185, filed 5/20/2021, and european patent application No. EP 21195067.0, filed 9/6/2021, which are incorporated herein by reference in their entirety.

Technical Field

The present disclosure relates to artificial polymers constructed from synthetic and natural components, wherein in one embodiment the natural components comprise an oligosaccharide or polysaccharide that has been intentionally modified on its terminal groups to substantially eliminate aldehyde functionality when the terminal groups are in open chain form; and in another embodiment has a narrow oligosaccharide profile prepared by enzymatic degradation of the polysaccharide. The artificial polymers have improved properties compared to known counterparts.

Background

Various synthetic polymers constructed from a combination of synthetic and naturally derived materials are known in the art, wherein the naturally derived materials act as chain transfer agents. See, for example, U.S. patent No. 7,666,963;8,674,021;8,227,381;7,666,963;8,058,374;9,109,068;9,321,873;9,988,526; and 9,051,406, published PCT application WO 2015/124384; WO 2018/206811; and WO 2018/206812, the entire contents of which are incorporated herein by reference. These artificial polymers are advantageous over synthetic polymers that have been used prior to their development because they are derived at least in part from renewable natural sources and thus have improved reproducibility and biodegradability compared to fully synthetic counterparts.

U.S. patent No. 8,058,374, for example, describes such artificial polymers comprising long chains of synthetic monomers at the chain ends that are bound to a moiety derived from natural materials that are so-called "chain transfer agents". In one embodiment, the chain transfer agent is a hydroxyl-containing naturally derived material, for example a monosaccharide, oligosaccharide or polysaccharide, such as granulated sugar, corn syrup, maltodextrin or starch.

Although the known synthetic polymers have found wide application in a variety of industries, they have been found to change color under conditions of elevated pH and elevated temperature during processing, storage and end use. Such discoloration is undesirable because end-use manufacturers and their consumers have strong and specific desires for the color of their products. Thus, the problem of discoloration places these artificial polymers at an increasing commercial disadvantage by reducing the chances that the manufacturer will choose these artificial polymers for their products or the consumer will choose to purchase such products.

EP 0 087 995 B1 describes copolymers of acrylamide and polysaccharide resins as electrophoretic gel media. According to this teaching, when agar and agarose are reacted in solution with acyl and alkylating agents such as alkenyl halides, allyl glycidyl ether, acryloyl chloride, crotonyl chloride, methacryloyl chloride and 3-butenoyl under basic conditions to form a derivatized polyol precursor and reacting the derivatized polyol precursor with polyacrylamide in a subsequent step to form a copolymer, some discoloration of the solution may occur, which may be avoided by blocking the aldehyde end groups of the agarose.

US 5,578,678 describes graft polymers of mono-, oligo-and polysaccharides obtained by free radical polymerization of open-chain N-vinylformamide, which are used as dry and wet strength agents for paper, paperboard and cardboard. It teaches that the first step in preparing such graft polymers involves enzymatic degradation of the polysaccharide. It further teaches that the N-vinyl-carboxamide is preferably N-vinyl-carboxamide and that the polymer is subjected to hydrolysis to eliminate 2 to 100% of the formyl groups. The patent also teaches that color stability in storage can be improved by adding a reducing agent or aldehyde acceptor during or after hydrolysis.

EP 0 725 A1 describes the preparation of graft polymers of mono-, oligo-and polysaccharides, which are obtained by free-radical-initiated polymerization of monomer mixtures containing 40 to 100% by weight of monoethylenically unsaturated C ₃ To C ₁₀ Monocarboxylic and/or monoethylenically unsaturated C ₄ To C ₈ Dicarboxylic acids, anhydrides, alkali metal salts and/or ammonium salts thereof for use as additives for certain dishwashing detergents containing at least 5% by weight of at least one ammonium or alkali metal carbonate or ammonium or alkali metal sulfate and at least 2% by weight of sodium silicate. Phosphate-free low-foam dishwashing detergents are known from this teaching, but the cleaning effect produced by the use of such detergents is not always satisfactory. The object was to provide a sodium silicate-containing dishwashing detergent which leaves little silicate deposits on machine-washed Tao Ju, tableware and glassware in use and whose polymer component is produced partly using renewable raw materials and thus has a significantly improved biodegradability. It further teaches that in order to prepare a colorless or only slightly colored graft polymer, it is necessary to carry out the polymerization in the presence of a water-soluble phosphorus compound, preferably phosphorous acid. Virtually all polymer preparation examples in this document involve the addition of a certain amount of phosphorous acid. However, this is disadvantageous because phosphorus is incorporated into the resulting polymer and is therefore present when the cleaning formulation is used. These phosphorus are then released into the environment with the used dish wash water, resulting in eutrophication of water bodies such as lakes, rivers and oceans.

It is an object of the present disclosure to produce an artificial polymer that is substantially free of added phosphorus that does not discolor even under extreme pH and/or temperature conditions, during processing, or upon storage, or even when used by a consumer.

Disclosure of Invention

In one embodiment, the present invention relates to an artificial polymer comprising a synthetic component (a) covalently bonded to a natural component (B), wherein the natural component comprises an oligosaccharide or polysaccharide, and wherein the terminal groups of the oligosaccharide or polysaccharide are substantially free of aldehyde functionality when in an open chain form.

In another embodiment, the invention relates to an artificial polymer comprising a synthetic component (a) covalently bonded to a natural component (B), wherein the natural component comprises a mixture comprising monosaccharides having an oligomerization degree DP1, disaccharides having an oligomerization degree DP2, tetrasaccharides having an oligomerization degree DP4, pentasaccharides having an oligomerization degree DP5, and hexasaccharides having an oligomerization degree DP6, wherein the sum of dp1+dp2 is less than 30 wt% and the sum of dp4+dp5+dp6 is greater than 15 wt%, in each case based on the total weight of the polymer.

In another embodiment, the present disclosure relates to a method of making an artificial polymer as described herein, the method comprising the steps of: (A) Providing a polymer precursor mixture comprising (i) one or more monomer precursors of a synthesis component and (ii) an oligosaccharide or polysaccharide comprising a terminal group capable of existing in the form of an open chain comprising an aldehyde functional group; and (B) polymerizing the polymer precursor mixture to form an artificial polymer, wherein all or a substantial portion of the aldehyde functionality is eliminated before or after step (B).

In another embodiment, the present disclosure relates to a composition useful for preparing an artificial polymer as described herein, the composition comprising (a) one or more monomeric precursors of a synthetic component and (B) an oligosaccharide or polysaccharide comprising a terminal group that is substantially free of aldehyde functionality when in an open chain form.

In another embodiment, the present invention relates to a method of preparing an artificial polymer as described herein, comprising the steps of: (a) enzymatically degrading the polysaccharide to form an oligosaccharide; (B) Providing a polymer precursor mixture comprising (i) one or more monomer precursors of a synthesis component and (ii) the oligosaccharides prepared in (a); and (C) polymerizing the polymer precursor mixture to form the artificial polymer.

In another embodiment, the present disclosure relates to a composition useful for preparing an artificial polymer as described herein, the composition comprising (a) one or more monomeric precursors of the synthetic component and (B) a mixture comprising a monosaccharide having a degree of oligomerization DP1, a disaccharide having a degree of oligomerization DP2, a tetrasaccharide having a degree of oligomerization DP4, a pentasaccharide having a degree of oligomerization DP5, and a hexasaccharide having a degree of oligomerization DP6, wherein the sum of dp1+dp2 is less than 30 wt% and the sum of dp4+dp5+dp6 is greater than 15 wt%, in each case based on the total weight of the composition.

In another embodiment, the present disclosure relates to an artificial polymer prepared according to the above method.

In another embodiment, the present disclosure relates to a formulation comprising an artificial polymer as described herein and at least one additional ingredient.

In another embodiment, the present disclosure relates to a method of preparing a formulation as described above, comprising adding an artificial polymer to the at least one additional ingredient.

In another embodiment, the present disclosure is directed to a method of cleaning a surface comprising contacting the surface with an effective amount of the formulation described above.

In another embodiment, the present disclosure relates to a method of controlling fouling in an aqueous system comprising introducing an effective amount of an artificial polymer as described herein into the aqueous system.

In another embodiment, the present disclosure relates to a method of dispersing particles in an aqueous system comprising adding an effective amount of an artificial polymer as described herein to the aqueous system.

In another embodiment, the present disclosure relates to a method of treating skin or hair comprising applying an effective amount of an artificial polymer as described herein.

In another embodiment, the present disclosure relates to a method of modifying the rheological properties of a formulation comprising incorporating an effective amount of an artificial polymer as described herein into such a formulation.

Drawings

The present disclosure will now be described in more detail with reference to the accompanying drawings, in which:

FIG. 1 illustrates maltodextrin end group functionalities in the form of "closed chains" and "open chains".

Definition of the definition

As used herein, the term "synthetic" refers to non-naturally occurring.

As used herein, the term "natural" refers to naturally occurring.

As used herein, the term "man-made polymer" refers to a polymer that does not exist in nature but is prepared synthetically. The term includes "hybrid polymer" and "graft polymer" as defined below.

As used herein, the term "hybrid polymer" refers to a polymer that contains a backbone that contains both synthetic and natural monomer residues.

As used herein, the term "graft polymer" refers to a polymer that contains a backbone that itself may be a synthetic homopolymer, a natural homopolymer, or a synthetic/natural copolymer, to which synthetic and/or natural monomer chains are attached.

As used herein, the term "sugar" refers to the unit structure of a carbohydrate. Sugars are typically present in either a cyclic ("closed chain form") or short chain conformation ("open chain form") and typically contain 4 to 6 carbon atoms.

As used herein, the term "oligosaccharide" refers to a sugar unit chain of 1 to 20 sugar units in length.

As used herein, the term "polysaccharide" refers to a chain of saccharide units that is greater than 21 saccharide units in length.

As used herein, the term "substantially free", particularly when it relates to phosphorus content, means that the phosphorus in the polymer is less than 0.1 wt%, preferably less than 0.05 wt%, most preferably less than 0.01 wt% of the phosphorus in the polymer.

As used herein, the term "substantially free of added phosphorus" means that in addition to phosphorus naturally contained in the natural component (e.g., potato starch), such as by using an additive, such as a water-soluble phosphorus compound, e.g., phosphorous acid or a salt thereof, the amount of phosphorus introduced during the preparation of the polymer and/or during processing, transportation and/or storage prior to end use is no more than 0.1 wt.% of the phosphorus in the polymer, preferably no more than 0.05 wt.% of the phosphorus in the polymer, and most preferably no more than 0.01 wt.% of the phosphorus in the polymer.

As used herein, the term "substantially eliminate" means that more and more preferably less than 10% is left, or less than 5% is left, or less than 2% is left, or less than 1% is left, or none is present, as compared to the starting amount.

As used herein, the term "substantially free" means that the inclusion in the precursor that has been eliminated is less than 10%, or less than 5%, or less than 2%, or less than 1%, or is completely absent, as compared to the precursor.

As used herein, the term "known polymer precursor" refers to a known polymer comprising terminal groups that can exist in the form of open chains comprising aldehyde functional groups. Such known polymer precursors may be modified by the techniques described herein to substantially eliminate aldehyde functionality, thereby stabilizing the resulting synthetic polymer against discoloration.

Detailed Description

As shown in fig. 1, at any given point in time, a very small portion of the sugar end groups may be present in an "open chain form" having aldehyde functionality. Without wishing to be bound by theory, it is believed that under conditions of elevated temperature (e.g., above 20-40 ℃) and alkaline pH (above pH 7), the aldehyde functionality reacts with the residual protein/amino acid and other materials that may be present from the polysaccharide source in a process known as Maillard (Maillard) reactions. This initiates a complex series of reactions that ultimately discolor the artificial polymer.

Too low or too high a pH (e.g. below pH 3 or above pH 8) may also lead to depolymerization of the polysaccharide chains, especially during the polymerization process. The depolymerization of the polysaccharide chains in turn increases the number of aldehyde-containing end groups.

The discoloration we observe and addressed by the present disclosure includes not only the discoloration of clear products to yellow or even brown, but also the discoloration of colored products such as purposely dyed red or some other color together to a different shade of the same color or different colors. The color stability of the product over the entire lifetime, whether during initial polymerization, during transport, during storage, or during use, is desired.

In fact, without some preventive treatment, the artificial polymer usually becomes very dark in the reactor during polymerization at standard reaction temperatures (80-95 ℃) and a wide pH range. Also, without some prophylactic treatment, the artificial polymer may depolymerize and discolor during transportation and storage or during formulation. The same is true for man-made polymers in liquid or solid form. Solid forms of these polymers are used in powder laundry detergents and unit dose tablets.

Polymer

The range of man-made polymers that can benefit from the present disclosure is generally all known polymers having terminal group aldehyde functionality that may be susceptible to maillard reactions in the manner described herein. Such known polymers may be modified in accordance with the teachings herein to produce artificial polymers modified to substantially eliminate aldehyde functionality, and thus, are stable to discoloration.

In one embodiment, the synthetic polymer is a hybrid copolymer. Known polymer precursors of this type are described, for example, in U.S. patent No. 7,666,963, the entire contents of which are incorporated herein by reference. The present disclosure extends to any polymer described herein modified by the techniques described herein to substantially eliminate aldehyde functionality in the terminal group saccharide moiety.

In one embodiment, the synthetic polymer is a sulfonated graft copolymer. Known polymer precursors of this type are described, for example, in U.S. patent No. 8,674,021, the entire contents of which are incorporated herein by reference. The present disclosure extends to any polymer described herein modified by the techniques described herein to substantially eliminate aldehyde functionality in the terminal group saccharide moiety.

In one embodiment, the synthetic polymer is a low molecular weight graft copolymer. Known polymer precursors of this type are described, for example, in U.S. patent No. 8,227,381, the entire contents of which are incorporated herein by reference. Such polymers have a number average molecular weight of about 100,000 daltons or less, preferably about 25,000 daltons or less, more preferably about 10,000 daltons or less. The method for determining the number average molecular weight of the graft copolymer and the polysaccharide used to prepare the graft polymer is as described in column 24 of the 8,227,381 patent and incorporated herein by reference. The present disclosure extends to any polymer described herein modified by the techniques described herein to substantially eliminate aldehyde functionality in the terminal group saccharide moiety.

The molecular weight of the artificial polymers described herein can be determined by aqueous gel permeation chromatography ("GPC") using a range of polymer standards. If the synthetic moiety contains an acid moiety, the standard used is typically a polyacrylic acid (PAA) standard. The method uses 0.05M sodium phosphate (0.025M NaH) ₂ PO ₄ And 0.025M Na ₂ HPO ₄ ) Buffered to pH 7.0 and treated with NaN ₃ As mobile phase. The columns used in this method are: TSKgel PWx1 guard column, TSKgel; g6000PWxl, G4000PWxl, G3000PWxl, G2500PWx1 were set at 32 ℃. The flow rate was 1 mL/min and the injection volume was 450. Mu.L. The instrument was calibrated using five different polymer standards injected at five different concentrations: PAA1K (2.0 mg/mL), PAASK (1.75 mg/mL), PAA85K (1.25 mg/mL), PAA495K (0.75 mg/mL) and PAA1700K (0.2 mg/mL), all from American Polymer Standards Corporation.

The molecular weight of the starting polysaccharide used to prepare the artificial polymers described herein can be determined by aqueous Gel Permeation Chromatography (GPC) using a series of Hydroxyethyl (HETA) starch standards. The method uses 0.05M sodium phosphate (0.025M NaH) ₂ PO ₄ And 0.025M Na ₂ HPO ₄ ) Buffered to pH 7.0 and treated with NaN ₃ As mobile phase. The columns used in this method are: TSKgel PWx1 protectionColumn, TSKgel; g6000PWxl, G4000PWxl, G3000PWxl and G2500PWx1 were set at a temperature of 32 ℃. The flow rate was 1 mL/min and the injection volume was 450. Mu.L. The instrument was calibrated using five different hydroxyethyl starch standards injected at five different concentrations: HETA10K (2.0 mg/mL), HETA17K (1.75 mg/mL), HETA40K (1.25 mg/mL), HETA95K (0.75 mg/mL) and HETA205K (0.2 mg/mL), all from American Polymer Standards Corporation.

In one embodiment, the artificial polymer is a graft dendrite copolymer. Known polymer precursors of this type are described, for example, in U.S. patent No. 9,051,406, the entire contents of which are incorporated herein by reference. The present disclosure extends to any polymer described herein modified by the techniques described herein to substantially eliminate aldehyde functionality in the terminal group saccharide moiety.

In one embodiment, the artificial polymer is a hybrid dendrite copolymer. Known polymer precursors of this type are described, for example, in U.S. patent No. 9,988,526, the entire contents of which are incorporated herein by reference. The present disclosure extends to any polymer described herein modified by the techniques described herein to substantially eliminate aldehyde functionality in the terminal group saccharide moiety.

In a particular embodiment, the synthetic polymer comprises the following general structure:

wherein the method comprises the steps of

Re ₁ Represents a non-aldehyde functional group, preferably an alcohol or carboxylic acid;

m ₁ represents the number of repeating units of the natural component and is from-1 to 98, preferably from 0 to 48, most preferably from 1 to 10;

n ₁ represents the number of repeating units of the synthetic moiety and is 20 to 100, preferably 25 to 70, most preferably 30 to 50;

R ₁ is a single monomer residue constituting a synthetic part, but may be a residue of a monomer represented by (R ₁ )n ₁ Chain variation of the groups and preferably (meth) acrylic monomers, itaconic acid monomersA monomer, a maleic acid monomer, or a mixture of two or more of the foregoing monomers; and

Re ₂ represents a terminal functional group derived from an initiator fragment or from a chain transfer reaction.

R ₁ Bonding to the polysaccharide chain is via covalent carbon-carbon bonding, typically via one of the carbon atoms of the polysaccharide having hydroxyl groups, most preferably the C of the anhydroglucose unit ₂ Or C ₃ A carbon atom.

In a preferred embodiment, re ₂ Represents H, hydroxy, sulfate or ORe ₄ Wherein Re is ₄ C derived from initiator fragments ₁ -C ₁₀ Aliphatic or aromatic moieties. Re (Re) ₂ Preferably H or a sulfate group. Re (Re) ₂ Represents, for example, H which is generated when the chain is transferred to another monomer or polysaccharide. Re (Re) ₂ Represents, for example, OH generated when the initiator is hydrogen peroxide; ORe, for example, when the initiator is an organic peroxide ₄ . Finally, re ₂ Represents the sulfate radical generated when the initiator system is a persulfate. The foregoing is merely exemplary and other terminal functional groups are contemplated and form part of the present disclosure.

Synthetic polymers corresponding to the aforementioned general structure are particularly suitable for use as dispersants or scale inhibitors. As described above, m ₁ Is the number of sugar repeating units of the natural component. Degree of polymerization DP ₁ Is m ₁ +2. Thus, in another embodiment, for a dispersant or scale inhibitor, the DP ₁ Varying between 1-100, 2-50 and 3-20.

In one embodiment, the polymer comprises a mixture of chains having the aforementioned general structure, and in some cases Re is present ₁ Some chains of aldehyde functions, i.e., treatment according to the methods described herein, do not completely eliminate aldehyde functions, although the aldehyde functions have been significantly eliminated.

In one embodiment, re ₁ The mole% of the aldehydes is less than 10 mole%, preferably less than 5 mole%, preferably less than 2 mole%, preferably less than 1.5 mole%,more preferably less than 1.0 mole% of the number of saccharide units and most preferably is absent.

In another particular embodiment, the synthetic polymer comprises the following general structure:

wherein the method comprises the steps of

m ₂ represents the number of repeating units of the natural component and is 0 to 9998, preferably 1 to 998, most preferably 2 to 98;

n ₂ represents the number of repeating units forming part of the synthetic moiety and is preferably greater than 1000, more preferably greater than 5000 and most preferably greater than 10,000;

R ₂ is a single monomer residue constituting a synthetic part, but may be a residue of a monomer represented by (R ₂ )n ₂ The chain of the groups varies and is preferably derived from anionic ethylenically unsaturated monomers and is preferably a (meth) acrylic monomer;

n ₃ represents the number of repeating units forming part of the synthetic moiety and is preferably greater than 1000, more preferably greater than 5000 and most preferably greater than 10,000;

R ₃ is a single monomer residue constituting a synthetic part, but may be a residue of a monomer represented by (R ₃ )n ₃ The chain of the radicals varies and is preferably derived from a hydrophobic ethylenically unsaturated monomer and is preferably an ethyl acrylate, methyl (meth) acrylate or butyl (meth) acrylate monomer or a mixture of two or more of the aforementioned monomers; and

Re ₂ Represents a terminal functional group derived from an initiator fragment or from a chain transfer reaction, preferably H or a sulfate group.

