Nothing Special   »   [go: up one dir, main page]

WO1997003961A1 - Imido peroxides as initiators of polymerization processes - Google Patents

Imido peroxides as initiators of polymerization processes Download PDF

Info

Publication number
WO1997003961A1
WO1997003961A1 PCT/EP1996/003108 EP9603108W WO9703961A1 WO 1997003961 A1 WO1997003961 A1 WO 1997003961A1 EP 9603108 W EP9603108 W EP 9603108W WO 9703961 A1 WO9703961 A1 WO 9703961A1
Authority
WO
WIPO (PCT)
Prior art keywords
methoxy
tri
groups
substituted
alkylphosphineoxide
Prior art date
Application number
PCT/EP1996/003108
Other languages
French (fr)
Inventor
Leonie Arina Stigter
Andreas Petrus Van Swieten
Auke Gerardus Talma
John Meijer
Original Assignee
Akzo Nobel N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to AU66570/96A priority Critical patent/AU6657096A/en
Publication of WO1997003961A1 publication Critical patent/WO1997003961A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/5537—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom the heteroring containing the structure -C(=O)-N-C(=O)- (both carbon atoms belong to the heteroring)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings

Definitions

  • initiators for polymer production A wide variety of peroxy compounds is known from the literature as initiators for polymer production. A fairly great number of these are commercially used. See, for example, the product catalogue of Akzo Nobel entitled “Initiators for polymer production", 1992, in which several dozens of initiators for radical polymerization have been mentioned under the trademarks Laurox ® , Lucidol ® , Perkadox ® and Trigonox ® . Other examples of commercially available initiators are included in the Akzo Nobel range of products sold under the trademarks Butanox ® and Cyclonox ® , respectively 1) .
  • initiators for polymer production may be classified in different chemical groups, which include diacylperoxides, peroxydicarbonates, dialkylperoxides, peroxyesters, peroxyketals, hydroperoxides, and ketone peroxides.
  • the present invention relates to a new group of peroxides which have highly interesting properties making them suitable for use in industrial applications. More particularly, the invention relates to imidoperoxides having the following general formula:
  • X is C(R 4 ,R 5 ), OC(O), C(R 6 ,OR 7 ), C(OR 8 ,OR 9 ), C(R 10 ,OOR 11 ) n is 1, 2 or 3;
  • Y is H , C (R 12 , R 13 , R 14 ) , C (0) R 15 , C (O) OR 16 , C (R 17 , R 18 , OR 19 ) ,
  • Y is C 7-22 alkylene having a tertiary structure at both ends, C 722 alkenylene having a tertiary structure at both ends, C 8-22 alkynylene having a tertiary structure at both ends, a group of the general formula: -C(CH 3 ) 2 -C 6 H 4-q -(R 26 ) q -C(CH 3 ) 2 - wherein q is 0 or 1 and R 26 is isopropyl, isopr ⁇ penyl or 2-hydroxyisopropyl, A[C(O)] 2 , wherein A is a covalent bond, C 1-22 alkylene, C 2-22 alkenylene, C 2-22 alkynylene, C 6-22 arylene, C 7-22 alkarylene, C 7-22 arylalkylene, or C 3-22 cycloalkylene, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amid
  • Y is 1,2,4-triisopropylbenzene- ⁇ , ⁇ ', ⁇ "-triyl, 1,3,5-triisopropylbenzene- ⁇ , ⁇ ', ⁇ "-triyl, E[C(O)] 3 , wherein E is selected from C 1-22 alkatriyl, C 2-22 alkenetriyl, C 2-22 alkyntriyl, C 6-22 aryltriyl, C 7-22 alkaryltriyl, C 7-22 arylalkatriyl, or C 3-22 cycloalkatriyl, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C 1-20 alkoxy, C 6-20 aryloxy, ketone, nitrile, C 1-20 alkylcarbonate, C 1-20 alkylsulfoxide, C 1-20 alkylsulfone, di(C 1-20 )alkylphosphineoxide, di(C 1
  • R 1 and R 2 are independently selected from H, C 1-22 alkyl, C 2-22 alkenyl, C 2-22 alkynyl, C 6-22 aryl, C 7-22 aralkyl and C 7-22 alkaryl, which groups may be linear or branched and be substituted with one or more functional groups selected from hydroxy, halogen, ester, carboxy, amido, C 1-20 alkoxy, C 6-20 aryloxy, ketone, nitrile, C 1-20 alkylcarbonate, C 1-20 alkylsulfoxide, C 1-20 alkylsulfone, di(C 1-20 )alkylphosphineoxide, di(C 1-20 )alkylphosphonate, tri(C 1-20 )alkylsilane and tri(C 1-20 )alkoxysilane;
  • R 28 and R 29 are independently selected from C 1-22 alkyl, C 2-22 alkenyl, C 2-22 alkynyl, C 6-22 aryl, C 7-22 aralkyl, and C 7-22 alkaryl, which groups may be linear or branched and be substituted with one or more functional groups selected from hydroxy, halogen, ester, acid, amido, C 1-20 alkoxy, C 6-20 aryloxy, ketone, nitrile, C 1-20 alkylcarbonate, C 1-20 alkylsulfoxide, C 1-20 alkylsulfone, di(C 1-20 )alkylphosphineoxide, di(C 1-20 )alkylphosphonate, tri(C 1- 20 )alkylsilane and tri(C 1-20 )alkoxysilane;
  • R 7 , R 8 , R 9 ., R 19 , R 21 , R 22 and R 30 are independently selected from C 1-22 alkyl, C 6-22 aryl, C 7 , 22 aralkyl, and C 7-22 alkaryl, which groups may be linear or branched and be substituted with one or more functional groups selected from hydroxy, halogen, ester, acid, amido, C 1-20 alkoxy, C 6-20 aryloxy, ketone, nitrile, C 1-20 alkylcarbonate, C 1-20 alkylsulfoxide, C 1-20 alkylsulfone, di(C 1-20 )-alkylphosphineoxide, di(C 1-20 )alkylphosphonate, tri(C 1-20 ) alkylsilana and tri(C 1-20 )alkoxysilane; or R 4 /R 5 , R 6 /OR 7 , OR 8 /OR 9 , R 12 /R 13 , R 17 /R 18
  • the imidoperoxides of the above formula (I) are new. They are highly interesting for industrial applications, such as initiation of polymerization processes, polymer modification and cross-linking. For example, the compounds show excellent properties in producing high molecular weight polystyrene (co)-polymers, the crosslinking of rubbers and elastomers, and in the curing of unsaturated polyesters.