Synthetic polymers corresponding to this general structure are particularly suitable for use as rheology modifiers. As described above, m ₂ Number of sugar repeating units which are natural components and degree of polymerization DP ₁ Is m ₂ +2. Thus, in another embodiment, the DP for the rheology modifier ₂ Ranging from 2 to 10,000, 3 to 1,000 and 4 to 100.

In one embodiment, the polymer comprises a mixture of chains having the general structure described above, and in some cases, some Re is present ₁ Chains of aldehyde functions, i.e., treatments according to the methods described herein do not completely eliminate aldehyde functions, although the aldehyde functions have been significantly eliminated.

In one embodiment, re ₁ The mole% of the aldehyde is less than 10 mole%, preferably less than 5 mole%, preferably less than 2 mole%, preferably less than 1.5 mole%, more preferably less than 1.0 mole% and most preferably no saccharide unit number.

In yet another embodiment, the synthetic polymer comprises the following general structure:

wherein the method comprises the steps of

Re ₁ Represents an aldehyde, alcohol or carboxylic acid functional group;

m ₃ Represents the number of repeating units of the natural component and is from-1 to 98, preferably from 0 to 48, most preferably from 1 to 10;

n ₄ represents the number of repeating units of the synthetic moiety and is 20 to 100, preferably 25 to 70, most preferably 30 to 50;

R ₄ is a single monomer residue constituting a synthetic part, but may be a residue of a monomer represented by (R ₄ )n ₃ The chain of the groups varies and is preferably (meth) acrylic monomer, itaconic acid monomer, maleic acid monomer or a mixture of two or more of the foregoing monomers; and

Synthetic polymers having narrow distributions of oligosaccharides corresponding to the general structure described above are particularly suitable for use as dispersants or scale inhibitors. As described above, m ₃ Is the number of sugar repeating units of the natural component. Degree of polymerization DP ₃ Is m ₃ +2. Thus, in another embodiment, the DP for the dispersant or scale inhibitor ₃ From 1 to 100, preferably from 2 to 50 and most preferably from 3 to 20, and is an oligosaccharide having an oligomerization Degree (DP), wherein the sum of dp1+dp2 is less than 30% of the total oligosaccharides or polysaccharides and the sum of dp4+dp5+dp6 is greater than 15% of the total oligosaccharides or polysaccharides. DPn represents the number n of repeating units in the particular oligosaccharide chain, where DP1 is 1 repeating unit and DP6 is 6 repeating units.

The polymerization of the artificial polymer needs to be modified by the technique of the invention as described below in order to substantially eliminate aldehyde functionality in the terminal group saccharide moiety. In one embodiment, hydrogenated starch hydrolysates, also known as polyols, may be used for these reactions. These materials have a minimum amount of aldehyde end groups or no aldehyde groups at all. However, aldehyde end groups may be generated during the hybrid polymerization process. For example, if the duration of the initiator feed is much longer than the duration of the monomer feed, excess initiator can depolymerize the sugar chains, resulting in the creation of aldehyde end groups during the polymerization process. To minimize this, the initiator feed should be shorter than the monomer feed when using these polyols as exemplified in examples 1-5. Those skilled in the art will recognize that these initiators have half-lives at the polymerization temperature and that it is important to ensure that the initiator feed takes into account the initiator half-life. The initiator feed and initiator concentration should be such that there is sufficient initiator to polymerize the monomer (especially at the end of the monomer feed) as compared to the monomer concentration, but not so much initiator that the oligosaccharides or polysaccharides are depolymerized after the monomer has been polymerized, as exemplified in examples 1-5. In one embodiment, conventional oligosaccharides and polysaccharides such as corn syrup and maltodextrin can be used, and the aldehyde end groups can be eliminated at the end of the reaction by treatment with sodium borohydride (as shown in examples 10-12) or hydrogenation (as exemplified in example 24) of the aldehyde end groups to form alcohol end groups. In one embodiment, conventional oligosaccharides and polysaccharides such as corn syrup and maltodextrin may be used, and the aldehyde end groups may be eliminated by oxidizing the aldehyde groups to form carboxylic acid end groups at the end of the reaction.

Such synthetic polymers, such as hybrid copolymers or graft copolymers, may be prepared in a manner currently known to those skilled in the art, for example, from at least one hydrophilic acid monomer as a synthetic component. Examples of such hydrophilic acid monomers include, but are not limited to, acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylate, beta-methacrylic acid (crotonic acid), alpha-phenylacrylic acid, beta-acryloxypropionic acid, sorbic acid, alpha-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid, beta-styrylacrylic acid (1-carboxy-4-phenyl-1, 3-butadiene), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxyethylene, 2-acryloxypropionic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, sodium methallylsulfonate, sulfonated styrene, allyloxybenzenesulfonic acid, and maleic acid. Moieties derivable into acid-containing groups such as maleic anhydride or acrylamide may be used. Combinations of acid-containing hydrophilic monomers may also be used. In one aspect, the acid-containing hydrophilic monomer is acrylic acid, maleic acid, itaconic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, or mixtures thereof.

In a preferred embodiment, the synthetic polymer is free of polyacrylamide.

In addition to the above hydrophilic monomers, hydrophobic monomers may be used as synthetic components. Such hydrophobic monomers include, for example, ethylenically unsaturated monomers having saturated or unsaturated alkyl, hydroxyalkyl, alkylalkoxy, arylalkoxy, alkylarylalkoxy, aryl, and aryl-alkyl groups, alkylsulfonates, arylsulfonates, siloxanes, and combinations thereof. Examples of the hydrophobic monomer include styrene, α -methylstyrene, methyl methacrylate, methyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl acrylamide, octyl acrylamide, lauryl acrylamide, stearyl acrylamide, behenyl acrylamide, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzyl styrene and 4- (phenylbutyl) styrene. Combinations of hydrophobic monomers may also be used.

The polymerization process may be a solution, dispersion or self-stabilizing emulsion or suspension process. The process involves polymerization with one or more of the above hydrophilic and/or hydrophobic monomers using a free radical initiator and a hydroxyl-containing natural product (e.g., a monosaccharide, oligosaccharide or polysaccharide, such as a sugar, maltodextrin or starch) that acts as a chain transfer agent or chain terminator. These chain transfer agents may be added at the beginning of the reaction or as the monomer is added during the reaction.

Polysaccharides useful in the present disclosure (i.e., in this embodiment, as well as in other embodiments) may be derived from plant, animal, and microbial sources. Examples of such polysaccharide sources include starch, cellulose, gums (e.g., gum arabic, guar gum, and xanthan gum), alginates, pectins, and gellan gum. Starches include those derived from corn and conventional corn hybrids, such as waxy corn and high amylose (i.e., amylose greater than 40%) corn, as well as other starches such as potato, tapioca, wheat, rice, pea, sago, oat, barley, rye and amaranth (amaranth), including conventional hybrids or genetically engineered materials. Hemicellulose or plant cell wall polysaccharides such as D-xylan are also included. Examples of plant cell wall polysaccharides include arabinoxylans (arabino-xylan) such as corn fiber gums (which are a component of corn fibers).

In one embodiment, the useful polysaccharide is water-soluble. This means that the polysaccharide either has a molecular weight low enough to be water-soluble or can be hydrolyzed in situ during the reaction to become water-soluble. For example, undegraded starch is insoluble in water. However, degraded starch is water soluble and may be used.

Hydroxyl-containing natural materials (monosaccharides, oligosaccharides and polysaccharides) can be degraded oxidatively, hydrolytically or enzymatically. In general, degraded polysaccharides according to the present disclosure can have a number average molecular weight (Mn) of about 100,000 or less. In one aspect, the hybrid copolymer has a number average molecular weight of about 25,000 or less. In another aspect, the degraded polysaccharide has a number average molecular weight of about 10,000 or less.

These mono-, oligo-and polysaccharides may optionally be chemically modified. Chemically modified derivatives include carboxylic acid esters, sulfonic acid esters, phosphoric acid esters, phosphonic acid esters, aldehydes, silanes, alkyl glycosides, alkyl hydroxyalkyl compounds (alkyl-hydroxy-alkyl) and carboxy-alkyl ethers and other derivatives. The polysaccharide may be chemically modified before, during or after the polymerization reaction.

Oligosaccharides useful in the present disclosure include corn syrup. Corn syrup is defined as a degraded starch product having a DE of 27 to 95. Examples of specialty corn syrups include high fructose corn syrup and high maltose corn syrup. Monosaccharides and disaccharides such as galactose, mannose, sucrose, maltose, ribose, trehalose, and lactose may also be used.

Other polysaccharides useful in the present disclosure include maltodextrins, which are polymers having D-glucose units linked primarily by alpha-1, 4 linkages and a dextrose equivalent ("DE") of less than about 20. Maltodextrin is available as a white powder or concentrated solution and is prepared by partial hydrolysis of starch with acid and/or enzymes. Maltodextrin generally has a distribution of chain lengths depending on the number of repeating units of anhydrous dextrose. The number of repeating units may be from 1 to more than 10. (e.g., a DE of about 20 will have about 5 repeat units, a DE of 100 corresponds to about 1 repeat unit, and a DE of 1 corresponds to about 100 repeat units.) in maltodextrin, a greater weight fraction of the sample has more than 10 anhydroglucose repeat units. Thus, conventionally, maltodextrins are considered polysaccharides, even though they may have a composition falling within the definition of oligosaccharides.

Polysaccharides useful in the present disclosure also include pyrodextrins. Pyrodextrins are prepared by heating acidified, commercially available dry starch to an elevated temperature. Due to the usual presence of moisture in starch, deep degradation initially occurs. However, unlike the above-described reaction in an aqueous solution, pyrodextrins are formed by heating powders. When the water is driven off by heating, the hydrolysis is stopped and the hydrolysed starch fragments recombine. This recombination reaction makes these materials different from maltodextrin, which is a hydrolyzed starch chip. The resulting pyrodextrin products also have a much lower reducing sugar content, as well as color and unique odor.

The polysaccharide may be modified or derivatized by etherification (e.g., via treatment with propylene oxide, ethylene oxide, 2, 3-epoxypropyltrimethylammonium chloride), esterification (e.g., via reaction with acetic anhydride, octenyl succinic anhydride ('OSA'), acid hydrolysis, paste refining, oxidation, or enzymatic treatment (e.g., starch modified with alpha-amylase, beta-amylase, pullulanase, isoamylase, or glucoamylase), or various combinations of these treatments. These treatments may be performed before or after the polymerization process.

The weight of the natural component may range from 10 to 98 weight percent of the total weight of the copolymer. In one embodiment, the natural component is 20 to 95 weight percent of the total weight of the copolymer. In another embodiment, the natural component is 25 to 90 weight percent of the total weight of the copolymer. In another embodiment, the natural component is 30 to 85 weight percent of the total weight of the copolymer. In another embodiment, the natural component is 35 to 80 weight percent of the total weight of the copolymer.

The artificial polymers are hybrid polymers or graft polymers, the main difference being their initiation systems. Hybrid polymers are synthesized using "hybrid initiators" which are free radical initiators or initiator systems that do not include metal ion based initiators or initiator systems. While not being bound by theory, the hybrid initiator is preferably not a radical extractant but rather promotes chain transfer. Furthermore, in one embodiment of the present disclosure, the hybrid initiator is water soluble. Exemplary hybrid initiators include, but are not limited to, peroxides, azo initiators, and redox systems, like t-butyl hydroperoxide and isoascorbic acid, peroxides such as persulfates and amines such as hydroxylamine sulfate, persulfates and sodium formaldehyde sulfoxylate, and the like. The hybrid initiator may include both inorganic and organic peroxides. Suitable inorganic peroxides include sodium persulfate, potassium persulfate, and ammonium persulfate. Azo initiators, such as water-soluble azo initiators, may also be suitable hybrid initiators. Inorganic peroxides such as persulfates are preferred initiation systems for hybrid polymers.

The initiator or initiator system used to produce the graft copolymer is typically a redox system of metal ions and hydrogen peroxide. These initiating systems will extract protons from the natural hydroxyl-containing component, thereby facilitating the grafting reaction. Graft copolymers, on the other hand, are prepared using redox free radical initiation systems such as metallic iron and peroxides. Metal ions include, but are not limited to, iron, copper, vanadium, and the like, which are capable of forming redox systems with peroxides. Peroxides include, but are not limited to, hydrogen peroxide, inorganic peroxides such as persulfates, and combinations thereof; see, wurzburg, O.B., modified Starches: properties and Uses, grafted starch, chapter 10, pages 149-72, CRC Press, boca Raton (1986)). Other initiation systems include ceric ammonium nitrate. While not being bound by theory, the graft copolymers are produced by selectively generating initiation sites (e.g., free radicals) to grow monomer side chains from an existing polymer backbone (CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, J.I.Kroschwitz, editions, wiley-Interscience, new York, page 436 (1990). Preferred initiation systems for the graft copolymers are iron and hydrogen peroxide and mixtures of iron and hydrogen peroxide with persulfates.

The synthetic polymer is substantially free of phosphorus moieties. These phosphorus fractions lead to eutrophication of bodies of water such as lakes, rivers and oceans and are not preferred. Thus, in one embodiment, the synthetic polymer is completely free of phosphorus moieties. In another embodiment, the phosphorus is not present in any starting material used to prepare the artificial polymer and/or is not a component of any agent used in any process for preparing the artificial polymer, nor is it a component of any additive that is combined with or used to further carry out the post-polymerization of the artificial polymer. Thus, for example, in one embodiment, a water-soluble phosphorus compound such as phosphorous acid or a salt thereof is not added to the polymer for color stabilization purposes or for any other reason.

In yet another aspect, the present disclosure relates to a blend of an artificial polymer and a builder or chelating agent. Exemplary chelating agents suitable for use in the present invention include, but are not limited to, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal citrates, alkali metal or alkaline earth metal silicates, glutamic acid N, N-diacetic acid (GLDA), methylglycine N, N-diacetic acid (MGDA), and combinations thereof. In one embodiment according to the present disclosure, the blend may be particles containing a homogeneous dispersion of the artificial polymer and the builder or chelating agent. The particles may also be powders or granules.

In yet another aspect, the present disclosure relates to an artificial polymer containing both anionic and cationic groups, thereby rendering the artificial polymer amphoteric. The anionic moiety may be located on the naturally derived hydroxyl containing chain transfer agent and the cationic moiety may be located on the synthetic component, or the cationic moiety may be located on the naturally derived hydroxyl containing chain transfer agent and the anionic moiety may be located on the synthetic component, or a combination thereof. When the natural component is a polysaccharide, the anionic material may be oxidized starch and the cationic moiety may be derived from a cationic ethylenically unsaturated monomer such as diallyldimethylammonium chloride. Alternatively, the oxidized starch itself may be reacted first with a cationic substituent such as 3-chloro-2-hydroxypropyl trimethylammonium chloride and then with a synthetic anionic or cationic monomer or mixture thereof. In another embodiment, the cationic starch may be reacted with an anionic monomer. Finally, cationic and anionic moieties may be located on the synthetic components of these polymers, in which case one monomer is anionic and the other monomer is cationic. These synthetic polymers are particularly useful in hard surface cleaning applications. It will be appreciated that these polymers will contain both natural and synthetic components. The cationic moiety is preferably present in the range of 0.001 to 40 mole% of the anionic moiety, more preferably the cationic moiety is present in the range of 0.01 to 20 mole% of the anionic moiety, and most preferably the cationic moiety is present in the range of 0.1 to 10 mole% of the anionic moiety.

In another aspect, this aspect of the disclosure relates to an artificial polymer containing at least one non-anionic ethylenically unsaturated monomer. As used herein, non-anionic ethylenically unsaturated monomers include those that are non-anionic. That is, these non-anionic ethylenically unsaturated monomers may include, but are not limited to, cationic ethylenically unsaturated monomers, nonionic ethylenically unsaturated monomers, amphoteric ethylenically unsaturated monomers, and zwitterionic ethylenically unsaturated monomers, and mixtures thereof. As used herein, an artificial polymer comprises a synthetic polymer produced from at least one cationic ethylenically unsaturated monomer or at least one nonionic ethylenically unsaturated monomer grafted onto a natural hydroxyl-containing component.

As used herein, the term "cationic ethylenically unsaturated monomer" refers to an ethylenically unsaturated monomer capable of introducing a positive charge to a non-anionic graft copolymer composition. Examples of cationic monomers include, but are not limited to, acrylamidopropyl trimethyl ammonium chloride (APTAC), methacrylamidopropyl trimethyl ammonium chloride (MAPTAC), diallyl dimethyl ammonium chloride (DADMAC), acryloyloxyethyl trimethyl ammonium chloride (AETAC), methacryloyloxyethyl trimethyl ammonium chloride. In one embodiment of the present disclosure, the cationic ethylenically unsaturated monomer has at least one amine functional group. The cationic derivatives of these non-anionic grafted dendritic copolymers may be formed by forming amine salts of all or part of the amine functions, by quaternizing all or part of the amine functions to form quaternary ammonium salts, or by oxidizing all or part of the amine functions to form N-oxide groups.

As used herein, the term "amine salt" refers to the amine functional group nitrogen atom covalently bonded to one to three organic groups and associated with an anion.

As used herein, the term "quaternary ammonium salt" refers to the amine functional group nitrogen atom covalently bonded to four organic groups and associated with an anion. These cationic derivatives can be synthesized by functionalizing the monomer prior to polymerization or functionalizing the polymer after polymerization. These cationic ethylenically unsaturated monomers are, howeverNot limited to N, N-dialkylaminoalkyl (meth) acrylates, N-alkylaminoalkyl (meth) acrylates, N-dialkylaminoalkyl acrylamides, N-dialkylaminoalkyl (meth) acrylamides, and N-alkylaminoalkyl (meth) acrylamides, wherein alkyl is independently C _1-18 Cyclic compounds such as 1-vinylimidazole and the like. Monomers containing aromatic amines, such as vinyl pyridine, may also be used. In addition, monomers that generate amine moieties upon hydrolysis, such as vinylformamide, vinylacetamide, and the like, may also be used. Preferably, the cationic ethylenically unsaturated monomers are N, N-dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate and N, N-dimethylaminopropyl methacrylamide. In one embodiment of the present disclosure, the amine monomer is selected from the group consisting of N, N-dimethylaminoethyl methacrylate, N-dimethylaminopropyl methacrylamide and N, N-diethylaminoethyl methacrylate. In one embodiment, the vinylpyridine and other amine monomers may be oxidized or quaternized.

In a preferred embodiment, the synthetic polymer is free of monomers such as vinylformamide, vinylacetamide, etc., which upon hydrolysis generate primary amine moieties.

The cationic ethylenically unsaturated monomers that can be used are quaternized derivatives of the above monomers, diallyldimethylammonium chloride (also known as dimethyldiallylammonium chloride), acrylamidopropyltrimethylammonium chloride, 2- (meth) acryloyloxyethyl trimethylammonium sulfate, 2- (meth) acryloyloxyethyl trimethylammonium chloride, N-dimethylaminoethyl (meth) acrylate methylammonium chloride (Dimethylaminoethyl (meth) acrylate methyl chloride quaternary), methacryloyloxyethyl betaine and other betaines and sulfobetaines, 3- (meth) acryloyloxyethyl dimethylammonium hydrogen acetate, 2- (meth) acryloyloxyethyl dimethylhexadecylammonium chloride, 2- (meth) acryloyloxyethyl diphenylammonium chloride, and the like. In one embodiment, suitable cationic ethylenically unsaturated monomers for use in the present disclosure are N, N-dialkylaminoalkyl (meth) acrylates, N-dialkylaminoalkyl acrylamides, and quaternized derivatives of N, N-dialkylaminoalkyl (meth) acrylamides. Those skilled in the art will recognize that these may be quaternized with methyl chloride (as described above), but they may also be quaternized with dimethyl sulfate, diethyl sulfate, ethyl chloride and benzyl chloride, as well as other quaternizing agents.

As used herein, the term "nonionic ethylenically unsaturated monomer" refers to an ethylenically unsaturated monomer that does not introduce a charge into the artificial polymer. These nonionic ethylenically unsaturated monomers include, but are not limited to, C of (meth) acrylic acid ₁ -C ₆ Alkyl esters and their alkali metal or alkaline earth metal or ammonium salts, acrylamides and C ₁ -C ₆ Alkyl-substituted acrylamides, N-alkyl-substituted acrylamides and N-alkanol-substituted acrylamides, hydroxyalkyl acrylates and acrylamides. Also suitable are C's of unsaturated ethylene acids such as maleic acid and itaconic acid ₁ -C ₆ Alkyl esters and C ₁ -C ₆ Alkyl half esters, C of saturated aliphatic monocarboxylic acids such as acetic acid, propionic acid and valeric acid ₁ -C ₆ Alkyl esters. In embodiments, the nonionic ethylenically unsaturated monomer is selected from the group consisting of acrylamides, methacrylamides, N-alkyl (meth) acrylamides, N-dialkyl (meth) acrylamides such as N, N-dimethylacrylamides, hydroxyalkyl (meth) acrylates, alkyl (meth) acrylates such as methyl acrylate and methyl methacrylate, vinyl acetate, vinyl morpholine, vinyl pyrrolidone, vinyl caprolactam, ethoxylated alkyl, alkylaryl or aryl monomers such as methoxypolyethylene glycol (meth) acrylate, allyl glycidyl ether, allyl alcohol, glycerol (meth) acrylate, monomers containing silane, silanol and siloxane functionalities, and the like. The nonionic ethylenically unsaturated monomer is preferably water soluble. In one other embodiment, the nonionic ethylenically unsaturated monomer is selected from the group consisting of acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-dimethyl (meth) acrylamide, methyl methacrylate, methyl acrylate, hydroxyethyl (meth) acrylate, and (meth) ) Hydroxypropyl acrylate, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide and acryloylmorpholine, vinylpyrrolidone and vinylcaprolactam.

Enzymatic degradation of starch

In one embodiment, the polymer precursor mixture comprises enzymatically degraded starch. In a preferred embodiment, degradation of starch or starch derivatives to their alpha limit by alpha-amylase results in periodic digestion of the polysaccharide, resulting in a narrow range of digested fragments. Enzymatic degradation maximizes the degree of oligomerization (DP) or the number of repeat units 4, 5, 6 content while minimizing the DP1 and 2 content to improve anti-redeposition performance (as shown in example 39) and carbonate inhibition performance (as shown in example 40) when used in hybridization reactions.

The enzymatically degraded starch preferably has a sum of DP1 and DP2 of less than 30, more preferably less than 25, more preferably less than 20 and most preferably less than 16, and preferably the sum of DP4, 5 and 6 is greater than 15, more preferably greater than 25, more preferably greater than 30 and most preferably greater than 35.

When these digested fragments are introduced sequentially into the polymer precursor mixture, they are incorporated into the man-made polymer in a subsequent polymerization. Hybrid polymers incorporating enzymatically degraded polysaccharides with the specific distribution properties described above impart performance advantages, including improved anti-redeposition in laundry and improved calcium carbonate inhibition, which provide better anti-scaling in laundry and minimize filming in automatic dishwashing applications.

Most polysaccharides from any source can be degraded in the manner contemplated herein, including, for example, waxy corn and dent corn starch, potato starch, wheat starch, sago starch, pea starch, tapioca starch, and maltodextrin, from DE 1 to DE 24, or DE 1 to DE 18, or DE 1 to DE 10, or DE 1 to DE 5.

If raw starch is the starting material, the starch granules may be swollen and broken up prior to enzymatic degradation by a number of methods known to those skilled in the art, including spraying or batch cooking.

Many enzymes are useful for degrading polysaccharides, including alpha-and beta-amylases, glucoamylases, and pullulanases, with alpha-amylases being preferred for the present disclosure. Any of these enzymes may be used alone or in combination with other enzymes and the degree of degradation is controlled using techniques known to those skilled in the art. Preferred embodiments utilize alpha-amylase to produce alpha-limit dextrins (i.e., materials that have undergone complete degradation until no significant change in molecular weight distribution occurs). Degradation is typically carried out in starch dispersions or aqueous solutions, with the polysaccharide concentration (on a dry basis) being selected to facilitate handling and subsequent polymerization. The reaction temperature is typically between 50 and 100 ℃, but lower temperatures may also be used.

Although the pH will be adjusted based on the particular enzyme solution used, if an alpha-amylase is used, the pH of the dispersion or solution will typically be about pH 5.5-6.5. This can be achieved by conditioning with an acid or base or a buffer solution can be used.

Calcium may be added to the dispersion or solution, typically in an amount of 50-100ppm based on the weight of the dispersion/solution. Those skilled in the art will recognize that the action of some enzymes may benefit from the presence of calcium. Calcium is typically present in millimole amounts and can stabilize the enzyme against heat. In any process involving enzymatic degradation of starch, consideration should be given to whether calcium is required as well as the amount of calcium.

The amount of enzyme dosed to the starch dispersion or solution will depend on the batch material used and the strength of the particular enzyme material. The amount of enzyme used and the amount of cooking time in the presence of the enzyme may vary, but is generally selected to be sufficient to bring the enzyme-catalyzed hydrolysis to the alpha limit. Sometimes, kilo Novo Units (KNU) are used as a measure of the expected degradation of a given amount of starch material under given conditions. 1KNU (T) is the amount of alpha-amylase that gelatinizes 5.26g of starch dry matter (Merck Amylum soluble No.9947275 or equivalent) per hour under standard conditions (pH 7.1;37 ℃).

The action of the enzyme may be terminated by lowering the pH to about pH 5 or less, for example, with an acid. In most reactions, the addition of acrylic acid to initiate the polymerization reaction will prevent enzymatic degradation.

Aldehyde elimination

As discussed herein, it has been found that aldehyde functionality in the sugar terminal group moiety results in color instability of the resulting polymer. We have further found that colour stability can be significantly enhanced by eliminating such aldehyde functions. Any suitable method of doing so is contemplated, as long as the elimination does not result in a significant reduction in the end-use performance of the artificial polymer.

In one embodiment, the aldehyde functionality is converted to an alcohol functionality by treatment with a suitable reducing agent.

In another embodiment, the aldehyde functionality is converted to an alcohol functionality by treatment or hydrogenation with sodium borohydride or lithium aluminum hydride. Hydrogenation is typically carried out with hydrogen in the presence of a catalyst such as nickel, platinum or palladium.

In one embodiment, the aldehyde functionality is converted to carboxylic acid functionality by treatment with a suitable oxidizing agent.

In another embodiment, the aldehyde functionality is converted to a carboxyl functionality by oxidation, which may involve treatment with hydrogen peroxide, potassium permanganate, potassium chromate. Those skilled in the art will recognize that other oxidants may be used.

Other methods of eliminating aldehyde end groups include addition of grignard reagents, aldol condensation, reaction with amines, and the like. Those skilled in the art are generally familiar with such methods and understand how to use them in the context of this disclosure.

Preferred methods are reduction and oxidation. Most preferred is the reduction to an alcohol using sodium borohydride or hydrogenation.

Color control during polymerization

In one embodiment, the color is controlled during the polymerization by one or a combination of polyols or hydrogenated starch hydrolysates as natural components, judicious choice of the amount of initiator and the way the initiator is added and/or controlling the pH. These factors serve to minimize depolymerization of the polyol during the polymerization process to give the advantage of minimizing formulation color development during alkaline storage, where most of the color development occurs. In addition, small amounts of hydrogen peroxide and/or vinyl acetate as comonomers can be used in combination with the other means described above, but the two additives themselves have little effect on color, especially when stored under alkaline conditions. It is very important to note that while the initial color of the polymer may be light, as evidenced by the use of some hydrogen peroxide, the color may darken under alkaline storage conditions when hydrogen peroxide is used alone. The goal is to minimize or eliminate color, especially under long-term alkaline storage conditions, since most formulations are in the alkaline region.

Commercially available polyols have very low levels of aldehyde end groups and in most cases are free of aldehyde end groups. It is therefore important to minimize or eliminate depolymerization of the polyol during the polymerization reaction, as this would result in aldehyde end groups. This is achieved by controlling the pH during polymerization in combination with initiator control. A pH below 3.5 or 4 will result in depolymerization of the polyol during the reaction. Alkaline pH may initiate maillard reactions that darken the product upon polymerization and are therefore not preferred. The preferred pH range for polymerization is between 3.5 and 8, preferably 4.5 and 7.5 and most preferably 4 and 7. The pH is maintained by feeding a neutralizing agent such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and mixtures thereof slowly, optionally simultaneously with the monomer. Controlling the amount of initiator and its feed time as compared to the monomer is also critical to minimize the polyol polymerization while ensuring that the monomer is polymerized. This is demonstrated by the reduction in the amount of persulfate initiator in example 1 as illustrated in examples 2, 3 and 4, with a further reduction in color in proportion to the reduction in persulfate initiator as illustrated by the alkaline aging test in example 5. Reducing the initiator and shortening its addition time compared to the monomer can minimize depolymerization of the polyol, which results in additional aldehyde end groups, especially when the initiator is added after monomer feed or is present due to a long half-life at reaction temperature. Those skilled in the art will recognize that the reaction temperature plays an important role. The initiator needs to be present at the end of the monomer feed and this is determined by the half-life of the initiator at that temperature. The initiator feed may be shortened to ensure conversion of the monomers and to minimize any excess initiator after all monomers are converted to polymer, as this excess initiator may subsequently depolymerize the polyol. The color of the solution of example 4 was about one order of magnitude lower than the color of the solution of example 1 and about two orders of magnitude lower than the color of the solution of comparative example 1. These examples demonstrate that the initiator feed can be controlled to minimize depolymerization of the polyol while ensuring that the monomer is polymerized as indicated by the conversion of the monomer in these samples.

In addition, hydrogen peroxide may be contained in the initial reactor charge and/or in the slow initiator feed or as a post-treatment, as it may oxidize some of the colored impurities in the system. However, the use of hydrogen peroxide in the presence of metal ions such as iron (Fe) is not recommended because very reactive hydroxyl radicals are generated. These hydroxyl radicals are very reactive and facilitate the polymerization of inert monomers such as maleic acid. However, they have the disadvantage of strongly depolymerizing the polyol and generating a large number of aldehyde end groups during polymerization, which is contrary to the purpose of using expensive polyols. In one embodiment, hydrogen peroxide is contained only in the initial reactor charge. In this embodiment, the amount of hydrogen peroxide is from 1 to 10 wt%, preferably from 1.5 to 8 wt%, and most preferably from 2 to 5 wt%, based on the total mass of polysaccharide and water present in the initial feed. In another embodiment, hydrogen peroxide is contained only in the slow initiator feed. In this embodiment, the amount of hydrogen peroxide is from 1 to 12 wt%, preferably from 1.5 to 10 wt%, and most preferably from 2 to 8 wt%, based on the mass of polysaccharide used. In yet another embodiment, hydrogen peroxide is contained in both the initial reactor charge and the slow initiator feed. In this embodiment, the hydrogen peroxide introduced into the initial reactor charge is from 1 to 10 wt%, preferably from 1.5 to 8 wt%, and most preferably from 1.8 to 5 wt%, based on the total mass of polysaccharide and water present in the initial charge; the hydrogen peroxide is introduced into the slow initiator feed in an amount of 0.01 to 12 wt.%, more preferably 1 to 10 wt.%, and most preferably 1.5 to 8 wt.%, based on the mass of polysaccharide used. We have found that it is desirable to add hydrogen peroxide during initial heating after the reactor has reached at least 60 ℃, preferably at least 20 ℃ and more preferably at least 35 ℃.

As with hydrogen peroxide described above, vinyl acetate has been used to minimize color, especially when used in combination with polyols, pH control, and initiator feed control. We have found that the substitution of vinyl acetate for small amounts of polymer weight (typically less than 5%, preferably less than 2%, most preferably less than 1% of the total monomer is required) has an unexpected positive effect on color retention during the reaction. For example, if the polymer is a 50/50 weight percent mixture of acrylic acid and polyol, the new polymer will be 48/2/50 (based on weight percent) acrylic acid/vinyl acetate/polyol.

In a preferred embodiment, the use of polyols and pH control in combination with judicious choice of the amount of initiator and the manner of addition of the initiator are alternative techniques to minimize reaction discoloration, with the addition of hydrogen peroxide and/or the inclusion of vinyl acetate being employed as the case may be.

Color control after polymerization

If a polyol is used during polymerization and appropriate measures are taken to ensure that depolymerization is minimized during the polymer reaction, a post-treatment may not be required, but may be included if desired.

If conventional maltodextrins and corn syrups are used in the polymerization reaction, the aldehyde end groups must be minimized after polymerization. This is accomplished by reducing the aldehyde terminal group to an alcohol or oxidizing it to a carboxylic acid. We have found that reduction to alcohol is easier to carry out. The reduction is generally carried out by adding a reducing agent such as sodium borohydride, lithium aluminum hydride, sodium cyanoborohydride and a dithionite, for example sodium dithionite, potassium dithionite or zinc dithionite. The preferred reducing agent is sodium borohydride. In addition, the aldehyde terminal groups can be reduced by reaction with hydrogen. The reaction with hydrogen is typically carried out in the presence of a metal catalyst such as nickel. When sodium borohydride is used as reducing agent, the pH of the polymer solution is generally raised to 7-9 and the borohydride is added over 0.5-2 hours at 30-50℃and the temperature is maintained for an additional 1-3 hours with stirring. Qualitative color testing as shown in example 5 can be performed and additional borohydrides can be added if desired to meet predetermined basic aging color requirements or a certain amount of aldehyde end groups. This is illustrated in example 46, where the first amount of borohydride added is insufficient to give a sufficiently light color in a quick test that simulates alkaline aging conditions, and then additional borohydride is added to meet the desired color specification. The borohydride solution typically contains sodium hydroxide and the final pH of the polymer solution can be very high and can be adjusted to a pH range of 7-10 using a suitable acid such as sulfuric acid as exemplified in examples 10-12. Similarly, as illustrated in example 24, the reduction can be performed with hydrogen in the presence of a metal catalyst to a predetermined basic aging color requirement or amount of aldehyde end groups. Typical oxidants such as hydrogen peroxide and periodate can be used to convert aldehyde end groups to carboxylic acid end groups.

End use applications and formulations

The synthetic polymers described herein are typically solution polymers that are used to minimize fouling and act as dispersants in a variety of end use applications, principally cleaning applications, laundry, automatic dishwashing, and hard surface cleaning.

A subset of these molecules are emulsion polymers and can be used as rheology modifiers.

Cleaning applications

The artificial polymers according to the present disclosure may be used in a variety of cleaning formulations. Such formulations include powder and liquid laundry formulations such as concentrated and heavy duty detergents (e.g., builders, surfactants, enzymes, etc.), automatic dishwashing detergent formulations (e.g., builders, surfactants, enzymes, etc.), light duty liquid formulations, rinse aid formulations (e.g., acids, nonionic low foaming surfactants, carriers, etc.), and/or hard surface cleaning formulations (e.g., zwitterionic surfactants, bactericides, etc.).

The synthetic polymers are useful as viscosity reducers in process powder detergents. They can also be used as anti-redeposition agents, dispersants, scale inhibitors and deposition inhibitors, as well as crystal modifiers, to provide whiteness maintenance during laundering.

Any suitable auxiliary ingredient in any suitable amount may be used in the cleaning formulations described herein. Useful adjunct ingredients include, for example, aesthetic agents, anti-filming agents, anti-redeposition agents, anti-soil agents, anti-ash agents, beads, binders, bleach activators, bleach catalysts, bleach stabilization systems, bleaches, brighteners, buffers, builders, carriers, chelants, clays, stains, controlled release agents, corrosion inhibitors, dish care agents, disinfectants, dispersants, drainage promoters, drying agents, dyes, dye transfer inhibitors, enzymes, enzyme stabilization systems, fillers, radical inhibitors, fungicides, bactericides, hydrotropes, opacifiers, perfumes, pH adjusting agents, pigments, processing aids, silicates, soil release agents, suds suppressors, surfactants, stabilizers, thickening agents, zeolites, and mixtures thereof.

The cleaning formulations may also include builders, enzymes, surfactants, bleaching agents, bleach modifying materials, carriers, acids, corrosion inhibitors and aesthetic agents. Suitable builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphoric acid; alkali metal silicates, alkaline earth metal and alkali metal carbonates, nitrilotriacetic acid, polycarboxylates (such as citric acid, mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3, 5-tricarboxylic acid, carboxymethyl oxydisuccinic acid and water-soluble salts thereof), phosphates (e.g., sodium tripolyphosphate), and mixtures thereof. Suitable enzymes include, but are not limited to, proteases, amylases, cellulases, lipases, carbohydrases, bleaching enzymes, cutinases, esterases, and wild-type enzymes. Suitable surfactants include, but are not limited to, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. Suitable bleaching agents include, but are not limited to, common inorganic/organic chlorine bleaching agents (e.g., sodium or potassium dichloroisocyanurate dihydrate, sodium hypochlorite (sodium hypochlorite), sodium hydrochloride (sodium hypochloride)), hydrogen peroxide releasing salts such as sodium perborate monohydrate (PB 1), sodium perborate tetrahydrate (PB 4), sodium percarbonate, sodium peroxide, and mixtures thereof. Suitable bleach modifying materials include, but are not limited to, hydrogen peroxide source bleach activators (e.g., TAEDs), bleach catalysts (e.g., transition metals including cobalt and manganese). Suitable carriers include, but are not limited to: water, low molecular weight organic solvents (e.g., primary alcohols, secondary alcohols, monohydric alcohols, polyhydric alcohols, and mixtures thereof), and mixtures thereof.

Suitable acids include, but are not limited to, acetic acid, aspartic acid, benzoic acid, boric acid, hydrobromic acid, citric acid, formic acid, gluconic acid, glutamic acid, hydrochloric acid, lactic acid, malic acid, nitric acid, sulfamic acid, sulfuric acid, tartaric acid, and mixtures thereof. Suitable corrosion inhibitors include, but are not limited to, soluble metal salts, insoluble metal salts, and mixtures thereof. Suitable metal salts include, but are not limited to, aluminum, zinc (e.g., hydrozincite), magnesium, calcium, lanthanum, tin, gallium, strontium, titanium, and mixtures thereof. Suitable aesthetic agents include, but are not limited to, opacifiers, dyes, pigments, stains, beads, whitening agents, and mixtures thereof.

By adding suitable adjunct agents, the cleaning formulations described herein can be used as automatic dishwashing detergent ("ADD") compositions (e.g., builders, surfactants, enzymes, etc.), light duty liquid dishwashing compositions, laundry compositions such as concentrated and heavy duty detergents (e.g., builders, surfactants, enzymes, etc.), rinse aid compositions (e.g., acids, nonionic low foaming surfactants, carriers, etc.), and/or hard surface cleaning compositions (e.g., zwitterionic surfactants, bactericides, etc.).

Suitable adjunct ingredients are disclosed in one or more of the following: U.S. Pat. nos. 2,798,053;2,954,347;2,954,347;3,308,067;3,314,891;3,455,839;3,629,121;3,723,322;3,803,285;3,929,107,3,929,678;3,933,672;4,133,779,4,141,841;4,228,042;4,239,660;4,260,529;4,265,779;4,374,035;4,379,080;4,412,934;4,483,779;4,483,780;4,536,314;4,539,130;4,565,647;4,597,898;4,606,838;4,634,551;4,652,392;4,671,891;4,681,592;4,681,695;4,681,704;4,686,063;4,702,857;4,968,451;5,332,528;5,415,807;5,435,935;5,478,503;5,500,154;5,565,145;5,670,475;5,942,485;5,952,278;5,990,065;6,004,922;6,008,181;6,020,303;6,022,844;6,069,122;6,060,299;6,060,443;6,093,856;6,130,194;6,136,769;6,143,707;6,150,322;6,153,577;6,194,362;6,221,825;6,365,561;6,372,708;6,482,994;6,528,477;6,573,234;6,589,926;6,627,590;6,645,925; and 6,656,900; international publication No. 00/23548;00/23549;00/47708;01/32816;01/42408;91/06637;92/06162;93/19038;93/19146;94/09099;95/10591;95/26393;98/35002;98/35003;98/35004;98/35005;98/35006;99/02663;99/05082;99/05084;99/05241;99/05242;99/05243;99/05244;99/07656;99/20726; and 99/27083; european patent No. 130756; uk publication No. 1137741 a; chemtech, pp.30-33 (3 months 1993); american Chemical Soc.,115,10083-10090 (1993); and Kirk Othmer Encyclopedia of Chemical Technology, 3 rd edition, volume 7, pages 430-447 (John Wiley & Sons, inc., 1979).