  • R 1 and R 2 are independently hydrogen or C 1-6 alkyl.
  • alkyl groups are methyl and ethyl.
  • (I) are maleimido, citraconimido and dimethylmaleimido.
  • n is 1.
  • One sub-class of the compounds of formula I in accordance with the present invention is constituted by the "dialkyls", in which X is C(R 4 ,R 5 ) and n, Y and R 1-30 are as defined above.
  • Y is t-butyl, t-amyl, pinanyl, t-hexyl, p-menthyl, of-cumyl or 2,4,4,-trimethylpentyl-2
  • n is 1. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following: 2-t-butylperoxy-2-methyl-4-citraconimidobutane
  • Another sub-class of the compounds of formula I in accordance with the present invention is constituted by the imidoperoxycarbonates, in which X is OC(O) and n, Y and R 1-30 are as defined above. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following:
  • Still another sub-class of the compounds of formula I in accordance with the present invention is constituted by the imidoperacetals, in which X is C(R 6 ,OR 7 ) and n, Y and R 1-30 are as defined above.
  • the term " imidoperacetal” or “peracetal” as used in this application should be interpreted to include peroxides derived from both aldehydes (“peracetals”) and ketones (“perketals”), unless stated otherwise. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following:
  • a further sub-class of the compounds of formula I in accordance with the present invention is constituted by the imidoperortho esters, in which X is C(OR 8 ,OR 9 ) and n, Y and R 1-30 are as defined above. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following:
  • Still a further sub-class of the compounds of formula I in accordance with the present invention is constituted by the imidodiperoxyketals, in which X is C (R 10 , OOR 11 ) and n, Y and R 1-30 are as defined above. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following: 1,1-di(t-butylperoxy)-2-citraconimidoethane
  • (co) polymer as used in this application should be interpreted to mean “polymers and copolymers”.
  • the imido peroxides of the formula I are prepared in conventional manner, for example by methods which are known in the art for the preparation of analogous compounds.
  • the imidodialkylperoxides according to the invention are prepared by reacting an imido tert alkyl alcohol with a hydroperoxide under acidic conditions in a suitable solvent, essentially according to the following reaction scheme:
  • Suitable solvents include chlorohydrocarbons, e.g. dichloromethane; alkanes, in particular n-hexane and n-heptane, and phlegmatizing agents.
  • Suitable acids are, for example, sulfuric acid, perchloric acid and p-toluenesulfonic acid.
  • the temperature at which the reaction is conducted is in the range of from about 0°C to about 50°C, depending upon the reactivity of the agents used.
  • the reaction time is usually from about 2 to about 20 hours.
  • isolation and recovery of the desired are also performed in conventional manner for isolating and recovering solids.
  • the imidopercarbonates of formula (I) are prepared by reacting an imido chloroformate with a hydroperoxide under alkaline conditions in a suitable solvent, essentially according to the following reaction scheme:
  • R 1 to R 3 and Y are as defined above.
  • a suitable base is, for example, pyridine, triethylamine, Li, Na or KOH, etc.
  • the reaction is carried out under phase transfer conditions.
  • the chloroformate precursor is conveniently made by reacting a primary, secondary or tert. alchol with phosgene in the presence of a suitable base at a temperature in the range of about -20 to +50°C.
  • the imidoperacetals of formula (I) can be suitably prepared by reacting an acetal in a suitable solvent, e.g. dichloromethane, with an acid, e.g. sulfuric acid, perchloric acid or p-toluenesulfonic acid. To this solution is added the hydroperoxide of choice.
  • the reaction conditions again depend on the reactiviy of the agents used. Usually the reaction time is between about two to about 72 hours and the reaction temperature between ambient temperature up to about 50°C.
  • the imidoperoxyorthoesters and the imidodiperoxyketals are conveniently prepared in a similar way as the imidoperacetals.
  • the starting materials for the preparation of the imidoperoxides according to the present invention are either commercially available or they can be prepared in a manner known per se, e.g. for the preparation of analogous compounds.