In one embodiment, a cleaning formulation according to the present disclosure may comprise suitable adjunct ingredients in an amount of from 0% to about 99.99% by weight of the formulation. In another aspect, the cleaning formulation may comprise from about 0.01% to about 95% by weight of the formulation of suitable adjunct ingredients. In other various aspects, the cleaning formulation may comprise from about 0.01% to about 90%, or from about 0.01% to about 80%, or from about 0.01% to about 70%, or from about 0.01% to about 60%, or from about 0.01% to about 50%, or from about 0.01% to about 40%, or from about 0.01% to about 30%, or from about 0.01% to about 20%, or from about 0.01% to about 10%, or from about 0.01% to about 5%, or from about 0.01% to about 4%, or from about 0.01% to about 3%, or from about 0.01% to about 2%, or from about 0.01% to about 1%, or from about 0.01% to about 0.5%, or from about 0.01% to about 0.1% by weight of a suitable adjunct ingredient.

The cleaning formulation may be provided in any suitable physical form. Examples of such forms include solids, particles, powders, liquids, pastes, creams, gels, liquid gels, and combinations thereof. Cleaning formulations for use herein include unitized doses in any of a variety of forms, such as tablets, multi-phase tablets, gel packs, capsules, multi-compartment capsules, water-soluble pouches or multi-compartment pouches. The cleaning formulation may be dispensed from any suitable device. Suitable devices include, but are not limited to, wipes, gloves, boxes, baskets, bottles (e.g., pourable bottles, pump assisted bottles, squeeze bottles), multi-compartment bottles, jars, paste dispensers, and combinations thereof.

In case the additive or multicomponent product is contained in a single-and/or multi-compartment bag, capsule or bottle, it is not required that the auxiliary ingredient or the cleaning formulation is in the same physical form. In one non-limiting embodiment, the cleaning formulation may be provided in the form of a multi-compartment, water-soluble pouch containing both solid and liquid or gel components in unit dosage form. The use of different forms may allow for controlled release (e.g., delayed, sustained, triggered, or slow release) of the cleaning formulation during surface treatment (e.g., during one or more wash and/or rinse cycles in an automatic dishwasher).

When the formulations are diluted to a 1% solution, the pH of these formulations may be from 1 to 14. Most formulations are neutral or alkaline, i.e., have a pH of 7 to about 13.5. However, certain formulations may be acidic, meaning that the pH is from 1 to about 6.5.

The copolymers according to the present disclosure may also be used in a variety of cleaning formulations containing builders. These formulations may be in the form of powders, liquids or unit doses (such as tablets or capsules) and may be used to clean a variety of substrates (such as clothing, cutlery) as well as hard surfaces (such as bathroom and kitchen surfaces). The formulations are also useful for cleaning surfaces in industrial and institutional cleaning applications.

In the cleaning formulation, the polymer may be diluted in a wash solution to an end use level. The polymers are typically formulated in aqueous wash solutions at 0.01 to 1000 ppm.

Optional components in the detergent formulation include, but are not limited to, ion exchangers, bases, corrosion resistant materials, anti-redeposition materials, optical brighteners, perfumes, dyes, fillers, chelants, enzymes, fabric brighteners and brighteners, suds controlling agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffers, soil release agents, fabric softeners, and opacifiers. These optional components may comprise up to about 90% by weight of the detergent formulation.

The artificial polymers according to the invention can be incorporated into manual dishwashing, automatic dishwashing and hard surface cleaning formulations. The polymers may also be incorporated into rinse aid formulations for use in automatic dishwashing formulations. Automatic dishwashing formulations may contain builders such as phosphates and carbonates, bleaching agents and bleach activators and silicates. These polymers are also useful in low phosphate formulations (i.e., less than 1500ppm in wash liquor) and zero phosphate automatic dishwashing formulations. In zero phosphate automatic dishwashing formulations, phosphate removal can negatively impact cleaning because phosphate provides chelation and calcium carbonate inhibition. The artificial polymers according to the present disclosure aid in chelation and threshold inhibition and soil removal and are therefore suitable for use in zero phosphate automatic cutlery formulations. In addition, the artificial polymers according to the present disclosure may be used to minimize stains and filming in rinse aid compositions for automatic dishwashing machine applications.

The formulations may also include other ingredients such as enzymes, buffers, fragrances, defoamers, processing aids, and the like. The hard surface cleaning formulation may contain other adjunct ingredients and carriers. Examples of adjunct ingredients include, but are not limited to, buffers, builders, chelating agents, filler salts, dispersants, enzymes, enzyme enhancers, perfumes, thickeners, clays, solvents, surfactants, and mixtures thereof.

Those skilled in the art will recognize that the amount of polymer required will depend on the cleaning formulations and the benefits they provide to the formulations. In one aspect, the level of use may be from about 0.01% to about 10% by weight of the cleaning formulation. In another embodiment, the level of use may be from about 0.1% to about 2% by weight of the cleaning formulation.

In one embodiment, the cleaning formulation is a dry cleaning agent.

In one embodiment, the cleaning formulation is a liquid detergent.

In one embodiment, the cleaning formulation is an automatic dishwashing detergent.

In one embodiment, the cleaning formulation is phosphate free.

In one embodiment, the cleaning formulation comprises a phosphate-free builder.

Rheology modifier

In one embodiment, the artificial polymer is a polysaccharide alkali swellable rheology modifier composition. Known polymer precursors of this type are described, for example, in U.S. patent No. 9,963,534, the entire contents of which are incorporated herein by reference. The present disclosure extends to any polymer described herein modified by the techniques described herein to substantially eliminate aldehyde functionality in the terminal group saccharide moiety.

In one embodiment, the present disclosure is a polysaccharide alkali swellable rheology modifier composition. The composition comprises a polysaccharide alkali swellable rheology modifier comprising a polysaccharide portion and a synthetic portion obtained from anionic ethylenically unsaturated monomers, hydrophobic ethylenically unsaturated monomers and optionally associative monomers, unreacted polysaccharide and water.

In one embodiment of the present disclosure, the polymer may be substantially free of surfactants, such as stabilizing surfactants, during the polymerization process. For the purposes of this disclosure, substantially free of surfactant means that the polymer has about 0.1 wt% or less surfactant based on the weight of polysaccharide and monomer in one embodiment, about 0.01 wt% or less surfactant based on the weight of polysaccharide and monomer in another embodiment, and no surfactant is present during the polymerization process in yet another embodiment. By polymerizing under conditions that minimize the amount of surfactant present, the opportunity for the monomer to react with the polysaccharide to form the polysaccharide alkali swellable rheology modifier increases. In one embodiment of the present disclosure, a stabilizing surfactant may be added after polymerization to stabilize the emulsion composition.

As used herein, the term "anionic ethylenically unsaturated monomer" refers to an ethylenically unsaturated monomer that is capable of generating a negative charge when the polysaccharide alkali swellable rheology modifier is in aqueous solution. Such anionic ethylenically unsaturated monomers may include, but are not limited to, acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylate, beta-methylacrylic acid (crotonic acid), alpha-phenylacrylic acid, beta-acryloxypropionic acid, sorbic acid, alpha-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid, beta-styrylacrylic acid (1-carboxy-4-phenyl-1, 3-butadiene), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxyethylene, muconic acid, 2-acryloxypropionic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, sodium methallylsulfonate, sulfonated styrene, allyloxybenzenesulfonic acid, vinylphosphonic acid, and maleic acid. Combinations of anionic ethylenically unsaturated monomers may also be used. In one embodiment of the present invention, the anionic ethylenically unsaturated monomer is preferably methacrylic acid, maleic acid, acrylic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, or mixtures thereof. In one embodiment, most preferably the anionic ethylenically unsaturated monomer is methacrylic acid or acrylic acid, or a combination thereof.

For the purposes of this disclosure, the term "hydrophobic ethylenically unsaturated monomer" refers to a monomer that is hydrophobic and forms an emulsion system when reacted with a polysaccharide and an anionic ethylenically unsaturated monomer. For the purposes of this disclosure, a hydrophobic monomer is an ethylenically unsaturated monomer, which is defined as any ethylenically unsaturated monomer having a water solubility of less than 3g per 100 milliliters of water at 25 ℃, preferably less than 1g per 100 milliliters of water at 25 ℃, most preferably less than 0.1g per 100 milliliters of water at 25 ℃. These hydrophobic monomers may contain linear or branched alk (en) yl, cycloalkyl, aryl, alk (en) aryl moieties. Suitable hydrophobic ethylenically unsaturated monomers include C1-C7 alkyl esters or amides of acrylic acid and methacrylic acid, including ethyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, styrene, vinyl toluene, t-butyl styrene, isopropyl styrene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caproate, acrylonitrile, vinyl methacrylate, butadiene, isobutylene, isoprene, vinyl chloride, vinylidene chloride, t-butyl acrylamide, benzyl (meth) acrylate, phenyl (meth) acrylate, ethoxylated benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-butyl octyl (meth) acrylate, 2-hexyl decyl (meth) acrylate, 2-octyl dodecyl (meth) acrylate, 2-decyl tetradecyl (meth) acrylate, 2-dodecyl hexadecyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl acrylamide, octyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl acrylamide, n-octyl acrylamide, lauryl acrylamide, allyl acrylate, vinyl 1-propyl acrylate, allyl acrylate, vinyl 1-butyl acrylate, vinyl acrylate, 2-vinyl naphthalene and combinations thereof. Ethyl (meth) acrylate, methyl (meth) acrylate, 2-ethylhexyl acrylate, butyl (meth) acrylate, vinyl acetate, t-butyl acrylamide, and combinations thereof are preferred. In one embodiment, ethyl acrylate, methyl acrylate, vinyl acetate, butyl acrylate, and combinations thereof are preferred.

For the purposes of this disclosure, associative monomers means ethylenically unsaturated monomers containing a hydrophobe (hydrophobe) and a spacer moiety that spaces the hydrophobe far enough away from the polymer backbone to form the hydrophobe in aqueous solution. The spacer moiety is typically an ethoxylated group, but any other group that extends the hydrophobe away from the polymer backbone may be used. Hydrophobes having spacer moieties include, but are not limited to, alcohol ethoxylates, alkylphenoxyethoxylates, propoxylated/butoxylated ethoxylates, ethoxylated silicones, and the like. In one embodiment, preferred hydrophobes having spacer moieties include alcohol ethoxylates and/or alkylphenoxyethoxylates. In another embodiment, alcohol ethoxylates having a carbon chain length of 6 to 40 and 6 to 100 moles of ethoxylation are more preferred. In yet another embodiment, alcohol ethoxylates containing alcohols having a carbon chain length of 12 to 22 and 15 to 30 moles of ethoxylation are particularly preferred. The hydrophobe may be a linear or branched alk (en) yl, cycloalkyl, aryl, alk (en) aryl or alkoxylated derivative. In one embodiment, the most preferred hydrophobes are linear or branched alcohols and amines containing from 12 to 32 carbons. The associative monomer may comprise an ethylenically unsaturated monomer covalently linked to a hydrophobe. In one embodiment, the ethylenically unsaturated monomer portion of the associative monomer is preferably a (meth) acrylate, itaconate, and/or maleate containing an ester linking group. However, associative monomers may also contain amides, ureas, carbamates, ethers, alkyl groups, aryl groups, and other suitable linking groups. The hydrophobe may be an alkylamine or dialkylamine ethoxylate. In one embodiment, the (meth) acrylate group is most preferred. In another embodiment, the preferred associative monomer is a C12-32 (EO) 10-30 methyl (acrylate) or a C12-32 (EO) 10-30 itaconate or a C12-32 (EO) 10-30 maleate. Such associative monomers are known to those skilled in the art and any known associative monomer may be used as part of the present invention.

In one embodiment, the minimum weight of anionic ethylenically unsaturated monomer is about 15% by weight or more of the total monomer added to the polymerization process, in another embodiment about 20% by weight or more of the total monomer added to the polymerization process, in another embodiment, and most preferably about 30% by weight or more of the total monomer added to the polymerization process. In one embodiment, the maximum weight of the anionic ethylenically unsaturated monomer is about 80% by weight or less of the total monomer added to the polymerization process, preferably about 70% by weight or less of the total monomer added to the polymerization process, and in another embodiment, most preferably about 60% by weight or less of the total monomer added to the polymerization process.

In one embodiment according to the invention, the minimum amount of hydrophobic ethylenically unsaturated monomer desired is the amount effective to form an emulsion, which may depend on the hydrophobicity of the monomer. That is, the more hydrophobic the less monomer is needed to form an emulsion. In one embodiment, the minimum weight of the hydrophobic ethylenically unsaturated monomer effective to form an emulsion is about 10% by weight or more of the total monomer added to the polymerization process, in another embodiment, preferably about 25% by weight or more of the total monomer added to the polymerization process, and in yet another embodiment, most preferably about 40% by weight or more of the total monomer added to the polymerization process. In one embodiment, the maximum weight of hydrophobic ethylenically unsaturated monomer is about 95% by weight or less of the total monomer added to the polymerization process, in another embodiment, preferably about 90% by weight or less of the total monomer added to the polymerization process, and in yet another embodiment, most preferably about 80% by weight or less of the total monomer added to the polymerization process.

In one embodiment, the minimum weight of associative monomers is about 0.1 wt% or more of the total monomers added to the polymerization process, in another embodiment, preferably about 1 wt% or more of the total monomers added to the polymerization process, and in yet another embodiment, most preferably about 2 wt% or more of the total monomers added to the polymerization process. In one embodiment, the maximum weight of associative monomer is about 30 wt% or less of the total monomer added to the polymerization process, in another embodiment about 25 wt% or less of the total monomer added to the polymerization process, and in yet another embodiment, most preferably about 20 wt% or less of the total monomer added to the polymerization process.

It has been found that styrene or substituted styrenes react poorly with the polymers of the present disclosure and can result in high residual monomer levels that cause undesirable odors. Thus, in one embodiment of the present invention, if styrene or substituted styrene is included as part of the hydrophobic ethylenically unsaturated monomer, the amount of such monomer is preferably about 10% by weight or less of the total monomer, more preferably about 5% by weight or less of the total monomer in another embodiment, and most preferably about 1% by weight or less of the total monomer in yet another embodiment.

In one aspect, the present disclosure relates to a method of preparing a polysaccharide alkali-swellable rheology modifier. The method comprises dissolving the polysaccharide in water and heating the solution to a temperature sufficient to initiate the reaction. In one embodiment, the temperature sufficient to initiate the reaction is about 25 to 95 ℃. In one embodiment, the polysaccharide may be depolymerized prior to or during the polymerization step to a molecular weight sufficient to provide a stable emulsion in the end product. In one embodiment, depolymerization may be accomplished using free radicals or enzymes or any other method known to one of ordinary skill in the art. In an exemplary method according to the present disclosure, a monomer mixture and an aqueous initiator solution are added over a period of time. In one embodiment, the monomer may be methacrylic acid mixed with a hydrophobic monomer such as ethyl acrylate. Optionally, associative monomers may be added to the monomer mixture. After the polymerization is completed, the reaction mixture is then cooked sufficiently to reduce the time for residual monomers. Additional initiator to scavenge any remaining monomer may then be added. The required temperature depends on the initiating system used and is known to the person skilled in the art. The residual level of each monomer is less than about 1000ppm of the emulsion polymer composition, more preferably less than about 500ppm of the emulsion polymer composition, and most preferably less than about 100ppm of the emulsion polymer composition.

In one embodiment, chain transfer agents and crosslinking agents may be added during the polymerization process. Suitable chain transfer agents include, but are not limited to, mercaptans such as dodecyl mercaptan, methyl mercaptopropionate, 3-mercaptopropionic acid, 2-mercaptoethanol, combinations thereof, and the like.

Suitable crosslinking agents include, but are not limited to, effectively crosslinked polyethylenically unsaturated copolymerizable monomers such as diallyl phthalate, divinylbenzene, vinyl crotonate, allyl methacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate or dimethacrylate, polyethylene glycol diacrylate or dimethacrylate, 1, 6-hexanediol diacrylate or dimethacrylate, diallyl benzene, combinations thereof, and the like.

The reaction product obtained may be in one or more forms. In one embodiment, the reaction product may be in the form of a stable emulsion composition containing water, the polymer of the present disclosure, and any unreacted polysaccharide, which is a liquid, and then ready for use by dilution to the necessary concentration and addition of a neutralizing agent.

For the purposes of this disclosure, a stable emulsion system is defined as comprising the polymer of this disclosure, unreacted polysaccharide, and water in liquid form and having about 10% or more by weight, preferably about 15% or more by weight, most preferably about 20% or more by weight solids, and in one embodiment the emulsion does not phase separate at 25 ℃ for about 1 month, and in another embodiment preferably does not separate at 25 ℃ for about 6 months.

The stabilized emulsion composition may be diluted with water and then neutralized to impart viscosity and rheology to the aqueous system. In one embodiment of the present disclosure, the stable emulsion composition can be easily diluted. For the purposes of this disclosure, "readily dilutable" means that the emulsion composition may be diluted to about 1-5 weight percent aqueous polymer solution or dispersion by adding water with stirring and if desired adding a neutralizing agent and heating, more preferably to about 1-5 weight percent aqueous polymer solution or dispersion by adding water and using stirring. After the neutralizing agent is added and the pH is raised, in one embodiment the pH is from about 5 to about 12, in another embodiment from about 5 to about 10, and in another embodiment from about 7 to about 10, the polymer dissolves in the water and forms a solution, i.e., it is no longer in the dispersed or emulsion phase. This was confirmed by visual change of the white emulsion to a clear solution. In one embodiment of the present disclosure, the stable emulsion composition or aqueous emulsion paste composition, when diluted to about 2% solids and neutralized to a pH of about 8 with a suitable neutralizing agent, produces a viscosity of about 500cps or greater at 10rpm at 25 ℃ as measured using a brookfield viscometer, in another embodiment, preferably about 2500cps or greater, in another embodiment, more preferably about 5000cps or greater.

In one embodiment, the polysaccharide alkali swellable rheology modifier or polysaccharide hydrophobically modified alkali swellable rheology modifier comprises an emulsion composition having a pH of from about 2 to about 5. Accordingly, these compositions need to be activated by neutralization with a neutralizing agent. Suitable neutralizing agents that may be included in the compositions of the present disclosure include, but are not limited to, alkyl monoamines containing from about 2 to about 22 carbon atoms, such as triethylamine, stearyl amine, and lauryl amine, amino alcohols, such as triethanolamine, 2-amino-2-methyl-1, 3-propanediol, and 2-amino-2-methyl-1-propanol, and inorganic neutralizing agents, such as sodium hydroxide and potassium hydroxide. Other combinations of useful neutralizing agents are described in U.S. Pat. No. 4,874,604 to Sramek, the entire contents of which are incorporated herein by reference. In one embodiment, the neutralizing agents may be used alone or in combination. In one embodiment, the polysaccharide alkali swellable rheology modifier or the polysaccharide hydrophobically modified alkali swellable rheology modifier is neutralized by an alkali. The neutralizing agent may be present in an amount effective to neutralize a portion of the free acid groups of the polymer and render the polymer water-soluble or water-dispersible. In one embodiment, the neutralizing agent may be present in an amount sufficient to neutralize the free acid groups of the polymer to a total free acid groups of the polymer of about 8% to about 100% neutralization. In another embodiment, about 25% to about 100% of the free acid groups of the polymer may be neutralized. In another embodiment, about 50% to about 100% of the free acid groups of the polymer may be neutralized. In another embodiment, from about 70% to about 100% of the free acid groups of the polymer are neutralized. In another embodiment, about 80 to about 100% of the free acid groups of the polymer may be neutralized. Bases with a degree of neutralization exceeding 100% may also be used to raise the solution pH. In another embodiment, when the final pH range of the aqueous system is desirably from about 5 to about 7, the solution comprising the polymer of the present disclosure may be neutralized to a pH of from about 7 to about 9, and then the pH is adjusted back to about 5 to about 7 with a suitable acid. This ensures that the polymer is fully extended and that the rheology modification properties are maximized.

As used herein, an initiating system is any free radical initiating system. In one embodiment, the initiating system is water soluble. Suitable initiators include, but are not limited to, peroxides, azo initiators, and redox systems, such as t-butyl hydroperoxide and isoascorbic acid, and metal ion based initiating systems. The initiator may also include inorganic and organic peroxides. In one embodiment, inorganic peroxides such as sodium persulfate, potassium persulfate, and ammonium persulfate are preferred. In another embodiment, a metal ion based initiator system comprising Fe and hydrogen peroxide, and a combination of Fe and other peroxides, is preferred. Azo initiators, in particular water-soluble azo initiators, may also be used. The water-soluble azo initiators include, but are not limited to, 2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ] disulfate dihydrate, 2' -azobis (2-methylpropionamidine) dihydrochloride, 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ] hydrate 2,2' -azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl ] propane } dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ], 2' -azobis (1-imino-1-pyrrolidinyl-2-ethylpropane) dihydrochloride, 2' -azobis { 2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide }, 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide }, and the like. When added prior to the monomer, an initiator may be used to depolymerize the polysaccharide to the desired molecular weight. Furthermore, different initiation systems may be used during the polymerization process. Finally, a third initiation system may be used to eliminate residual monomer. All 3 of these initiation systems may be the same or different. Thus, it is contemplated that in one embodiment of the present disclosure, combinations of initiating systems may also be used.

If persulfate is used in combination with undegraded starch, the persulfate initiator is preferably about 1 weight percent or less of the total weight of undegraded starch and monomer, preferably about 0.5 weight percent or less of the total weight of undegraded starch and monomer, and most preferably about 0.1 weight percent or less of the total weight of undegraded starch and monomer.

In one embodiment, the present disclosure relates to polysaccharide alkali swellable rheology modifiers and their use in personal care, fabric and cleaning, oilfield, agricultural, adhesives, paints and coatings, and other industrial applications. In one embodiment, the polymers of the present disclosure may be added to these formulations at least about 0.1% polymer by weight of the formulation, more preferably at least about 0.5% polymer by weight of the formulation, and most preferably at least about 1.0% polymer by weight of the formulation. In one embodiment, the polymers of the present disclosure may be added to these formulations at up to about 20% polymer by weight of the formulation, more preferably at up to about 15% polymer by weight of the formulation, and most preferably at least about 10% polymer by weight of the formulation.

Personal care application

Personal care applications include, but are not limited to, formulations for: hair styling gels, skin creams, black sun solutions, moisturizing solutions, toothpastes, medical and emergency ointments, cosmetic ointments, suppositories, cleaners, lipsticks, mascaras, hair dyes, hair conditioners, shampoos, bath soaps and deodorants, hair care and styling formulations, shaving formulations and hand washes (including alcohol-based hand washes).

Suitable personal care applications also include preparations for the skin, eyelashes, or eyebrows, including but not limited to cosmetic compositions such as mascara, facial foundations, eyeliners, lipsticks, and color products; skin care compositions such as moisturizers and creams, skin treatment products, skin protection products in the form of lotions, liquids, sticks or gels; sunscreen compositions such as sunscreens, sun-block emulsions, sun-block liquids, sun-block creams, sun-block emulsion sprays, liquid/alcohol sun-block sprays, sun-block hydrogels, broad spectrum sunscreens with UVA and UVB actives, sunscreens with organic and inorganic actives, sunscreens combined with organic and inorganic actives, tanning products, self-tanning products and post-sun products, and the like. Particularly suitable compositions are personal care emulsions, more particularly suitable are sunscreen compositions, such as sunscreen emulsions and sunscreen emulsion sprays. The personal care composition may be in any form including, but not limited to, sprays, emulsions, lotions, gels, liquids, sticks, waxes, pastes, powders, and creams.

The personal care compositions may also contain other optional components commonly used in the industry, and these vary widely depending on the type of composition and the desired function and performance. Without limitation, these components include thickeners, suspending agents, emulsifiers, UV filters, sunscreen actives, humectants, moisturizers, emollients, oils, waxes, solvents, chelating agents, vitamins, antioxidants, plant extracts, polysiloxanes, neutralizing agents, preservatives, fragrances, dyes, pigments, conditioning agents, polymers, antiperspirant actives, anti-acne agents, antidandruff actives, surfactants, exfoliants, film formers, propellants, tanning accelerators, hair fixatives, and colorants. The polymers of the present disclosure are compatible with most other components used in conventional personal care compositions. For example, the sunscreen composition may comprise at least one component selected from the group consisting of: organic UV filters, inorganic UV actives, UVA and/or UVB sunscreen actives, octyl methoxycinnamate (octisate), octyl salicylate (octisalate), oxybenzone (oxybenzone), homosalate, octocrylene, avobenzone (avobenzone), titanium dioxide, starch, conditioning agents, emulsifiers, other rheology modifiers and thickeners, neutralizing agents, emollients, solvents, film formers, humectants, antioxidants, vitamins, chelating agents, preservatives, fragrances and zinc oxide. The skin care and cosmetic composition may comprise at least one component selected from the group consisting of: vitamins, anti-aging agents, moisturizers, emollients, emulsifiers, surfactants, preservatives, pigments, dyes, colorants, and insect repellents.

When used in personal care formulations such as hair care and styling formulations, e.g., styling gels, optional other ingredients may be added to provide various other additional properties. Various other additives, such as active and functional ingredients, may be included in the personal care formulations as defined herein. These include, but are not limited to, emollients, humectants, thickeners, surfactants, UV light inhibitors, immobilizing polymers, preservatives, pigments, dyes, colorants, alpha-hydroxy acids, aesthetic agents (aesthetic enhancer) such as starches, perfumes and fragrances, film formers (waterproofing agents), disinfectants, antifungals, antimicrobial agents and other drugs, and solvents. Furthermore, conditioning agents such as cationic guar, cationic hydroxyethyl cellulose, cationic synthetic polymers, and cationic fatty amine derivatives may be used in combination with the polymers of the present disclosure. These blended materials help provide more substantivity and effective conditioning performance in the hair.

Some non-limiting examples of polymers that may be used with the polymers of the present disclosure are polyoxyethylated vinyl acetate/crotonic acid copolymers, vinyl acetate/crotonic acid (90/10) copolymers, vinyl acetate/crotonic acid/vinyl neodecanoate terpolymers, N-octyl acrylamide/methyl acrylate/hydroxypropyl methacrylate/acrylic acid/t-butylaminoethyl methacrylate copolymers, and methyl vinyl ether/maleic anhydride (50/50) copolymers mono-esterified with butanol or ethanol, acrylic acid/ethyl acrylate/N-t-butylacrylamide terpolymers, and poly (methacrylic acid/acrylamidomethylpropane sulfonic acid), acrylate copolymers, octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers, acrylate/octylacrylamide copolymers, VA/crotonate/vinyl neodecanoate copolymers, poly (N-vinylacetamide), poly (N-vinylformamide), modified cornstarch, sodium polystyrene sulfonate, polyquaternium such as polyquaternium-4, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-28, polyquaternium-29, polyquaternium-46, polyether-1, polyurethane, VA/acrylate/lauryl methacrylate copolymers, adipic acid/dimethylaminohydroxypropyl diethyleneglycol AMP/acrylate copolymers, methacryloyl ethyl betaine/acrylate copolymer, PVP/dimethylaminoethyl methacrylate copolymer, PVP/DMAPA acrylate copolymer, PVP/vinyl caprolactam/DMAPA acrylate copolymer, vinyl caprolactam/PVP/dimethylaminoethyl methacrylate copolymer, VA/butyl maleate/isobornyl acrylate copolymer, VA/crotonate copolymer, acrylate/acrylamide copolymer, VA/crotonate/vinyl propionate copolymer, vinyl pyrrolidone/vinyl acetate/vinyl propionate terpolymer, VA/crotonate, cationic and amphoteric guar gum, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone/vinyl acetate copolymer, PVP/acrylate copolymer, vinyl acetate/crotonic acid/vinyl propionate, acrylate/acrylamide, acrylate/octylacrylamide, acrylate/hydroxyacrylate copolymer, and alkyl esters of the following compounds: polyvinyl methyl ether/maleic anhydride, diethylene glycol/cyclohexanedimethanol/isophthalate/sulfoisophthalate copolymers, vinyl acetate/butyl maleate and isobornyl acrylate copolymers, vinyl caprolactam/PVP/dimethylaminoethyl methacrylate, vinyl acetate/alkyl half maleate/N-substituted acrylamide terpolymers, vinyl caprolactam/vinylpyrrolidone/methacrylamidopropyl trimethylammonium chloride terpolymers, methacrylate/acrylate copolymers/amine salts, polyvinyl caprolactam, polyurethanes, hydroxypropyl guar gum hydroxypropyl trimethylammonium chloride, poly (methacrylic acid/acrylamidomethyl propane sulfonic acid, polyurethane/acrylate copolymers and hydroxypropyl trimethylammonium chloride guar gum, in particular acrylate copolymers, octyl acrylamide/acrylate/butylaminoethyl methacrylate copolymers, acrylate/octyl acrylamide copolymers, VA/crotonate/vinyl neodecanoate copolymers, poly (N-vinylacetamide), poly (N-vinylformamide), polyurethane, modified corn starch, sodium polystyrene sulfonate, poly ammonium salt-4, poly ammonium salt-10 and quaternary ammonium salt/acrylate copolymers.

In addition to the polymers of the present disclosure, the personal care compositions of the present disclosure may also comprise cosmetically acceptable ingredients. The component may be an emollient, fragrance, exfoliant, drug, whitening agent, acne treatment, preservative, vitamin, protein, cleansing agent, or conditioning agent.

Examples of cleaning agents suitable for use in the present invention include, but are not limited to, sodium Lauryl Sulfate (SLS), sodium laureth sulfate (SLES), ammonium laureth sulfate (ALES), alkanolamides, alkylaryl sulfonates, alkylaryl sulfonic acids, alkylbenzenes, acetates, amine oxides, amines, sulfonated amines and amides, betaines, block polymers, carboxylated alcohols or alkylphenol ethoxylates, diphenylsulfonate derivatives, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated amines and/or amides, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters (other than ethylene glycol, glycerol, etc.), fluorocarbon-based surfactants, glycerol esters, glycol esters, heterocycles, imidazolines and imidazoline derivatives, isethionates, lanolin derivatives, lecithin and lecithin derivatives, lignin and lignin derivatives, methyl esters, monoglycerides and derivatives, olefin sulfonates, phosphate esters, phosphorus-containing organic derivatives, polymeric (polysaccharides, acrylic acid, acrylamide), propoxylated and ethoxylated fatty acids, propoxylated and ethoxylated fatty alcohols, propoxylated and ethoxylated alkylphenols, protein-based surfactants, ammonium salts, protein-based surfactants, sulfate salts, ethoxylated fatty alcohol-based surfactants, sulfate salts, sulfonates of benzene, cumene, toluene and xylene, sulfonates of condensed naphthalene, sulfonates of dodecyl and tridecyl benzene, naphthalene and alkyl naphthalene sulfonates, petroleum sulfonates, sulfosuccinamates, sulfosuccinates and derivatives.

Preservatives are commonly used in personal care formulations to provide long term storage stability. These may be selected from the group consisting of methyl parahydroxybenzoate, propyl parahydroxybenzoate, butyl parahydroxybenzoate, dimethyldimethylhydantoin, imidazolidinyl urea, glutaraldehyde (gluteraldehyde), phenoxyethanol, benzalkonium chloride, methanoammonium chloride, benzethonium chloride, benzyl alcohol, chlorobenzyl alcohol, methyl chloroisothiazolinone, methyl isothiazolinone, sodium benzoate, chloroacetamide, triclosan, iodopropynyl butylcarbamate, sodium 1-oxo-2-mercaptopyridine and zinc 1-oxo-2-mercaptopyridine.

In one embodiment of the present disclosure, particularly wherein the hair formulation is a shampoo, the formulation comprises a sulfate-free surfactant and a polymer of the present disclosure. Sulfate-free surfactants include, but are not limited to, ethoxylated alkylphenols, ethoxylated amines and/or amides, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters (other than ethylene glycol, glycerol, and the like), fluorocarbon-based surfactants, glycerides, glycol esters, heterocycles, imidazolines and imidazoline derivatives, isethionates, lanolin-based derivatives, lecithins and lecithin derivatives, lignin and lignin derivatives, methyl esters, monoglycerides and derivatives, phosphate esters, phosphorus-containing organic derivatives, polymeric (polysaccharides, acrylic acid, acrylamide), propoxylated and ethoxylated fatty acids, propoxylated and ethoxylated fatty alcohols, propoxylated and ethoxylated alkylphenols, protein-based surfactants, quaternary ammonium surfactants, sarcosine derivatives, polysiloxane-based surfactants, alpha-olefin sulfonates, alkylaryl sulfonates, oil and fatty acid sulfonates, ethoxylated alkylphenol sulfonates, benzene, cumene, toluene and xylene sulfonates, condensed naphthalene sulfonates, dodecyl and tridecyl benzene sulfonates, naphthalene and alkyl naphthalene sulfonates, petroleum sulfonates, and derivatives thereof. In one embodiment of the present disclosure, the sulfate-free surfactant is a sulfonate or ethoxylate.

In another embodiment, the formulation comprises a sulfated surfactant. Some non-limiting examples of sulfated surfactants are Sodium Lauryl Sulfate (SLS), sodium laureth sulfate (SLES), alkanolamides, alkylaryl sulfonic acids, sulfates of oils and fatty acids, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, sulfosuccinamates, sulfosuccinates and derivatives thereof.

In addition to the polymers of the present disclosure, the shampoo compositions may optionally comprise other components. Some non-limiting examples of these ingredients include, but are not limited to, conditioning agents such as silicone oils (volatile or non-volatile), natural and synthetic oils. Suitable silicone oils that may be added to the composition include dimethicone, dimethiconol, dimethicone, silicone oils from Dow Corning having various DC fluid ranges. Suitable natural oils may also be used, such as olive oil, almond oil, avocado oil, wheat germOils, castor oil, and synthetic oils such as mineral oil, isopropyl myristate, isopropyl palmitate, isopropyl stearate and isopropyl isostearate, oleyl oleate, isocetyl stearate, hexyl laurate, dibutyl adipate, dioctyl adipate, myristyl myristate, and oleyl erucate. Some examples of nonionic conditioning agents are polyols such as glycerol, glycols and derivatives, polyethylene glycol, which are available under the trade name Union Carbide Tradenames of PEG and Amerchol>The WSR series are known as polyglycerol, polyethylene glycol mono-or di-fatty acid esters.

Suitable cationic polymers that can be used in the formulation are those well known under their CTFA-type name polyquaternium. Some examples of such polymers are polyquaternium 6, polyquaternium 7, polyquaternium 10, polyquaternium 11, polyquaternium 16, polyquaternium 22 and polyquaternium 28, polyquaternium 4, polyquaternium 37, quaternium-8, quaternium-14, quaternium-15, quaternium-18, quaternium-22, quaternium-24, quaternium-26, quaternium-27, quaternium-30, quaternium-33, quaternium-53, quaternium-60, quaternium-61, quaternium-72, quaternium-78, quaternium-80, quaternium-81, quaternium-82, quaternium-83 and quaternium-84.

Polymer from AmercholNaturally derived cellulose polymers of the type known per se, polyquaternium 10 or from Rhone-Poulenc under the trade name +.>Cationic guar gum, guar hydroxypropyl trimethylammonium chloride, chitosan and chitin, which are known as cationic natural polymers, may also optionally be included with the polymers of the inventionIncluded in personal care formulations. Other gums including xanthan gum, dehydrogenated xanthan gum, carrageenan, gellan gum, locust bean gum, tara gum are also suitable for use in the formulations comprising the polymers of the invention. Starch-based rheology modifiers including hydroxypropyl starch phosphate and modified potato starch may also be used in these formulations.

The film-forming polymer may be included in the polymer of the present invention in the range of 0.1 to 10%; the dosage of the cleaning surfactant is 5-30%; the dosage of the cationic polymer is 0.1-5%; the amount of cellulose, gum and starch is 0.1-10%.

The present disclosure will now be described in more detail with reference to the following non-limiting examples.

Examples

In the examples, the following abbreviations or trade names are used.

Conventional maltodextrins and corn syrups (for comparative example):

staley 1300 = 82.1% de 42 solution from Tate & Lyle;

StarDRI240=95.2% DE 24 powder from Tate & Lyle;

StarDRI10=91.0% active DE 10 powder from Tate & Lyle.

Hydrogenated starch hydrolysates/polyols for use in embodiments of the present disclosure:

hystar 3375 = 76.7% active polyol (hydrogenated corn syrup) solution from Ingredion;

hystar 4075 = 76.7% active polyol (hydrogenated corn syrup) solution from Ingredion;

hystar 6075 = 77.3% active polyol (hydrogenated corn syrup) solution from Ingredion;

stabite SD 30 = 95.4% active polyol (hydrogenated maltodextrin) powder from ingrind;

polysorb 75/55=75.7% active (hydrogenated corn syrup) polyol solution from Roquette;

Polysorb 75/25=75.0% active (hydrogenated corn syrup) polyol solution from Roquette.

VenPure ^TM Solution-about 12% borohydride in 40% aqueous sodium hydroxide from Dow.

Comparative example 1 (DE) 42)

An initial charge of a solution containing 262.21 grams (g) of Staley 1300 (corn syrup from DE 42) and 224.92g of water was added to a 2 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.51g maleic anhydride was charged to the reactor. At 187°f, 8.98g of 35% hydrogen peroxide solution was charged to the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 72.0g of acrylic acid was added over 2 hours. A solution of 38.27g of 50% sodium hydroxide solution in 29.17g of water was added simultaneously over 2 hours. A solution of 9.50g sodium persulfate dissolved in 104.15g water was added over 2 hours and 30 minutes. At the end of the sodium persulfate solution feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. At the end of one hour, the reactor was cooled to 140°f. 5.6g sodium bisulfite was added to the reactor and the temperature was maintained at 140℃F. For 15 minutes. The reactor was then cooled to room temperature. Once the temperature had fallen below 113F, the pH of the polymer was adjusted to 8.0 with 37.67g of 50% sodium hydroxide solution. The final polymer solution was dark amber in color and had a solids content of 39.0%.

Comparative example 2 (DE) 10)

An initial charge of a solution containing 276.5g Star DRI 10 (maltodextrin from DE 10) and 292.5g of water was added to a 2 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.6g maleic anhydride was charged to the reactor. 10.8g of 35% hydrogen peroxide solution was charged to the reactor at 187F. Immediately after the addition of 35% hydrogen peroxide solution, 86.4g of acrylic acid were added over 2 hours. A solution of 24.0g of 50% sodium hydroxide solution in 69g of water was added simultaneously over 2 hours. A solution of 11.4g sodium persulfate dissolved in 125g water was added over 2 hours and 30 minutes. At the end of the sodium persulfate solution feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was yellow and had a solids content of 45.8%.

Comparative example 3 (DE) 24)

An initial charge of a solution containing 225.8g Star DRI 240 (corn syrup of DE 24) and 261.4g of water was added to a 2 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. At 187℃F. 8.9g of 35% hydrogen peroxide solution were charged into the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 72.0g of acrylic acid was added over 2 hours. A solution of 38.27g of 50% sodium hydroxide solution in 29.17g of water was added simultaneously over 2 hours. A solution of 9.5g sodium persulfate dissolved in 104.15g water was added over 2 hours and 30 minutes. At the end of the sodium persulfate solution feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. At the end of one hour, the reactor was cooled to 140°f. 5.6g sodium bisulfite was added to the reactor and the temperature was maintained at 140℃F. For 15 minutes. The reactor was then cooled to room temperature. Once the temperature had fallen below 113F, the pH of the polymer was adjusted to 8.0 with 37.67g of 50% sodium hydroxide solution. The final polymer solution was dark amber in color and had a solids content of 40.4%.

Comparative example 4 (DE) 10)

660.3g 94%StarDri 100 (maltodextrin from Tate and Lyle, DE 10) and 1128.1g of water were added to the glass reactor. The contents were heated to 60 ℃ with continuous stirring. 31.1g of 35% hydrogen peroxide was added to the reactor contents, which was then heated to 87 ℃. A solution of 321.3g acrylic acid and 26.2g vinyl acetate was slowly added to the reactor contents over 2.5 hours. Separately slowly added initiator solution containing 84.7g sodium persulfate, 482g water and 28.5g 35% hydrogen peroxide was added simultaneously to the reactor contents over the same period of time. A third slowly added caustic solution containing 311.8g of 50% sodium hydroxide and 86.6g of water was also added to the reactor contents over the same period of time. After all three feeds were completed, the reactor contents were again cooked for 30 minutes to give a pale yellow homogeneous polymer solution.

Comparative example 5 (75/25) DE 42/AA)

377.6g 81%Staley 1300 (available from Tate and Lyle) and 249.1g of water were added to the glass reactor. The contents were heated to 60 ℃ with continuous stirring. 13.0g of 35% hydrogen peroxide, 0.01g of maleic anhydride and 0.01g of itaconic acid were added to the reactor. The contents were cooked for 10 minutes and then the temperature was raised to 87 ℃. A monomer solution of 103.8g acrylic acid and 41.5g water was added to the reactor contents over 120 minutes. 13.7g of sodium persulfate dissolved in 149.4g of water were fed simultaneously over 135 minutes. After the feed was completed, the contents were again cooked for 1 hour, then cooled to ambient temperature and 51.9g of 50% naoh was added. As a result, a clear and homogeneous polymer solution was obtained.