  • the peroxides can be prepared, transported, stored and applied as such or in the form of, e.g., powders, granules, pellets, pastilles, flakes, slabs, solid masterbatches, solutions, suspensions, emulsions and pastes. These formulations may optionally be phlegmatized, as necessary, depending on the particular peroxide and its concentration in the formulation. Which of these forms is to be preferred partly depends on the application for which it will be used and partly on the manner that it will be mixed.
  • phlegmatizers may have to be incorporated in certain compositions to ensure their safety.
  • solid carrier materials such as inert plasticizers, solvents and inert diluents such as silicone oils, white oils, high boiling hydrocarbons such as isododecane, and water.
  • the present peroxides are well suited for use as initiators for polymer production, in particular the preparation of acrylic
  • the present invention comprises a process for the preparation of acrylic (co) polymers, ethylenic (co) polymers, styrenic (co) polymers and the curing of unsaturated polyesters, using the peroxides represented in formula I.
  • polymerization is conducted by any conventional process, except that a specified radical polymerization initiator (or composition) is used.
  • the polymerization processes may be carried out in the usual manner, for example in bulk, suspension, emulsion or solution.
  • the reaction is usually carried out under high pressure, e.g. about 1000 to about 3500 bar.
  • the peroxide may be brought into contact with the (co) polymer in various ways, depending upon the particular object of the modification process.
  • the peroxide is generally mixed with the material to be modified, which material may be in any physical form including finely divided particles (flake), pellets, sheet, in the melt, in solution, or, in the case of an elastomer, in a plastic state, and the like .
  • the amount of the initiator which may vary depending on the application and, more in particular, on the polymerization temperature, the capacity for removing the heat of polymerization, and, when applicable, the kind of monomer to be used and the applied pressure, should be an amount effective to achieve polymerization.
  • the temperature for most reactions within the present invention is usually from about 0°C to about 450°C, preferably from about ambient temperature (20°C) and more preferably from about 50°C to about 350°C.
  • the peroxide is spent in the initial stage of the reaction, making it difficult to attain a high conversion.
  • the peroxide is preferably used in combination with an accelerator.
  • a combination of two or more peroxides with different properties is used, for example peroxides with a higher and lower decomposition temperature (dual cure system).
  • a temperature profile e.g.
  • the formulations may also contain the usual additives and fillers.
  • additives such as stabilizers such as inhibitors of oxidative, thermal or ultraviolet degradation, lubricants, extender oils, pH controlling substances such as calcium carbonate, release agents, colorants, reinforcing or non-reinforcing fillers such as silica, clay, chalk, carbon black and fibrous materials such as glass fibers, plasticizers, diluents, chain transfer agents, accelerators and other types of peroxides.
  • stabilizers such as inhibitors of oxidative, thermal or ultraviolet degradation
  • lubricants such as lubricants, extender oils
  • pH controlling substances such as calcium carbonate, release agents, colorants, reinforcing or non-reinforcing fillers such as silica, clay, chalk, carbon black and fibrous materials such as glass fibers, plasticizers, diluents, chain transfer agents, accelerators and other types of peroxides.
  • Suitable monomers for polymerization using the peroxides according to the present invention are olefinic or ethylenically unsaturated monomers, for example substituted or unsubstituted vinyl aromatic monomers, including styrene, ⁇ -methylstyrene, p-methylstyrene and halogenated styrenes, divinylbenzene, ⁇ -pinene, ethylvinylbenzene and vinylnaphthalene; ethylene; ethylenically unsaturated carboxylic acids and derivatives thereof such as (meth) acrylic acids,
  • Unsaturated polyester resins that can be cured by the imidoperoxides according to the present invention usually include an unsaturated polyester and one or more ethylenically unsaturated monomers.
  • Suitable polymerizable monomers include styrene, ⁇ -methylstyrene, p-methylstyrene, chlorostyrenes, bromostyrenes, ⁇ -pinene, vinylbenzyl chloride, divinylbenzene, diallyl maleate, dibutyl fumarate, triallyl phosphate, triallyl cyanurate, diallylphthalate, diallyl fumarate, methyl
  • the unsaturated polyesters are, for example, polyesters as they are obtained by esterifying at least one ethylenically unsaturated di- or polycarboxylic acid, anhydride or acid halide, such as maleic acid, fumaric acid, glutaconic acid, itaconic acid, mesaconic acid, citraconic acid, allylmalonic acid, tetrahydrophthalic acid, and others, with saturated and unsaturated di- or polyols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediols, 1,2-, 1,3- and 1,4-butanediols, 2,2-dimethyl-1, 3-propanediols, 2-hydroxymethyl-2-methyl-1,3-propaned
  • the di- or polycarboxylic acids may be partially replaced by saturated di- or polycarboxylic acids, such as adipic acid, succinic acid and others, and/or by aromatic di- or polycarboxylic acids, such as phthalic acid, trimellitic acid, pyromellitic acid, isophthalic acid and terephthalic acid.
  • the acids used may be substituted by groups such as halogen. Suitable halogenated acids include, for example, tetrachlorophthalic acid and tetrabromophthalic acid.
  • the heating time is generally between 0.1 and 30 minutes and, more preferably, between 0.5 and 5 minutes.
  • the reaction is most preferably carried out in a moulding press or pulltrusion die. Due to the crosslinkable imido group the use of the imido ⁇ peroxides according to the present invention in UP applications will result in reduced amounts of volatiles and the absence of benzene.
  • any (co)polymer comprising abstractable hydrogen atoms can be modified by the present process.
  • polymers which tend to degrade include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, alkylene/ propylene copolymers such as ethylene/propylene random and block copolymers; propylene/diene monomer copolymers, propylene/styrene copolymers, poly(butene-1), poly (butene-2), polyisobutene, isoprene/isobutylene copolymers, chlorinated isoprene/isobutylene copolymers, poly(methylpentene), polyvinyl alcohol, polystyrene, poly ( ⁇ -methyl)styrene, 2, 6-dimethyl polyphenylene oxide and mixtures or blends of these polymers with one another and/or with other non-degradable polymers.
  • the imidoperoxides according to the present invention may also be employed in the crosslinking of polymers such as low, medium and high density polyethylene, ethylene/alkene copolymers, ethylene/propylene/diene monomer ter-polymers, chlorosulphonated polyethylene, chlorinated polyethylene, ethylene/ vinyl acetate copolymers, ethylene/propylene copolymers, propylene/diene monomer copolymers, brominated isoprene/ isobutylene copolymers, partially hydrogenated butadiene/ acrylonitrile copolymers, polyisoprene, polychloroprene, poly- (cyclopentadiene), poly (methylcyclopentadiene), polynorbornene, isoprene/styrene copolymers, butadiene/styrene copolymers, butadiene/acrylonitrile copolymers, acrylonitrile/butadiene/ st
  • the (co) polymer modification process of the present invention is also useful for the grafting of monomers onto polymers or for the production of graft-copolymers.
  • suitable (co) polymers which according to the present invention can be grafted by means of the imidoperoxides are copolymers and block copolymers of conjugated 1,3-dienes, and one or more copolymerizable monoethylenically unsaturated monomers such as aromatic monovinylidene hydrocarbons, halogenated aromatic monovinylidene hydrocarbons, (meth) acrylonitrile, alkyl (meth)- acrylates, acrylamides, unsaturated ketones, vinyl esters, vinylidenes and vinyl halides; ethylene/propylene copolymers and ethylene/propylene copolymers with other (poly) unsaturated compounds such as hexadiene-1,4, dicyclopentadiene and 5-ethylidenenorbornene; polyolefins
  • Such polyols include polyalkylene polyether polyols having from 2-6 carbon atoms per monomeric unit and an Mn of 400-2000, polyhydroxyl containing polyesters, hydroxy-terminated polyesters and aliphatic polyols.
  • Suitable monomers for grafting onto the above-mentioned polymers using the imidoperoxides of the present invention are olefinic or ethylenically unsaturated monomers such as: substituted or unsubstituted vinyl aromatic monomers including styrene and of-methylstyrene; ethylenically unsaturated carboxylic acids and derivatives thereof such as (meth) acrylic acids, (meth) acrylic esters and glycidyl methacrylate; ethylenically unsaturated nitriles and amides such as acrylonitrile, methacrylonitrile and acrylamide; substituted or unsubstituted ethylenically unsaturated monomers such as
  • the present invention provides a polymerization process which can be employed to introduce functional groups into (co) polymers. This may be accomplished by employing an imidoperoxide of the formula I which contains one or more functional "R" groups attached thereto. These functional groups will remain intact in the free radicals formed by the peroxides and thus are introduced into the (co) polymer. Conventional polymerization conditions and equipment may be used to achieve this object of the invention.
  • Residual monomer concentrations were determined by gas chromatography on a solution of the polymer in dichloromethane using n-butylbenzene or t-butylbenzene as an internal standard.
  • Example 1 but using a concentration of 0.375 meq t-butyl 2- (methylmaleimido)-1-methoxyethyl peroxide in 100 g of styrene monomer.
  • Example 1 but using a concentration of 0.563 meq t-butyl 2- (methylmaleimido)-1-methoxyethyl peroxide in 100 g of styrene monomer.
  • Example 1 but using a concentration of 0.750 meq t-butyl 2- (methylmaleimido)-1-methoxyethylperoxide in 100 g of styrene monomer.
  • Example 2 but using a concentration of 0.375 meq t-butyl 2- (maleimido)-1-methoxyethyl peroxide in 100 g of styrene monomer.
  • Example 8 but using a concentration of 0.375 meq t-butyl 2- (methylmaleimido)-1-methoxyethyl peroxide in 100 g of the styrene/ n-butylacrylate (80/20) monomer mixture.
  • Example 8 but using a concentration of 0.375 meq t-butyl 2- (dimethylmaleimido)-1-methoxyethyl peroxide in 100 g of the styrene/n-butyl acrylate (80/20) monomer mixture.
  • the application of the imidoperoxides in the curing of unsaturated polyesters has been evaluated for temperatures >100°C. Due to the polymerizable imido group the imidoperoxide will result in reduced amounts of volatiles.
  • Unsaturated Polyester (UP) resins at elevated or high temperatures comprises Hot Press Moulding (HPM) such as SMC, BMC, ZMC and TMC, pulltrusion, continuous laminating and sometimes RTM.
  • HPM Hot Press Moulding
  • a BMC formulation was prepared by mixing the ingredients by means of a Z-blade Mixer during 5 minutes. After a thickening period of 7 days, the BMC was pressed at 150°C/75 bar pressure during 150 sec on a SMC-Reactomer (SMC TECH Aachen) .
  • the BMC formulation consisted of:
  • Compound A was checked in three levels of addition.