Comparative example 6 (DE-42) 75/25)

218.3g 81%Staley 1300 (available from Cargill), 144g of water, 7.5g of 35% hydrogen peroxide, 0.01g of maleic anhydride and 0.01g of itaconic acid were added to a glass reactor. The contents were heated to 87 ℃. A monomer solution of 60g acrylic acid and 24g water was added to the reactor contents over 120 minutes. 7.9g of sodium persulfate dissolved in 86.4g of water was added simultaneously over 135 minutes. After the feed was completed, the contents were again cooked for 1 hour, then cooled to ambient temperature and 30g of 50% naoh was added. As a result, a clear and homogeneous polymer solution was obtained.

Comparative example 7 (DE-42) 75/15/10)

94.6g of 94.4% DE 42 maltodextrin (Star Dri 42 from Tate and Lyle) and 103.6g of water were added to the glass reactor. The contents were heated to 87 ℃ with continuous stirring. To this mixture was added 4.5g of 35% hydrogen peroxide. To this mixture were added 11.9g of maleic anhydride and 0.0050g of ferrous ammonium sulfate hexahydrate. After dissolution, the contents were partially neutralized with 9.8g of 50% naoh. 17.8g of acrylic acid in 15g of water were added to the reactor contents over 3 hours. 1.9g of sodium persulfate dissolved in 10g of water and 14.2g of 35% hydrogen peroxide were simultaneously fed over 3.25 hours. After the feed was completed, the contents were again cooked for 1 hour and then cooled to 50 ℃. The contents were further neutralized with 12.4g of 50% naoh. As a result, a clear and homogeneous polymer solution was obtained.

Comparative example 8

Polymer 4 from EP0725131A1 was repeated. This uses Polyol 300 from Cerestar, but this material is no longer commercially available. We replace this material with SD 30 used in this example 9, with SD 30 aldehyde end groups <0.1mol%, based on the total moles of saccharide units.

Comparative example 9

Polymer 3 from EP0725131A1 was repeated except that Cargill 01915 was used instead of Cerestar PUR 01915. (we believe that Cargill purchased Cerestar and renamed the product.)

Example 1 (Polysorb) 75/55)

The polymerization of comparative example 1 was repeated except that the Staley 1300 (corn syrup of DE 42) was replaced with an equal solids amount of Polysorb 75/55 (hydrogenated corn syrup). The final polymer solution was pale yellow and had a solids content of 40.5%. In contrast, the final polymer solution of comparative example 1 was dark amber in color.

Surprisingly, we found that even when a polyol is used in example 1, there is still a slight yellowing in the ageing test (see example 5). It appears that depolymerization of the polyol occurs, resulting in the production of additional aldehyde end groups, especially when the persulfate initiator is still added after the monomer and acrylic acid feeds.

In examples 2, 3 and 4, the sodium persulfate feed time was shortened to minimize depolymerization of the polyol during the polymerization process, and the color improved by making this change was shown in example 5 while ensuring polymerization of the monomer at a low residual acrylic acid value.

Example 2 (Polysorb) 75/22, persulfate feed is shorter than example 1)

An initial charge of solution containing 293.3g Polysorb 75/22 and 177.6g of water was added to a 2 liter 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. At 187℃F. 8.9g of 35% hydrogen peroxide solution were charged into the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 72.0g of acrylic acid was added over 2 hours. A solution of 20g of 50% sodium hydroxide solution in 57.5g of water was added simultaneously over 2 hours. A solution of 7.3g sodium persulfate dissolved in 104.15g water was added over 1 hour and 55 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 40.6%.

Example 3 (Polysorb) 75/22, persulfate feed is shorter than examples 1 and 2)

An initial charge of solution containing 293.3g Polysorb 75/22 and 177.6g of water was added to a 2 liter 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. At 187℃F. 8.9g of 35% hydrogen peroxide solution were charged into the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 72.0g of acrylic acid was added over 2 hours. A solution of 20g of 50% sodium hydroxide solution in 57.5g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 4.75g sodium persulfate and 104.14g water was added over 1 hour and 30 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 40.5%.

Example 4 (Polysorb) 75/22, persulfate feed was shorter than examples 1, 2 and 3)

An initial charge of solution containing 293.3g Polysorb 75/22 and 177.6g of water was added to a 2 liter 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. At 187℃F. 8.9g of 35% hydrogen peroxide solution were charged into the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 72.0g of acrylic acid was added over 2 hours. A solution of 20g of 50% sodium hydroxide solution in 57.5g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 4.75g sodium persulfate and 104.14g water was added over 1 hour and 15 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 40.3%.

Examples 5-examples 1-4 and comparative examples yellowing comparison

A 1% active polymer solution of comparative example 1 and examples 1, 2, 3 and 4 in a buffer solution at pH 9.2 was prepared, since discoloration was particularly pronounced under alkaline conditions. The buffer solution was prepared by dissolving 7.65g sodium bicarbonate and 0.96g sodium carbonate in 1L deionized water.

These 1% polymer solutions were aged at 178℃F. (80 ℃) for 6 hours. These polymer solutions were then cooled to room temperature and colorimetric analysis was completed by using absorbance measured at 520nm with Hach DR 5000. The higher the absorbance value, the darker the sample color or the greater the degree of discoloration.

Comparative example 1 was formulated identically to example 1 except that hydrogenated corn syrup Polysorb 75/22 was used in example 1, and conventional corn syrup was used in comparative example 1. The absorbance values indicate that the color of the solution produced by using example 1 was significantly lighter than the color of the solution produced by using comparative example 1. This difference can be seen by the naked eye: the color of the solution produced using example 1 was pale yellow, while the color of the solution produced using comparative example 1 was amber. The color of Polysorb 75/22 in this test was water white, indicating that it does not have a reducing end group. Thus, the polymer of example 1 is yellow in color, which indicates that there is some amount of depolymerization of the polyol during the polymerization of acrylic acid. By reducing the amount of persulfate in example 1 (as exemplified in examples 2, 3 and 4), this can be minimized, with the color being further reduced in proportion to the reduction in persulfate as shown in the above table. The reduction of persulfate and the reduction of the addition time compared to the acrylic acid monomer minimizes depolymerization of the polyol, which produces additional aldehyde end groups, especially when the persulfate initiator is added after the monomer and acrylic acid feeds. The color of the solution of example 4 was about one order of magnitude lighter than the color of the solution of example 1 and about two orders of magnitude lighter than the color of the solution of comparative example 1. In examples 1-4, the reaction temperature was 185℃F. And acrylic acid was added over 2 hours. The half-life of the sodium persulfate initiator at 185°f was about 1 hour. Thus, even if acrylic acid is added over 2 hours, the sodium persulfate feed can be shortened to 1 hour. These examples demonstrate that initiator feed can be controlled to minimize depolymerization of the polyol while ensuring polymerization of the monomer, as shown by less than 0.1 mole% residual acrylic acid in these samples. Those skilled in the art will recognize that if there is a significant amount of residual monomer, i.e., generally greater than 0.1 to 0.5 weight percent of the polymer solution (typically containing 30 to 50 weight percent polymer), it is indicated that the initiator feed is too short and may require extension.

Example 6

An initial charge of solution containing 293.3g Hystar 3375 and 177.6g of water was added to a 2 liter 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. At 187℃F. 8.9g of 35% hydrogen peroxide solution were charged into the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 72.0g of acrylic acid was added over 2 hours. A solution of 20g of 50% sodium hydroxide solution in 57.5g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 7.3g of sodium persulfate dissolved in 104.15g of water was simultaneously added over 1 hour and 55 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 40.7%.

Example 7

An initial charge of solution containing 1492g Hystar 4075 (hydrogenated corn syrup) and 957g of water was added to a 5 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 2.6g maleic anhydride was charged to the reactor. 46.7g of 35% hydrogen peroxide solution was charged to the reactor at 187F. Immediately after the addition of 35% hydrogen peroxide solution, 374.4g of acrylic acid were added over 2 hours. A solution of 103.9g of 50% sodium hydroxide solution in 299g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 37.9g of sodium persulfate dissolved in 542g of water was simultaneously added over 1 hour and 55 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 40.3%.

Example 8

An initial charge of solution containing 307.3g Hystar 6075 (hydrogenated corn syrup) and 201.3g of water was added to a 2 liter 5-neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirrer. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.54g maleic anhydride was charged to the reactor. 9.7g of 35% hydrogen peroxide solution was charged to the reactor at 187F. Immediately after the addition of 35% hydrogen peroxide solution, 77.8g of acrylic acid were added over 2 hours. A solution of 21.6g of 50% sodium hydroxide solution in 62g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 7.9g of sodium persulfate dissolved in 112.5g of water was simultaneously added over 1 hour and 55 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 39.8%.

Example 9

An initial charge of a solution containing 1432.5g Stabilite SD 30 (hydrogenated maltodextrin) and 1638g of water was added to a 5 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 3.3g maleic anhydride was charged to the reactor. 58.5g of 35% hydrogen peroxide solution was charged to the reactor at 187F. Immediately after the addition of 35% hydrogen peroxide solution, 469.5g of acrylic acid were added over 2 hours. A solution of 103.9g of 50% sodium hydroxide solution in 375g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 47.5g of sodium persulfate dissolved in 679g of water was simultaneously added over 1 hour and 55 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 40.8%.

EXAMPLE 10 borohydride aftertreatment

300g of the polymer solution of comparative example 1 was added to a 500ml 5-neck round-bottom flask with condenser. The reactor was then heated to 113℃F. And 23.95g VenPure was stirred highly over 30 minutes ^TM The solution (borohydride) is added below the liquid surface. During borohydride addition, the temperature was maintained below 120°f. At the end of borohydride addition, the reactor temperature was maintained at 113°f for 2 hours 30 minutes. The reaction mixture was then cooled to room temperature and pH 12.8. The pH was adjusted to 7.2 using 26.1g of 10.0N sulfuric acid. The final solution was pale yellow and solidThe volume content was 35.4%.

EXAMPLE 11 borohydride aftertreatment

300g of the polymer solution of comparative example 1 was added to a 500ml 5-neck round-bottom flask with condenser. The reactor was then heated to 113℃F. And 10.2g VenPure was added over 30 minutes with high stirring ^TM The solution (borohydride) is added below the liquid surface. During borohydride addition, the temperature was maintained below 120°f. At the end of borohydride addition, the reactor temperature was maintained at 113°f for 2 hours 30 minutes. The reaction mixture was then cooled to room temperature and pH 12.5. The pH was adjusted to 7.2 using 13.9g of 10.0N sulfuric acid. The final solution was light brown and had a solids content of 37.6%.

EXAMPLE 12 borohydride aftertreatment

300g of the polymer solution of comparative example 3 was added to a 500ml 5-neck round-bottom flask with condenser. The reactor was then heated to 113℃F. And 16.2g VenPure was added over 30 minutes with high stirring ^TM The solution (borohydride) is added below the liquid surface. During borohydride addition, the temperature was maintained below 120°f. At the end of borohydride addition, the reactor temperature was maintained at 113°f for 2 hours 30 minutes. The reaction mixture was then cooled to room temperature and pH 12.9. 26g of 10.0N sulfuric acid are used to adjust the pH to 7.2. The final solution was pale yellow and had a solids content of 35.6%.

Examples 13 a-h-post-treatment with Ca and Mg salts such as chlorides and hydroxides

An initial charge of solution containing 1870.15g Hystar 3375 and 1200.15g of water was added to a 5 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 3.2g maleic anhydride was charged to the reactor. 58.5g of 35% hydrogen peroxide solution was charged to the reactor at 187F. Immediately after the addition of 35% hydrogen peroxide solution, 469.5g of acrylic acid were added over 2 hours. A solution of 130.29g of 50% sodium hydroxide solution and 374.92g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 47.5g of sodium persulfate dissolved in 679g of water was simultaneously added over 1 hour and 55 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature.

The polymer solution was then divided into smaller batches and post-addition was completed as follows:

₂ ₂ ₂ ₂ examples 14 a-h-post-treatment with CaCl, mgCl, ca (OH) and Mg (OH)

An initial charge of solution containing 1870.15g Hystar 3375 and 1200.15g of water was added to a 5 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 3.2g maleic anhydride was charged to the reactor. 58.5g of 35% hydrogen peroxide solution was charged to the reactor at 187F. Immediately after the addition of 35% hydrogen peroxide solution, 469.5g of acrylic acid were added over 2 hours. A solution of 130.29g of 50% sodium hydroxide solution and 374.92g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 30.97g of sodium persulfate dissolved in 679g of water was simultaneously added over 1 hour and 15 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour.

The reactor was then cooled to room temperature and the polymer solution was then divided into smaller batches and post-addition was completed as follows:

example 15 (peroxide and maleic anhydride free)

An initial charge of solution containing 293.35g Polysorb 75/22 and 177.56g of water was added to a 2 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The contents of the reactor were heated to 187°f and 72g of acrylic acid was added over 2 hours. A solution of 20g of 50% sodium hydroxide solution in 57.5g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 4.8g of sodium persulfate dissolved in 104g of water was simultaneously added over 1 hour and 15 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. At the end of one hour, the reactor was cooled to 140°f. The reactor was then cooled to room temperature. The final polymer solution was dark yellow and had a solids content of 40.6%.

Example 16 (peroxide in feed without maleic anhydride)

An initial feed solution of 293.34g Polysorb 75/22 and 177.57g of water was added to a 2 liter 5 neck round bottom flask with condenser. The reactor contents were heated to 187°f. Once the temperature stabilized at 187°f, 72.0g AA was added over 2 hours. A solution of 19.97g of 50% sodium hydroxide solution and 57.51g of water was added simultaneously over 2 hours. One minute of feed, a solution of 4.75g sodium persulfate, 8.98g 35% hydrogen peroxide solution, and 104.16g water was added over 75 minutes. At the end of the monomer and 50% sodium hydroxide solution feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. At the end of the cooking, the polymer solution is cooled and collected. The final polymer solution was pale yellow and had a solids content of 40.5%.

Example 17 (peroxide in feed and maleic anhydride in feed)

An initial charge of solution containing 293.33g Polysorb 75/22 and 177.56g of water was added to a 2 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. 77.8g of acrylic acid and 0.50g of maleic anhydride were added over 2 hours. A solution of 19.98g of 50% sodium hydroxide solution and 57.5g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 4.8g of sodium persulfate, 8.99g of 35% hydrogen peroxide solution and 104.18g of water was simultaneously added over 1 hour and 15 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 40.8%.

Example 18

An initial charge of solution containing 293.3g Hystar 3375 and 177.6g of water was added to a 2 liter 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. At 187℃F. 8.9g of 35% hydrogen peroxide solution were charged into the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 72.0g of acrylic acid was added over 2 hours. A solution of 20g of 50% sodium hydroxide solution in 57.5g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 4.7g of sodium persulfate dissolved in 104.15g of water was simultaneously added over 1 hour and 15 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 40.5%.

EXAMPLE 19 post-treatment with borohydride

300g of the polymer solution of comparative example 3 was added to a 500ml 5-neck round-bottom flask with condenser. The reactor was then heated to 113℃F. And 32.4g VenPure was added over 30 minutes with high agitation ^TM The solution (12% borohydride caustic solution) was added below the liquid level. The temperature was maintained below 120°f during the borohydride addition. At the end of borohydride addition, the reactor temperature was maintained at 113°f for 2 hours 30 minutes. The reactor was then cooled to room temperature and the pH was adjusted to 7.2 using 42.4g of 10.0n sulfuric acid. The final solution was pale yellow and had a solids content of 33.4%.

Example 20 (results of yellowness screening test, NMR data)

The comparative examples and examples of the present disclosure were used to prepare 1% active polymer solutions in buffer solutions at pH 9.2, as discoloration is particularly pronounced under alkaline conditions. The buffer solution was prepared by dissolving 7.65g sodium bicarbonate and 0.96g sodium carbonate in 1L deionized water.

These 1% polymer solutions were then stored at 178℃F. (80 ℃) for 6 hours. These polymer solutions were then cooled to room temperature and subjected to colorimetric analysis by measuring absorbance at 520nm using Hach DR 5000. The higher the absorbance value, the darker the sample color or the greater the degree of discoloration.

	Absorbance of light
		Comparative example 1	0.135
Comparative example 2	0.100
		Comparative example 3	0.514
Comparative example 8	0.334
		Comparative example 9	0.441
Example 1	0.060
		Example 2	0.013
Example 3	0.011
		Example 4	0.007
Example 6	0.009
		Example 7	0.042
Example 8	0.013
		Example 9	0.009
Example 10	0.198
		Example 11	0.382
Example 12	0.032
		Example 15	0.027
Example 16	0.010
		Example 17	0.008
Example 14a	0.033
		Example 14b	0.077
Example 14c	0.050
		Example 14d	0.044
Example 14e	0.010
		Example 14f	0.030
EXAMPLE 14g	0.014
		Example 14h	0.009
Example 14i	0.007

Comparative example 2 and example 9 are similar polymers except that hydrogenated maltodextrin was used in example 9, and conventional maltodextrin was used in comparative example 2. The absorbance value indicated that the color (0.009) of the solution prepared by using example 9 was significantly lower than the color (0.100) of the solution prepared by using comparative example 2.

When corn syrup was used, the effect of minimizing aldehyde end groups by using different levels of borohydride post-treatment to reduce color was demonstrated by comparing examples 10 (0.198) and 11 with comparative example 1.

The effect of minimizing aldehyde end groups by post treatment with borohydride to reduce color is demonstrated by comparison of example 12, where absorbance 0.032 of example 12 is significantly lower than that of comparative example 2 when maltodextrin is used.

The calcium and magnesium salts appear to surprisingly reduce the color to less discolored and almost water-white solutions (14 e, h and i), as exemplified in the table above for examples 14 a-i.

¹ H NMR spectra were obtained on a Varian 400MHz NMR spectrometer using 90 ° pulses, water inhibition, 2 second saturation delay, 10 second relaxation delay and 16 scans. Spectra were collected at 90℃and water peaks referenced to 4.11ppm. The spectra are then analyzed to determine the aldehyde end groups or Reactive End Groups (REGs) of the polymer.

The integral in each spectrum was normalized to the integral of the peak corresponding to the alpha-1, 4 bond at 5.17ppm, set to 100.

Peaks corresponding to protons bound to the blocking end groups in the beta and alpha forms appear at 4.46ppm and 5.05ppm, respectively. The sum of these two integrals represents the total (relative) number of potential REGs.

If the polysaccharide has been treated with sodium borohydride or is a polyol/Hydrogenated Starch Hydrolysate (HSH), the peak corresponding to the proton of the 1,4 bond of the penultimate glucose unit occurs at 4.95 ppm. Proton at terminal unit ¹ Not observed in the H NMR spectrum, therefore the integral of the peak at 4.95ppm needs to be multiplied by 2 in the end group calculation.

The peak corresponding to the branching point on the proton or polysaccharide linked to the alpha-1, 6 bond appears at 4.78 ppm.

For conventional polysaccharides and their hybrids, the mole percent of aldehyde end groups is calculated based on the total moles of saccharide units using the integral of each peak shown in the formula:

(4.46ppm+5.05ppm)/(4.46ppm+5.05ppm+5.17ppm+4.78ppm)*100。

For hydrogenated starch hydrolysates/polyols and hybrids thereof, the mole percent of aldehyde end groups is calculated based on the total moles of saccharide units using the integral of each peak shown in the formula:

(4.46ppm+5.05ppm)/(4.46ppm+5.05ppm+5.17ppm+4.78ppm+2*4.95ppm)*100。

the mole percent of aldehyde end groups per sample, based on the total moles of saccharide units, is shown in the table below.

These data indicate that the mole percent of aldehyde end groups of comparative examples 1 and 3 are much higher than the examples of the present invention based on the total moles of saccharide units and that this results in lower discoloration or browning as shown by the discoloration test described above.

Comparative examples 8 and 9 from prior art EP0725131A1 have 28.6 and 15.0 mole% aldehyde end groups, respectively, based on the total moles of saccharide units, indicating that the incorporation of phosphorus in the polymer does not contribute to minimizing aldehyde end groups and therefore does not minimize discoloration. Further, the polyol used in comparative example 8 was the same as the polyol used in example 9. Example 9 has 1.9 mole% aldehyde end groups based on the total moles of saccharide units, in contrast to comparative example 8, which has 28.6% aldehyde end groups. In addition, the color measured by absorbance (higher value, more serious discoloration) was 0.009 in example 9, compared to 0.334 in comparative example 8. This is because the depolymerization of the polyol is minimized in example 9, but not in comparative example 8.