  • the composition of the three compounds is mentioned in Table 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A new group of imido peroxides is provided which are represented by general formula (I), wherein X is C(R4,R5), OC(O), C(R6,OR7), C(OR8,OR9), C(R10,OOR11); and n is 1, 2 or 3. These compounds are highly interesting for industrial applications, such as initiation of polymerization processes, polymer modification and cross-linking. For example, they show excellent properties in producing high molecular weight polystyrene (co)polymers, the cross-linking of rubbers and elastomers, and in the curing of unsaturated polyesters. Also compositions are provided comprising at least one imido peroxide of formula (I), as well as methods of preparing these peroxides.

Description

IMIDO PEROXIDES AS INITIATORS OF POLYMERIZATION PROCESSES
A wide variety of peroxy compounds is known from the literature as initiators for polymer production. A fairly great number of these are commercially used. See, for example, the product catalogue of Akzo Nobel entitled "Initiators for polymer production", 1992, in which several dozens of initiators for radical polymerization have been mentioned under the trademarks Laurox®, Lucidol®, Perkadox® and Trigonox®. Other examples of commercially available initiators are included in the Akzo Nobel range of products sold under the trademarks Butanox® and Cyclonox®, respectively 1).
Commercially available initiators for polymer production may be classified in different chemical groups, which include diacylperoxides, peroxydicarbonates, dialkylperoxides, peroxyesters, peroxyketals, hydroperoxides, and ketone peroxides.
The present invention relates to a new group of peroxides which have highly interesting properties making them suitable for use in industrial applications. More particularly, the invention relates to imidoperoxides having the following general formula:
Figure imgf000003_0001
wherein:
X is C(R4,R5), OC(O), C(R6,OR7), C(OR8,OR9), C(R10,OOR11) n is 1, 2 or 3; and,
1) Laurox®, Lucidol®, Perkadox®, Trigonox®, Butanox® and Cyclonox® are registered trademarks of Akzo Nobel N.V. if n is 1 ,
Y is H , C (R12 , R13 , R14 ) , C (0) R15 , C (O) OR16 , C (R17 , R18 , OR19) ,
C (R20 , OR21 , OR22 ) , or C ( R23 , R24 , OOR25) ; if n is 2 ,
Y is C7-22 alkylene having a tertiary structure at both ends, C722 alkenylene having a tertiary structure at both ends, C8-22 alkynylene having a tertiary structure at both ends, a group of the general formula: -C(CH3)2-C6H4-q-(R26)q-C(CH3)2- wherein q is 0 or 1 and R26 is isopropyl, isoprσpenyl or 2-hydroxyisopropyl, A[C(O)]2, wherein A is a covalent bond, C1-22 alkylene, C2-22 alkenylene, C2-22 alkynylene, C6-22 arylene, C7-22 alkarylene, C7-22 arylalkylene, or C3-22 cycloalkylene, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di (C1- 20) alkylphosphonate, tri (C1-20) alkylsilane and tri (C1-20) alkoxysilane; D[OC(O)]2, wherein D is C1-22 alkylene, C6-22 arylene, C7-22 alkarylene, C7-22 arylalkylene, or C3-22 cycloalkylene, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di (C1-20) alkylphosphineoxide, di (C1-20) alkylphosphonate, tri (C1-20) alkylsilane and tri (C1-20)-alkoxysilane; C(R27,R28) or C(R29,OR30); if n is 3,
Y is 1,2,4-triisopropylbenzene-α,α',α"-triyl, 1,3,5-triisopropylbenzene-α,α',α"-triyl, E[C(O)]3, wherein E is selected from C1-22 alkatriyl, C2-22 alkenetriyl, C2-22 alkyntriyl, C6-22 aryltriyl, C7-22 alkaryltriyl, C7-22 arylalkatriyl, or C3-22 cycloalkatriyl, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)alkoxysilane; or G[OC(O)]3, wherein G is selected from C1-22 alkatriyl, C6-22 aryltriyl, C7-22 alkaryltriyl, C7-22 arylalkatriyl, or C3-22 cycloalkatriyl, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)-alkoxysilane.