Example 21

The polymer solutions of comparative example 1 and example 3 were spray dried. 20g of the spray-dried powder was then placed in a humidity chamber at 45℃and a relative humidity of 85% for 24 hours. The spray-dried powder of example 3 had a white color and a moisture absorption of 12.1% after aging in a humidity chamber. In contrast, the spray-dried powder of comparative example 1 had a yellow color and a moisture absorption of 13.6% after aging in a humidity chamber. In subjective color scale 0-4, 0 indicates no yellowing and 4 indicates very yellow, the spray-dried powder of example 3 after aging in a humidity chamber was 0.5. In contrast, the yellowness rating of the spray-dried powder of comparative example 1 after aging in a humidity chamber was 4. These data indicate that the polymers of the present invention are less discolored and less hygroscopic than the polymers of the prior art.

EXAMPLE 22 rheology modifier Synthesis

An initial charge of solution containing 565.1g of water and 57.2g Stabilite SD 30 was charged to a 2 liter kettle reactor equipped with a 5 neck kettle top, condenser, heating mantle, temperature probe and controller, and overhead agitation. The initial charge was heated to 178°f and sparged with nitrogen. The reactor was maintained at 178°f for one hour. 99.1g of ethyl acrylate, 41.0g of methacrylic acid and 11.2g of 50% C were added as subsurface feed over 1 hour 30 minutes ₁₆ Mixtures of 18 alcohols with 20 mol of ethoxylate methacrylates (associative monomers), 25% methacrylic acid and 25% water. A solution of 0.54g ammonium persulfate in 61.4g water was added simultaneously over 1 hour and 30 minutes. At the end of the feed, the temperature was maintained at 178°f for 2 hours. The reactor was then cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was a white emulsion with a solids content of 23.5% and a pH of 2.5.

EXAMPLE 23 rheology modifier Synthesis

An initial charge of solution containing 608.0g of water and 161.1g Polysorb 75/22 was charged to a 2 liter kettle reactor equipped with a 5 neck kettle top, condenser, heating mantle, temperature probe and controller, and overhead agitation. The initial charge was heated to 178°f and sparged with nitrogen below the liquid surface. The reactor was maintained at 178°f for one hour. A monomer mixture of 28.0g of ethyl acrylate, 12.3g of methacrylic acid and 0.18g of trimethylolpropane triacrylate was added as a subsurface feed over 1 hour 30 minutes. A solution of 0.15g ammonium persulfate in 50.2g water was added simultaneously over 1 hour and 30 minutes. At the end of the feed, the temperature was maintained at 178°f for 2 hours. The reactor was then cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was a white emulsion with a solids content of 19.5% and a pH of 2.4.

Example 24: hydrogenation after hybrid copolymerization

880g of the polymer product of comparative example 4 dissolved in 22g of 50% aqueous activated nickel solution were added and stirred at room temperature for about 30 minutes. The mixture was transferred to a 2 liter Parr reactor. The reactor was sealed and stirred at 500 rpm. The reactor was pressurized to 1100psi with hydrogen and heated to 115 ℃ to initiate hydrogenation of the maltodextrin portion of the hybrid polymer. After 5 hours the reaction was stopped by cooling and the reactor was depressurized. The reaction mixture was filtered to remove the nickel catalyst and to give a clear polymer solution.

Enzymatic degradation examples

EXAMPLE 25 preparation of (alpha) Limit dextrins from waxy corn starch

A4L plastic beaker was charged with 3094g of water and 794.6g of waxy corn starch (AMIOCA available from Ingrerion; 88.1% solids). The resulting slurry was stirred with a paddle mixer at about 22-25 ℃ for 30 minutes to ensure uniform distribution of starch particles in the water.

The slurry was then jet cooked with steam using a laboratory-scale steam jet digester (custom made). The flow rate of the slurry to the digester was 128 mL/min; the steam mass flow rate is 8-9 lbs/hr; and the cooking temperature is 109-112 ℃. The yield of the cloudy, viscous aqueous starch dispersion was 4246g. Dispersed solids (determined gravimetrically in an oven at 130 ℃ C.; results of two determinations): 14.7%; this corresponds to a yield of 624g (89%) of cooked waxy corn (dry basis). pH of the dispersion: 8.45@18℃. The dispersion was stored overnight (no preservative added) at 2-8 ℃.

A5L jacketed beaker was charged with 4094g of a dispersion of waxy corn starch in water (602 g starch, dry basis). The dispersion was then heated to 50±1 ℃ while stirring with an overhead mechanical stirrer. When the temperature reached 50 ℃, the stirring rate was set at 500rpm and the pH was adjusted to 5.5 by dropwise addition of about 2g of dilute sulfuric acid (5.2 wt%).

In parallel, a dispersion of 1.05g of alpha-amylase (from Bacillus; obtained from Sigma; 330 KNU/g) in 23.93g of water was prepared.

A dispersion of 16.15g of alpha-amylase in water (224 KNU) was then added to the waxy maize dispersion. As the viscosity of the waxy corn dispersion decreased, the stirring rate was adjusted to 350rpm. The enzyme-catalyzed hydrolysis was allowed to continue at 50 ℃ for a total of 5 hours. The reaction mixture (less than about 60 g) was then freeze-dried (FTS Systems Inc. Dura-Top ^TM P (microprocessor controlled high capacity tray Dryer/Dura-Dry microprocessor controlled corrosion resistant freeze Dryer (Microprocessor Control Bulk Tray Dryer/Dura-Dry Microprocessor Control Corrosion Resistant Freeze-Dryer)). The yield of the solid product thus obtained was 672g. Solids content (determined gravimetrically in an oven at 130 ℃ C.; results of two determinations): 91.2%.

EXAMPLE 26 preparation of (alpha) Limit dextrins from waxy corn starch

Additional amounts of (alpha) limit dextrins were prepared from waxy corn starch using the procedure described in examples 2321-67.

The yield of the solid material obtained was 1269g. Solids content (determined gravimetrically in an oven at 130 ℃ C.; results of two determinations): 94.2%.

Example 27

100g of active DE 10 maltodextrin (Star Dri 10 from Tate and Lyle) was dissolved in 100g of potassium phosphate buffer pH 6.3 in a glass reactor with continuous stirring. 0.0475g of calcium chloride dihydrate and 0.0475g Validase HT 425L (from Valley Research) were added to the reactor and the contents heated to 95 ℃ for one hour twenty minutes with continuous stirring. The final solution had a solids content of 45%.

Example 28: molecular weight information of enzymatically degraded starch

The distribution of the degree of polymerization was determined by GPC/ELSD/MS analysis on TSK Oligo PW.

About 20.0mg of the sample was weighed and dissolved in 1.0ml of mobile phase. The injection volume was varied to obtain approximately the same amount of material in each chromatogram.

Solvent: 25mM ammonium formate pH 3.0% water/20% acetonitrile

Flow rate: 0.75 ml/min

And (3) detection: softa ELSD and Waters LCT

Calibration was performed using LC/MS, taking care of the degree of polymerization/residence time of DP1 to DP 25, and later compensating for this using the residence time of the DP 2 and DP 3 peaks as determined by GPC/RI.

From the resulting molecular weight/degree of polymerization distribution, it can be seen that the enzymatically degraded starches of examples 25, 26 and 27 have a low monosaccharide (DP 1)/disaccharide (DP 2) content and high oligomer contents DP 4, 5 and 6.

Importantly, when used in hybridization reactions, the levels of oligomeric DP 4, 5, 6 were maximized while minimizing the levels of DP1 and 2 to improve anti-redeposition performance (as shown in example 39) and carbonate inhibition performance (as shown in example 40). The enzymatically degraded starches of examples 25, 26 and 27 had a sum of DP1 and DP 2 of <13.5%, but comparative DE 42 had a sum of DP1 and DP 2 of > 30%. In addition, the enzymatically degraded starches of examples 25, 26 and 27 have a total of >39% DP 4, 5 and 6, whereas comparative DE 10 has only 13%. All the above% DP are determined by LC measurement as area% of total DP of the oligosaccharide or polysaccharide.

Enzymatically degraded starch has a sum of DP1 and DP 2 of <30, <25, <20 and preferably <16, and a sum of DP 4, 5 and 6 of >15, >20, >25 and most preferably > 35.

Example 29

50g of example 25 and 60g of water were added to the glass reactor. The contents were heated to 87 ℃ with continuous stirring. A monomer solution of 16.7g acrylic acid and 40g water was added to the reactor contents over 90 minutes. 2.2g of sodium persulfate dissolved in 60g of water were fed simultaneously over the same time interval. After the feed was completed, the contents were again cooked for 1 hour and then cooled to ambient temperature. As a result, a clear and homogeneous polymer solution was obtained.

Example 30

50g of example 25 and 60g of water were added to the glass reactor. The contents were heated to 87 ℃ with continuous stirring. A monomer solution of 8.8g acrylic acid and 40g water was added to the reactor contents for 90 minutes. 1.16g of sodium persulfate dissolved in 60g of water was fed simultaneously over the same time interval. After the feed was completed, the contents were again cooked for 1 hour and then cooled to ambient temperature. As a result, a clear and homogeneous polymer solution was obtained.

Example 31

78.65g of example 25, 16.78g of maleic anhydride and 74.69g of water were added to the glass reactor. The contents were heated to 87 ℃ with continuous stirring. When the contents reached 60 ℃, 17.32g of 50% naoh was slowly added to the reactor. 0.00825g of ferrous ammonium sulphate hexahydrate was added to 1mL of water. A monomer solution of 25.3g acrylic acid and 3g water was added to the reactor contents over 4 hours. 1.84g of sodium persulfate dissolved in 7.33g of water and 14.85g of 35% hydrogen peroxide were simultaneously fed over 4.25 hours. After the feed was completed, the contents were again cooked for 1 hour and then cooled to ambient temperature. As a result, a clear, dark homogeneous polymer solution was obtained.

Example 32

30g of example 25 and 60g of water were added to the glass reactor. The contents were heated to 98 ℃ with continuous stirring. A monomer solution of 48g 50% amps, 6g methacrylic acid and 18g water was added to the reactor contents over 90 minutes. 0.83g of sodium persulfate dissolved in 60g of water was fed simultaneously over the same time interval. After the feed was completed, the contents were again cooked for 1 hour and then cooled to ambient temperature. As a result, a clear and homogeneous polymer solution was obtained.

Example 33

30g of example 25 and 60g of water were added to the glass reactor. The contents were heated to 98 ℃ with continuous stirring. A monomer solution of 48g 50% amps, 6g acrylic acid and 18g water was added to the reactor contents over 90 minutes. 0.89g of sodium persulfate dissolved in 60g of water was fed simultaneously over the same time interval. After the feed was completed, the contents were again cooked for 1 hour and then cooled to ambient temperature. As a result, a clear and homogeneous polymer solution was obtained.

Example 34

38g of example 25 and 160g of water were added to the glass reactor. The contents were heated to 98 ℃ with continuous stirring. 99.4g of 50% AMPS and 62.8g of acrylic acid in monomer solution were added to the reactor contents over 90 minutes. 5g of sodium persulfate dissolved in 40g of water were fed simultaneously over the same time interval. After the feed was completed, the contents were again cooked for 1 hour and then cooled to ambient temperature. As a result, a clear and homogeneous polymer solution was obtained.

Example 35

To a glass reactor was added 189g 94.4% DE 10 maltodextrin (Star Dri 10 from Tate and Lyle), 207.2g potassium phosphate buffer pH 6.3, 0.0898g Validase HT 425TL and 0.0842g calcium sulfate. The contents were heated to 92.5 ℃ with continuous stirring and cooked for 1 hour after reaching temperature. To this mixture was added 9g of 35% hydrogen peroxide. The mixture was further cooked for 10 minutes. A monomer solution of 55.4g of acrylic acid and 5.8g of 80% ethyl (2-dimethylamino) methacrylate methyl chloride quaternary ammonium salt was added to the reactor contents over 120 minutes. 7.6g of sodium persulfate dissolved in 86.4g of water were simultaneously fed over 145 minutes. After the feed was completed, the contents were again cooked for 1 hour and then cooled to 50 ℃. The contents were partially neutralized with 30g of 50% naoh. As a result, a clear and homogeneous polymer solution was obtained.

Example 36

94.6g of 94.4% DE 10 maltodextrin (Star Dri 10 from Tate and Lyle), 103.6g of water, 0.02g of 25% NaOH, 0.0449g Validase HT 425TL and 1.24g of a 1% calcium ion solution from calcium sulfate and water were added to a glass reactor. The contents were heated to 92.5 ℃ with continuous stirring and cooked for 1 hour after reaching temperature. The contents were cooled to 87 ℃. To this mixture was added 4.5g of 35% hydrogen peroxide. The mixture was further cooked for 10 minutes. 30g of acrylic acid was added to the reactor contents over 120 minutes. 3.95g of sodium persulfate dissolved in 43.2g of water were fed simultaneously over 145 minutes. After the feed was completed, the contents were again cooked for 1 hour and then cooled to 50 ℃. The contents were partially neutralized with 15g of 50% naoh. As a result, a clear and homogeneous polymer solution was obtained.

Example 37

94.6g of 94.4% DE 10 maltodextrin (Star Dri 10 from Tate and Lyle), 103.6g of potassium phosphate buffer pH 6.3, 0.0449g Validase HT 425TL and 0.0421g of calcium sulfate in 5mL of water were added to the glass reactor. The contents were heated to 92.5 ℃ with continuous stirring and cooked for 1 hour after reaching temperature. The contents were cooled to 87 ℃. To this mixture was added 4.5g of 35% hydrogen peroxide. The mixture was further cooked for 10 minutes. To this mixture were added 11.9g of maleic anhydride and 0.0050g of ferrous ammonium sulfate hexahydrate. After dissolution, the contents were partially neutralized with 9.8g of 50% naoh. 17.8g of acrylic acid in 15g of water were added to the reactor contents over 3 hours. 1.9g of sodium persulfate dissolved in 10g of water and 14.2g of 35% hydrogen peroxide were simultaneously fed over 3.25 hours. After the feed was completed, the contents were again cooked for 1 hour and then cooled to 50 ℃. The contents were partially neutralized with 12.4g of 50% naoh. As a result, a clear and homogeneous polymer solution was obtained.

Example 38

38g of 94.4% DE 10 maltodextrin (Star Dri 10 from Tate and Lyle), 41.6g of potassium phosphate buffer solution having a pH of 6.3, 0.0180g Validase HT 425TL in 1mL of water and 0.0169g of calcium sulfate in 1mL of water are added to the glass reactor. The contents were heated to 92.5 ℃ with continuous stirring and cooked for 1 hour after reaching temperature. The contents were cooled to 87 ℃. To this mixture was added 1.8g of 35% hydrogen peroxide. The mixture was further cooked for 10 minutes. 12.1g of acrylic acid in 5.5g of water were added to the reactor contents over 120 minutes. 1.6g of sodium persulfate dissolved in 17.4g of water was fed simultaneously over 145 minutes. After the feed was completed, the contents were again cooked for 1 hour and then cooled to 50 ℃. The contents were partially neutralized with 6g of 50% naoh. As a result, a clear and homogeneous polymer solution was obtained.

Example 39

Washing: anti-redeposition

Anti-redeposition test description:

clay anti-redeposition properties were evaluated using a terotometer (model 7243E, from TestFabrics, inc.).

For each polymer (or non-polymer blank to be tested), an initial wash test was performed with the addition of each of the following components:

1 piece Bradley clay cloth (. About.500 mg dirty mud)

1L local municipal water, with water hardness adjusting salt (to 250 ppm): 0.50g CaCl ₂ .2H ₂ O and 0.66g MgCl ₂ .6H ₂ O

1.00g basic detergent (Natural powder detergent (Natural Powder Detergent), free and Clear from th Generation)

20ppm of polymer additive (not present in the negative control).

(2) 100% cotton knit fabric swatches 3 inches by 4 inches (model 460-60)

(2) 3 inch by 4 inch 50/50 polyester/cotton swatch (model 7422)

* Cloth sample was purchased from: testfabrics, inc.

Pre-scanning of swatches has been performed using spectrophotometers (L a b and WI, minolta Spectrophotometer CM-508-d). The washing process was carried out at 30℃and stirring continued for 15 minutes. Pour each Terg tank and introduce 1L of unregulated municipal water. Rinse for 5 minutes with agitation at 23 ℃. The rinsing procedure was repeated but for a duration of 3 minutes. Pouring rinse water; the test swatches were manually wrung out and dried at high temperature in a conventional dryer. After drying, the swatches were scanned again. Whiteness index of the cloth before and after the test was measured. Δwi is the difference in whiteness index measured before and after the test. The smaller Δwi, the whiter the swatch, and the better the anti-redeposition performance.

Results:

anti redeposition WI of cotton swatches from termotometer test CIE value

ΔWI value	Test 1	Test 2	Test 3	Test 4
					Polymer-free	87.4	74.8	89.2	81.4
Comparative example 6	23.1			29.6
					Comparative example 7		32.4	32.7
Example 38			14.5	16.3
					Example 37			18.8	21.8

Anti redeposition WI from termotometer test of polyester/cotton swatches CIE value

ΔWI value	Test 1	Test 2	Test 3	Test 4
					Polymer-free	76.5	65.7	79.8	67.9
Comparative example 6	16.9			20.2
					Comparative example 7		23.4	23.1
Example 38			10.3	12.8
					Example 37			13.3	14.2

These data in the above table show that the anti-redeposition properties of the hybrids of enzymatically degraded starch from examples 37 and 38 are better than those of comparative examples 6 and 7, which are hybrids from corn syrup or maltodextrin, because the Δwi values are much lower for both cotton and polyester/cotton samples.

Example 40: calcium carbonate inhibition

The performance of the various examples as calcium carbonate threshold inhibitors was evaluated by a static, uncapped calcium carbonate inhibition test.

Preparing a solution:

all chemicals used were reagent grade and weighed on an analytical balance to the indicated value +/-0.0005g. All solutions were prepared within thirty days prior to the test day. Hardness and alkalinity solutions were prepared by filling a one liter volumetric flask with deionized water to volume after adding the following amounts of salts:

Hardness solution for 250 cycles:

36.6838g CaCl.2H ₂ O

25.0836g MgC1.6H ₂ O

0.6127g of lithium chloride

Alkalinity solution was cycled 250 times:

48.98.63g NaHCO ₃

7.0659g Na ₂ CO ₃

test procedure:

the incubator shaker was turned on and the temperature was set to 50 ℃ to preheat. 97.6g deionized water was dispensed into each Erlenmeyer flask: each example dose was tested in triplicate. A flask without any treatment agent was prepared as a blank. 1.20mL of the hardness solution was added to each flask using a 2.5mL electrokinetic pipette, followed by dispensing of the treatment polymer solution to produce the desired treatment dose, and finally 1.20mL of alkalinity solution was added to each flask. All flasks were placed uncapped into a shaker oven at 250rpm and 50 ℃ for 17 hours. A "total" solution was prepared with 97.6g deionized water, 1.20mL of the hardness solution, and another 1.20mL of deionized water and left outside the shaker for the same time at ambient temperature, capped.

The flask was removed, capped and allowed to cool. Each sample solution (including blank solution and total solution) was filtered through a 0.2um filter and a sufficient 10% nitric acid solution was formulated to obtain 2.5% of the nitric acid in the filtered solution. Samples were analyzed for calcium and lithium content via inductively coupled plasma (Inductively Couple Plasma, ICP) optical emission system. After correction for dilution during acidification, the% inhibition is determined by:

(Ca in ppm in sample: li in total solution/Li in ppm in sample: ca in ppm in blank: li in ppm in total solution/Li in blank: li in ppm)

(Ca in ppm Total solution-Ca in ppm in blank x Li in ppm Total solution/Li in ppm in blank) x 100%

The higher the calcium carbonate inhibition value, the better the performance. These data clearly demonstrate that the calcium carbonate inhibition values of the hybrid polymers produced by enzymatic degradation of starch are superior to those of the comparative polymers produced by conventional corn syrup DE 42.

Example 41: calcium phosphate inhibition at 20ppm

Two brines were prepared.

Brine 1 was prepared as follows:

4.401g CaCl ₂ .2H ₂ O

0.028g Fe(NH ₄ ) ₂ (SO ₄ ) ₂ .6H ₂ O

the salt was added to a 3L volumetric flask and filled to volume with deionized water.