R1 and R2 are independently selected from H, C1-22 alkyl, C2-22 alkenyl, C2-22 alkynyl, C6-22 aryl, C7-22 aralkyl and C7-22 alkaryl, which groups may be linear or branched and be substituted with one or more functional groups selected from hydroxy, halogen, ester, carboxy, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)alkoxysilane;
R3 is a covalent bond, C1-22 alkylene, C2-22 alkenylene, C2-22 alkynylene, C6-22 arylene, C7-22 alkarylene, C7-22 arylalkylene, C3- 22 cycloalkylene, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkyl- sulfone, di(C1-20)alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)alkoxysilane, maleimido, citraconimido (= methylmaleimido) and dimethylmaleimido; R4 , R5 , R6 , R10 , R12 , R13 , R14 , R15 , R16 , R17 , R18 , R20 , R23 , R24 , R27 ,
R28 and R29 are independently selected from C1-22 alkyl, C2-22 alkenyl, C2-22 alkynyl, C6-22 aryl, C7-22 aralkyl, and C7-22 alkaryl, which groups may be linear or branched and be substituted with one or more functional groups selected from hydroxy, halogen, ester, acid, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1- 20)alkylsilane and tri(C1-20)alkoxysilane;
R7, R8, R9., R19, R21, R22 and R30 are independently selected from C1-22 alkyl, C6-22 aryl, C7,22 aralkyl, and C7-22 alkaryl, which groups may be linear or branched and be substituted with one or more functional groups selected from hydroxy, halogen, ester, acid, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)-alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20) alkylsilana and tri(C1-20)alkoxysilane; or R4/R5, R6/OR7, OR8/OR9, R12/R13, R17/R18, R17/OR19, R20/OR21, OR21/OR22, R23/R24 may individually, together with the carbon atom to which they are attached, form a ring up to 20 atoms, optionally substituted; R11 and R25 are independently selected from C4-22 tertiary alkyl, tertiary cycloalkyl, tertiary alkenyl and tertiary alkynyl, and a group of the general formula: -C(CH3)2C-C6H5-p-(R26)p, wherein p is 0,1 or 2 and R26 has the above defined meaning. The imidoperoxides of the above formula (I) are new. They are highly interesting for industrial applications, such as initiation of polymerization processes, polymer modification and cross-linking. For example, the compounds show excellent properties in producing high molecular weight polystyrene (co)-polymers, the crosslinking of rubbers and elastomers, and in the curing of unsaturated polyesters.
Preferably, R1 and R2 are independently hydrogen or C1-6 alkyl.
The most preferred alkyl groups are methyl and ethyl. Particularly preferred imido groups of the compounds of formula
(I) are maleimido, citraconimido and dimethylmaleimido.
Preferably, n is 1. One sub-class of the compounds of formula I in accordance with the present invention is constituted by the "dialkyls", in which X is C(R4,R5) and n, Y and R1-30 are as defined above. Preferably, Y is t-butyl, t-amyl, pinanyl, t-hexyl, p-menthyl, of-cumyl or 2,4,4,-trimethylpentyl-2, and n is 1. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following: 2-t-butylperoxy-2-methyl-4-citraconimidobutane
2-t-amylperoxy-2-methyl-4-citraconimidobutane
2-t-hexylperoxy-2-methyl-4-citraconimidobutane
2-α-cumylperoxy-2-methyl-4-citraconimidobutane
2-pinanylperoxy-2-methyl-4-citraconimidobutane
2-p-menthylperoxy-2-methyl-4-citraconimidobutane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methyl-4-citraconimidobutane
2-t-butylperoxy-2-methyl-3-citraconimidopropane
2-t-amylperoxy-2-methyl-3-citraconimidopropane
2-t-hexylperoxy-2-methyl-3-citraconimidopropane
2-α-cumylperoxy-2-methyl-3-citraconimidopropane
2-pinanylperoxy-2-methyl-3-citraconimidopropane
2-p-menthylperoxy-2-methyl-3-citraconimidopropane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methyl-3-citraconimidopropane
1-t-butylperoxyisopropyl-3-citraconimidobenzene
1-t-amylperoxyisopropyl-3-citraconimidobenzene
1-t-hexylperoxyisopropyl-3-citraconimidobenzene
1-α-cumylperoxyisopropyl-3-citraconimidobenzene
1-pinanylperoxyisopropyl-3-citraconimidobenzene
1-p-menthylperoxyisopropyl-3-citraconimidobenzene
1-(2,2,4-trimethylpent-2-yl)peroxyisopropyl-3-citraconimidobenzene
2-t-butylperoxy-2-methyl-4-maleimidobutane
2-t-amylperoxy-2-methyl-4-maleimidobutane
2-t-hexylperoxy-2-methyl-4-maleimidobutane
2-α-cumylperoxy-2-methyl-4-maleimidobutane 2-pinanylperoxy-2-methyl-4-maleimidobutane
2-p-menthylperoxy-2-methyl-4-maleimidobutane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methyl-4-maleimidobutane 2-t-butylperoxy-2-methyl-3-maleimidopropane
2-t-amylperoxy-2-methyl-3-maleimidopropane
2-t-hexylperoxy-2-methyl-3-maleimidopropane
2-α-cumylperoxy-2-methyl-3-maleimidopropane
2-pinanylperoxy-2-methyl-3-maleimidopropane
2-p-menthylperoxy-2-methyl-3-maleimidopropane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methyl-3-maleimidopropane 1-t-butylperoxyisopropyl-3-maleimidobenzene
1-t-amylperoxyisopropyl-3-maleimidobenzene
1-t-hexylperoxyisopropyl-3-maleimidobenzene
1-α-cumylperoxyisopropyl-3-maleimidobenzene
1-pinanylperoxyisopropyl-3-maleimidobenzene
1-p-menthylperoxyisopropyl-3-maleimidobenzene
1-(2,2,4-trimethylpent-2-yl)peroxyisopropyl-3-maleimidobenzene 2-t-butylperoxy-2-methyl-4-dimethylmaleimidobutane
2-t-amylperoxy-2-methyl-4-dimethylmaleimidobutane
2-t-hexylperoxy-2-methyl-4-dimethylmaleimidobutane
2-α-cumylperoxy-2-methyl-4-dimethylmaleimidobutane
2-pinanylperoxy-2-methyl-4-dimethylmaleimidobutane
2-p-menthylperoxy-2-methyl-4-dimethylmaleimidobutane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methyl-4-dimethyl¬mameimidobutane
2-t-butylperoxy-2-methyl-3-dimethylmaleimidopropane
2-t-amylperoxy-2-methyl-3-dimethylmaleimidopropane
2-t-hexylperoxy-2-methyl-3-dimethylmaleimidopropane
2-α-cumylperoxy-2-methyl-3-dimethylmaleimidopropane
2-pinanylperoxy-2-methyl-3-dimethylmaleimidopropane
2-p-menthylperoxy-2-methyl-3-dimethylmaleimidopropane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methyl-3-dimethylmaleimidopropane
1-t-butylperoxyisopropyl-3-dimethylmaleimidobenzene
1-t-amylperoxyisopropyl-3-dimethylmaleimidobenzene
1-t-hexylperoxyisopropyl-3-dimethylmaleimidobenzene
1-α-cumylperoxyisopropyl-3-dimethylmaleimidobenzene 1-pinanylperoxyisopropyl-3-dimethylmaleimidobenzene
1-p-menthylperoxyisopropyl-3-dimethylmaleimidobenzene
1-(2,2,4-trimethylpent-2-yl)peroxyisopropyl-3-dimethylmaleimidobenzene.
Another sub-class of the compounds of formula I in accordance with the present invention is constituted by the imidoperoxycarbonates, in which X is OC(O) and n, Y and R1-30 are as defined above. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following:
OO-t-butyl O-2-citraconimidoethyl monoperoxycarbonate
OO-t-amyl O-2-citraconimidoethyl monoperoxycarbonate
OO-t-hexyl O-2-citraconimidoethyl monoperoxycarbonate
OO-α-cumyl O-2-citraconimidoethyl monoperoxycarbonate
OO-pinanyl O-2-citraconimidoethyl monoperoxycarbonate
OO-p-menthyl O-2-citraconimidoethyl monoperoxycarbonate
OO-(2,2,4-trimethylpent-2-yl) O-2-citraconimidoethyl monoperoxycarbonate
OO-t-butyl O-3-citraconimidopropyl monoperoxycarbonate
OO-t-amyl O-3-citraconimidopropyl monoperoxycarbonate
OO-t-hexyl O-3-citraconimidopropyl monoperoxycarbonate
OO-α-cumyl O-3-citraconimidopropyl monoperoxycarbonate
OO-pinanyl O-3-citraconimidopropyl monoperoxycarbonate
OO-p-menthyl O-3-citraconimidopropyl monoperoxycarbonate
OO-(2,2,4-trimethylpent-2-yl) O-3-citraconimidopropyl monoperoxycarbonate
OO-t-butyl O-2-citraconimidopropyl monoperoxycarbonate
OO-t-amyl O-2-citraconimidopropyl monoperoxycarbonate
OO-t-hexyl O-2-citraconimidopropyl monoperoxycarbonate
OO-α-cumyl O-2-citraconimidopropyl monoperoxycarbonate
OO-pinanyl O-2-citraconimidopropyl monoperoxycarbonate
OO-p-menthyl O-2-citraconimidopropyl monoperoxycarbonate
OO-(2,2,4-trimethylpent-2-yl) O-2-citraconimidopropyl monoperoxycarbonate OO-t-butyl O-2-maleimidoethyl monoperoxycarbonate
OO-t-amyl O-2-maleimidoethyl monoperoxycarbonate
OO-t-hexyl O-2-maleimidoethyl monoperoxycarbonate
OO-α-cumyl O-2-maleimidoethyl monoperoxycarbonate
OO-pinanyl O-2-maleimidoethyl monoperoxycarbonate
OO-p-menthyl O-2-maleimidoethyl monoperoxycarbonate
OO-(2,2,4-trimethylpent-2-yl) O-2-maleimidoethyl monoperoxycarbonate
OO-t-butyl O-3-maleimidopropyl monoperoxycarbonate
OO-t-amyl O-3-maleimidopropyl monoperoxycarbonate
OO-t-hexyl O-3-maleimidopropyl monoperoxycarbonate
OO-α-cumyl O-3-maleimidopropyl monoperoxycarbonate
OO-pinanyl O-3-maleimidopropyl monoperoxycarbonate
OO-p-menthyl O-3-maleimidopropyl monoperoxycarbonate
OO-(2,2,4-trimethylpent-2-yl) O-3-maleimidopropyl monoperoxycarbonate
OO-t-butyl O-2-maleimidopropyl monoperoxycarbonate
OO-t-amyl O-2-maleimidopropyl monoperoxycarbonate
OO-t-hexyl O-2-maleimidopropyl monoperoxycarbonate
OO-α-cumyl O-2-maleimidopropyl monoperoxycarbonate
OO-pinanyl O-2-maleimidopropyl monoperoxycarbonate
OO-p-menthyl O-2-maleimidopropyl monoperoxycarbonate
OO-(2,2,4-trimethylpent-2-yl) O-2-maleimidopropyl monoperoxycarbonate
OO-t-butyl O-2-dimethylmaleimidoethyl monoperoxycarbonate
OO-t-amyl O-2-dimethylmaleimidoethyl monoperoxycarbonate
OO-t-hexyl O-2-dimethylmaleimidoethyl monoperoxycarbonate
OO-α-cumyl O-2-dimethylmaleimidoethyl monoperoxycarbonate
OO-pinanyl O-2-dimethylmaleimidoethyl monoperoxycarbonate
OO-p-menthyl O-2-dimethylmaleimidoethyl monoperoxycarbonate
OO-(2,2,4-trimethylpent-2-yl) O-2-dimethylmaleimidoethyl monoperoxycarbonate
OO-t-butyl O-3-dimethylmaleimidopropyl monoperoxycarbonate
OO-t-amyl O-3-dimethylmaleimidopropyl monoperoxycarbonate
OO-t-hexyl O-3-dimethylmaleimidopropyl monoperoxycarbonate
OO-α-cumyl O-3-dimethylmaleimidopropyl monoperoxycarbonate
OO-pinanyl O-3-dimethylmaleimidopropyl monoperoxycarbonate OO-p-menthyl O-3-dimethylmaleimidopropyl monoperoxycarbonate
OO-(2,2,4-trimethylpent-2-yl) O-3-dimethylmaleimidopropyl monoperoxycarbonate
OO-t-butyl O-2-dimethylmaleimidopropyl monoperoxycarbonate
OO-t-amyl O-2-dimethylmaleimidopropyl monoperoxycarbonate
OO-t-hexyl O-2-dimethylmaleimidopropyl monoperoxycarbonate OO-α-cumyl O-2-dimethylmaleimidopropyl monoperoxycarbonate
OO-pinanyl O-2-dimethylmaleimidopropyl monoperoxycarbonate
OO-p-menthyl O-2-dimethylmaleimidopropyl monoperoxycarbonate
OO-(2,2,4-trimethylpent-2-yl) O-2-dimethylmaleimidopropyl monoperoxycarbonate.