Brine 2 was prepared as follows:

0.09g Na ₂ HPO ₄

0.072g Na ₂ B4O ₇ .10H ₂ O

For each sample to be prepared, 50g of brine 1 was added to a 125mL Erlenmeyer flask, followed by the desired amount of polymer treatment (added as a 1% solution) and 50g of brine 2 was added thereto. Each polymer sample was formulated and prepared in triplicate at 20ppm active. A blank sample without polymer and a total solution sample containing only 50g of brine 2 and 50g of deionized water were also prepared. The samples were capped and placed in an oven at 70 ℃ overnight. The sample was then filtered through 2um filter paper and analyzed for phosphate content via Hach method 480.

Phosphate inhibition was determined by the following formula:

(P in ppm in sample-P in ppm in blank)/(P in ppm in total solution-P in ppm in blank) x 100%

Example% phosphate inhibition

Example 32 82

Example 34 92

Phosphate inhibition performance of greater than 80% was considered good in this test. These data indicate that the polymers of the present invention are good phosphate scale inhibitors.

Example 42:

automatic zero phosphate dishwashing formulations.

Example 43

Automatic zero phosphate dishwashing powder formulations

Example 44 personal Care formulations Using rheology modifiers

200g of personal care shower gel were prepared by adding 23.5g of example 22 (2.5% active polymer) to 54.4g of deionized water in a 250ml beaker. A 1.5 inch flash mixer blade was inserted into the beaker and connected to the overhead mixer. The batch was mixed with a vortex extending to the middle of the beaker. Then 100g of sodium laureth sulfate (25.2% active, standapol ES-2 from BASF) was added. Mix it for 15 minutes. 1.97g of 25% sodium hydroxide was added dropwise and the solution was mixed for 15 minutes. Then, 14.8g of cocoamidopropyl betaine (cropatric CAB 30, croda Inc.) was added and mixed for an additional 15 minutes. 0.1g of ethylenediamine tetraacetic acid tetrasodium salt was added and the batch was mixed until homogeneous. 0.5g of sodium benzoate was added to the batch and mixed until homogeneous. The pH was then adjusted to 5.0+/-0.2 using 7.2g of 20% citric acid. The batch was mixed for 15 minutes and then left to stand for 24 hours before centrifugation. Viscosity was measured using a Brookfield DV-I+ viscometer using a number 6 spindle at 10rpm and clarity was measured using a HACH 2100AN turbidimeter. The bath gel has a viscosity of 9500cps and a clarity of 40NTU.

Example 45 personal Care formulations Using rheology modifiers

200g of a typical shampoo formulation was prepared by adding 26.6g of example 23 (2.5% active polymer) to 50.3g of deionized water in a 250ml beaker. A 1.5 inch flash mixer blade was inserted into the beaker and connected to the overhead mixer. The batch was mixed with a vortex extending to the middle of the beaker. Then 100g of sodium laureth sulfate (25.2% active, standapol ES-2 from BASF) was added. Mix it for 15 minutes. 1.97g of 25% sodium hydroxide was added dropwise and the solution was mixed for 15 minutes. Then, 14.8g of cocoamidopropyl betaine (Crodatric CAB 30, croda Inc.) was added and mixed for an additional 15 minutes. 0.1g of ethylenediamine tetraacetic acid tetrasodium salt was added and the batch was mixed until homogeneous. 0.5g of sodium benzoate was added to the batch and mixed until homogeneous. The pH was then adjusted to 5.0+/-0.2 using 7.2g of 20% citric acid as required. The batch was mixed for 15 minutes and then left to stand for 24 hours before centrifugation. Viscosity was measured using a Brookfield DV-I+ viscometer using a number 6 spindle at 10rpm and clarity was measured using a HACH 2100AN turbidimeter. The final formulation had a viscosity of 3500cps and a clarity of 350NTU.

Example 46

92.27g of water and 97g of the enzymatically degraded starch of example 25 (91.2%) were added to a glass reactor. The mixture was heated to 85 ℃ with continuous stirring. 29.57g of acrylic acid were added over 2 hours. A solution of 15.52g of water and 29.56g of 50% NaOH was added simultaneously to the reactor over the same period of time. A third solution of 3.9g sodium persulfate dissolved in 42.9g water was added simultaneously with the other two additives, but over a period of 2.5 hours. After the slow addition of sodium persulfate was completed, the reactor contents were cooked at 85 ℃ for 1 hour. The contents were then cooled to room temperature and the product was a brown homogeneous solution polymer. When tested as in example 5, the absorbance at 520nm was 0.438.

50g of this polymer were adjusted to pH 9 with continuous stirring using 1.4g of 25% NaOH solution. In a glass reactor, the solution polymer was heated to 45 ℃ with vigorous stirring. 3.27g of a 12% sodium borohydride solution diluted with water to 10mL was added to the reactor contents below the liquid level over 0.5 hours. After the sodium borohydride addition was complete, the contents were stirred at this temperature for an additional 2.5 hours. The absorbance value at 520nm was 0.210 when tested as in example 5.

The color was determined to be too dark and thus an additional 1.6g of 12% sodium borohydride diluted to 10mL with water was added to the reactor contents below the liquid level over 0.5 hours. After the sodium borohydride addition was complete, the contents were stirred at this temperature for an additional 2.5 hours. The material was cooled to room temperature and the pH was adjusted to 7.23 with 13g of 25% aqueous sulfuric acid. The solids content of the final product was 34.1%. The absorbance value at 520nm was 0.016 when tested as in example 5. This color is considered acceptable. This example illustrates how the addition of borohydride can be controlled to provide the desired low color level in a simulated alkaline aging test.

Example 47

Step I: synthesis of hybrid polymers

An initial charge of a solution containing 262.2g Staley 1300 (DE 42 corn syrup, 83% aqueous solution from Tate and Lyle) and 225g of water was added to a 2 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. At 187℃F. 8.9g of 35% hydrogen peroxide solution were charged into the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 72.0g of acrylic acid was added over 2 hours. 29g of 50% sodium hydroxide solution in 38g of water are added simultaneously over 2 hours. After one minute of feeding, a solution of 9.5g of sodium persulfate dissolved in 104.15g of water was simultaneously added over 1 hour and 55 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution had 38.5mol% of reducing end groups as determined by NMR as described in example 20.

Step II: hydrogenation of hybrid polymers

Into a 600mL autoclave were added 85.1g of the above polymer solution, 4.2g of Raney nickel A-7000 (lot No. 70001732, johnson) &Matthey) catalyst and 0.3g Calcinet filter aid. The reactor was heated to 120℃with N ₂ Fill to 5psig and use H ₂ Pressurized to 700psig. The reactor was sampled and filtered for NMR analysis using a syringe fitted with a 1 μm filter. After 7 hours, the reaction product had 3.1mol% of the reducing end groups as determined by NMR, and the reaction was stopped.

Example 48

Step I: synthesis of hybrid polymers

An initial charge of solution containing 262.2g Star Dri 240 (DE 24 corn syrup from Tate and Lyle) and 225g of water was added to a 2 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. 9g of 35% hydrogen peroxide solution was charged to the reactor at 187℃F. Immediately after the addition of 35% hydrogen peroxide solution, 72.0g of acrylic acid was added over 2 hours. 29g of 50% sodium hydroxide solution in 38g of water are added simultaneously over 2 hours. After one minute of feeding, a solution of 9.5g of sodium persulfate dissolved in 104.15g of water was simultaneously added over 1 hour and 55 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution had 23.2mol% of reducing end groups as determined by NMR.

Step II: hydrogenation of hybrid polymers

118.4g of the above polymer solution, 5.9g of Raney nickel A-7000 (batch No. 70001732, johnson) were added to a 600mL autoclave&Matthey) catalyst and 0.5g Calcinet filter aid. The reactor was heated to 120℃with N ₂ Fill to 5psig and use H ₂ Pressurized to 700psig. The reactor was sampled and filtered for NMR analysis using a syringe fitted with a 1 μm filter. After 9 hours, the reaction product had 3.1mol% of the reducing end groups as determined by NMR and the reaction was stopped.

Example 49

An initial charge of solution containing 277.2g Hystar 3375 and 224g of water was added to a 2 liter 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.6g maleic anhydride was charged to the reactor. At 187°f, 10g of 35% hydrogen peroxide solution was charged to the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 114.5g of acrylic acid were added over 2 hours. A solution of 31.8g of 50% sodium hydroxide solution in 64.4g of water was added over 2 hours. After one minute of feeding, a solution of 7.56g sodium persulfate and 116.6g water was added over 1 hour and 15 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 40.7%.

Example 50

An initial charge of solution containing 217.5g Hystar 3375 and 224g of water was added to a 2 liter 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. At 187℃F. 8.9g of 35% hydrogen peroxide solution were charged into the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 160.3g of acrylic acid were added over 2 hours. A solution of 44.5g of 50% sodium hydroxide solution in 64.4g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 10.6g sodium persulfate and 116.7g water was added over 1 hour and 15 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 41%.

Example 51

An initial charge of solution containing 177g of Hystar 3375 and 184g of water was added to a 2 liter, 5 neck round bottom flask equipped with a condenser, heating mantle, temperature probe and controller, and overhead stirring. The reactor contents were initially heated to 187°f. When the temperature of the initial charge reached 140°f, 0.5g maleic anhydride was charged to the reactor. At 187℃F. 8.9g of 35% hydrogen peroxide solution were charged into the reactor. Immediately after the addition of 35% hydrogen peroxide solution, 160.3g of acrylic acid and 80g of 50% sodium 2-acrylamido-2-methylpropanesulfonate solution were added over 2 hours. A solution of 44.5g of 50% sodium hydroxide solution in 64.4g of water was added simultaneously over 2 hours. After one minute of feeding, a solution of 10.6g sodium persulfate and 116.7g water was added over 1 hour and 15 minutes. At the end of the feed, the reactor temperature was maintained at 185-189℃F. For an additional hour. The reactor was then cooled to room temperature. The final polymer solution was pale yellow and had a solids content of 41.6 and a pH of 4.5%.

Example 52

The polymers of the present invention were tested in Automatic Dishwashing (ADW) applications. The test conditions were as follows:

machine: miele GSL2

The procedure is as follows: R65/10/Kl65 run time was about 1 hour 35 minutes, wash, 2 rinses and dry

Hardness of water: 21 (German hardness) Ca to Mg ratio of 3:1, caCl ₂ 、MgSO ₄ And NaHCO ₃ Is made into

Each cycle of formulation powder: 18g

And (3) circulation: 10. films and stains were evaluated by the panel on a scale of 1-9, with 9 being the best and 1 being the worst.

Ballast soil (ballast soil): 25g. The composition of the ballast soil is as follows:

composition of the components	Quantity (g)
		Softened water	11.54
Milk	2.61
		Yolk powder	1.50
Meat juice powder	1.25
		Potato starch	0.26
Margarine oil	5.22
		Mustard	1.31
Tomato sauce	1.31

The formulations tested were as follows:

composition of the components	Measuring amount	Function of
			Builder agent	25％	Builder and calcium ion binder
Polymer	5％	CaCO ₃ Soil control and dispersants
			Na ₄ HEDP	1.5 or 0.5%	Chelating agent, transition metal binder
25 moles of ethoxylated C16-C18 fatty alcohol	5％	Surfactant, cleaning and rinsing
			Sodium percarbonate	15％	Oxidizing agent, bleaching agent
Sodium carbonate	25％	Buffer, pH control
			TAED	2％	Bleaching activator
Protease enzyme	2.5％	Enzyme, cleaning
			Amylase enzyme	1.5％	Enzyme, cleaning
Zinc sulfate	0.2％	Glass corrosion inhibitor
			Sodium disilicate	5.0％	Buffer, pH control
Sodium sulfate	12.8 or 13.8%	Filler (B)

The test results after 20 cycles are as follows:

these data demonstrate that the polymers of the present invention are excellent in minimizing filming and staining in automatic dishwashing applications.

Example 53

Phosphates are subject to increasing regulatory pressures. The phosphate-free formulation of the present invention is as follows:

example 54

Liquid laundry formulations

Composition of the components	Weight percent of active ingredient
		C9-C13 alkylbenzene sulfonate	0-20
Sodium lauryl ether sulfate	0-20
		C12-C14 fatty acids	0-20
C12-C15 alcohol ethoxylates	0-20
		The polymers of examples 4 or 10 or 48 or 51	0.5-5
GLDA/MGDA	1-10
		Sodium chloride or sodium sulfate	1-10
Protease enzyme	0.1-1
		Amylase enzyme	0.1-1
Mannanase	0.1-1
		Sodium hydroxide	0.1-5
Water and its preparation method	To 100%

While the present disclosure has been described in conjunction with the specific embodiments described above, many alternatives, modifications, and other variations thereof will be apparent to those skilled in the art. All such alternatives, modifications, and variations are intended to fall within the spirit and scope of the present disclosure.

Claims

1. An artificial polymer comprising a synthetic component (a) covalently bonded to a natural component (B), wherein the natural component comprises an oligosaccharide or polysaccharide, and wherein the terminal groups of the oligosaccharide or polysaccharide are substantially free of aldehyde functionality when in an open chain form.

2. The synthetic polymer of claim 1 derived from a polymer precursor that is terminated with aldehyde functionality when in an open chain form, the synthetic polymer containing less than 5%, or less than 2%, or less than 1% of the aldehyde functionality of the polymer precursor as compared to the polymer precursor.

3. The synthetic polymer of claim 1 which is completely free of terminal group aldehyde functionality.

4. The synthetic polymer of any one of claims 1-3, which contains alcohol functionality instead of the aldehyde functionality.

5. The artificial polymer of any of claims 1-3 containing a carboxyl functionality instead of the aldehyde functionality.

6. The artificial polymer of any one of claims 1-5 selected from the group consisting of hybrid copolymers, sulfonated graft copolymers, low molecular weight graft copolymers, hybrid dendritic copolymers, graft dendritic copolymers.

7. The synthetic polymer of any one of claims 1-6, comprising the following general structure:

wherein the method comprises the steps of

m ₁ represents the number of repeating units of the natural component and is 0 to 98, preferably 0 to 48, most preferably 1 to 10;

n ₁ represents the number of repeating units of the synthetic moiety and is 20 to 100, preferably 25 to 70, most preferably 3 to 20;

R ₁ Is a single monomer residue that forms part of the synthesis and is preferably a (meth) acrylic monomer, itaconic acid monomer, maleic acid monomer or mixtures thereof; and

8. The synthetic polymer of any one of claims 1-6, comprising the following general structure:

wherein the method comprises the steps of

m ₂ represents the number of repeating units of the natural component and is 0 to 9998, preferably 1 to 998, most preferably 2 to 98; and

R ₂ is a single monomer residue constituting a synthetic part and preferably derived from an anionic ethylenically unsaturated monomer and preferably a (meth) acrylic monomer;

R ₃ is a single monomer residue constituting a synthetic part and preferably derived from a hydrophobic ethylenically unsaturated monomer and preferably an ethyl acrylate, methyl (meth) acrylate or butyl (meth) acrylate monomer or a mixture thereof; and

9. The synthetic polymer of any one of claims 1-8, which is substantially free of added phosphorus.

10. An artificial polymer comprising a synthetic component (a) covalently bonded to a natural component (B), wherein the natural component comprises a mixture comprising monosaccharides having an oligomerization degree DP1, disaccharides having an oligomerization degree DP2, tetrasaccharides having an oligomerization degree DP4, pentasaccharides having an oligomerization degree DP5, and hexasaccharides having an oligomerization degree DP6, wherein the sum of dp1+dp2 is less than 30 and the sum of dp4+dp5+dp6 is greater than 15.

11. The synthetic polymer of claim 10 selected from the group consisting of hybrid copolymers, sulfonated graft copolymers, low molecular weight graft copolymers, hybrid dendritic copolymers, graft dendritic copolymers.

12. The synthetic polymer of claim 10 or 11 comprising the following general structure:

wherein the method comprises the steps of

Re ₁ Represents an aldehyde, alcohol or carboxylic acid functional group;

R ₄ Is a single monomer residue that forms part of the synthesis and is preferably a (meth) acrylic monomer, itaconic acid monomer, maleic acid monomer, and mixtures thereof; and

13. A method of preparing the artificial polymer according to any one of claims 1-9, the method comprising the steps of: (A) Providing a polymer precursor mixture comprising (i) one or more monomer precursors of the synthesis component and (ii) an oligosaccharide or polysaccharide comprising a terminal group capable of existing in the form of an open chain comprising an aldehyde functional group; (B) Polymerizing the polymer precursor mixture to form an artificial polymer, wherein all or most of the aldehyde functionality is eliminated before or after step (B).

14. The method of claim 13, further comprising adding hydrogen peroxide to the polymer precursor mixture prior to step (B) to reduce aldehyde functionality.

15. The method of claim 14, comprising removing residual hydrogen peroxide prior to step (B).

16. The method of any one of claims 13-15, further comprising adding sodium borohydride to the artificial polymer after step (B) to reduce aldehyde functionality.

17. A composition useful for preparing the artificial polymer of any one of claims 1-9, the composition comprising (a) one or more monomeric precursors of the synthetic component and (B) an oligosaccharide or polysaccharide, wherein the oligosaccharide or polysaccharide comprises terminal groups that are substantially free of aldehyde functionality when in an open chain form.

18. An artificial polymer prepared according to the method of any one of claims 13-16.

19. A method of preparing an artificial polymer according to any one of claims 10-12, the method comprising the steps of: (a) enzymatically degrading the polysaccharide to form an oligosaccharide; (B) Providing a polymer precursor mixture comprising (i) one or more monomer precursors of a synthesis component and (ii) the oligosaccharides prepared in (a); and (C) polymerizing the polymer precursor mixture to form the artificial polymer.

20. An artificial polymer prepared according to the method of claim 19.

21. A formulation comprising the artificial polymer of any one of claims 1-12, 18 and 20 and at least one additional ingredient.

22. The formulation of claim 21, which is a cleaning formulation selected from the group consisting of: powdered laundry detergents, liquid laundry detergents, and automatic dishwashing detergents; and the at least one additional ingredient is selected from the group consisting of a builder, a surfactant, and an enzyme.

23. The formulation of claim 22, which is phosphate-free and/or the at least one additional ingredient is a phosphate-free builder.

24. The formulation of claim 21, which is a water treatment formulation; and the at least one additional ingredient is selected from corrosion inhibitors.

25. The formulation of claim 21, which is a personal care formulation selected from the group consisting of: skin lotions and creams, skin gels, essences and liquids, facial and body cleansing products, wipes, liquids and bar soaps, make-up preparations, cosmetics, foundations, sun protection products, sun protection creams, sunless tanning preparations, shampoos, hair conditioners, hair dyes, hair straighteners, products containing AHA (alpha-hydroxy acids) and BHA (beta-hydroxy acids); and the at least one additional ingredient is selected from the group consisting of sunscreens or actives, beautifiers, conditioners, anti-acne agents, antimicrobial agents, anti-inflammatory agents, analgesics, anti-erythema agents, anti-itching agents, anti-edema agents, anti-psoriasis agents, antifungal agents, skin protectants, vitamins, antioxidants, scavengers, anti-irritants, antibacterial agents, antiviral agents, anti-aging agents, photoprotectants, hair growth promoters, hair growth inhibitors, depilatories, anti-dandruff agents, anti-seborrhea agents, exfoliants, wound healing agents, anti-ectoparasites agents, sebum regulators, immunomodulators, hormones, botanicals, moisturizers, astringents, cleaners, sensates, antibiotics, anesthetics, steroids, tissue healing substances, tissue regeneration agents, hydroxyalkyl ureas, amino acids, peptides, minerals, ceramides, biopesthesia, vitamins, skin lightening agents, tanning agents, coenzyme Q10, niacinamide, capsaicin, caffeine, and combinations thereof.

26. A method of preparing the formulation of any one of claims 21-25, comprising adding an artificial polymer to the at least one additional ingredient.

27. A method of cleaning a surface comprising contacting the surface with an effective amount of the synthetic polymer according to any one of claims 1-12, 18 and 20.

28. A method of controlling fouling in an aqueous system comprising introducing into the aqueous system an effective amount of the synthetic polymer of any one of claims 1-12, 18, and 20.

29. A method of dispersing particles in an aqueous system comprising adding an effective amount of the synthetic polymer of any one of claims 1-12, 18, and 20 to the aqueous system.

30. A method of treating skin or hair comprising applying to the skin or hair an effective amount of the artificial polymer of any one of claims 1-12, 18 and 20.

31. A method of modifying the rheological properties of a formulation comprising incorporating an effective amount of the artificial polymer of any one of claims 1-12, 18 and 20 into such a formulation.