Still another sub-class of the compounds of formula I in accordance with the present invention is constituted by the imidoperacetals, in which X is C(R6,OR7) and n, Y and R1-30 are as defined above. The term " imidoperacetal" or "peracetal" as used in this application should be interpreted to include peroxides derived from both aldehydes ("peracetals") and ketones ("perketals"), unless stated otherwise. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following:
1-t-butylperoxy-1-methoxy-2-citraconimidoethane
1-t-amylperoxy-1-methoxy-2-citraconimidoethane
1-t-hexylperoxy-1-methoxy-2-citraconimidoethane
1-α-cumylperoxy-1-methoxy-2-citraconimidoethane
1-pinanylperoxy-1-methoxy-2-citraconimidoethane
1-p-menthylperoxy-1-methoxy-2-citraconimidoethane
1-(2,2,4-trimethylpent-2-yl)peroxy-1-methoxy-2-citraconimidoethane
1-t-butylperoxy-1-methoxy-3-citraconimidopropane
1-t-amylperoxy-1-methoxy-3-citraconimidopropane
1-t-hexylperoxy-1-methoxy-3-citraconimidopropane
1-α-cumylperoxy-1-methoxy-3-citraconimidopropane
1-pinanylperoxy-1-methoxy-3-citraconimidopropane
1-p-menthylperoxy-1-methoxy-3-citraconimidopropane 1-(2,2,4-trimethylpent-2-yl)peroxy-1-methoxy-3-citraconimidopropane
1-t-butylperoxy-1-methoxy-2-citraconimidopropane
1-t-amylperoxy-1-methoxy-2-citraconimidopropane
1-t-hexylperoxy-1-methoxy-2-citraconimidopropane
1-α-cumylperoxy-1-methoxy-2-citraconimidopropane
1-pinanylperoxy-1-methoxy-2-citraconimidopropane
1-p-menthylperoxy-1-methoxy-2-citraconimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1-methoxy-2-citraconimidopropane
1-(1-t-butylperoxy-1-methoxy)ethyl-4-citraconimidobenzene 1-(1-t-amylperoxy-1-methoxy)ethyl-4-citraconimidobenzene 1-(1-t-hexylperoxy-1-methoxy)ethyl-4-citraconimidobenzene 1-(1-α-cumylperoxy-1-methoxy)ethyl-4-citraconimidobenzene 1-(1-pinanylperoxy-1-methoxy)ethyl-4-citraconimidobenzene 1-(1-p-menthylperoxy-1-methoxy)ethyl-4-citraconimidobenzene 1-[1-(2,2,4-trimethylpent-2-yl)-1-methoxy)]ethyl-4-citraconimidobenzene
1-(2-t-butylperoxy-2-methoxy)ethyl-2-citraconimidobenzene 1-(2-t-amylperoxy-2-methoxy)ethyl-2-citraconimidobenzene 1-(2-t-hexylperoxy-2-methoxy)ethyl-2-citraconimidobenzene 1-(2-α-cumylperoxy-2-methoxy)ethyl-2-citraconimidobenzene 1-(2-pinanylperoxy-2-methoxy)ethyl-2-citraconimidobenzene 1-(2-p-menthylperoxy-2-methoxy)ethyl-2-citraconimidobenzene1-[2-(2,2,4-trimethylpent-2-yl)-2-methoxy)]ethyl-2-citraconimidobenzene
1-(3-t-butylperoxy-3-methoxy)propyl-2-citraconimidobenzene 1-(3-t-amylperoxy-3-methoxy)propyl-2-citraconimidobenzene 1-(3-t-hexylperoxy-3-methoxy)propyl-2-citraconimidobenzene 1-(3-α-cumylperoxy-3-methoxy)propyl-2-citraconimidobenzene 1-(3-pinanylperoxy-3-methoxy)propyl-2-citraconimidobenzene 1-(3-p-menthylperoxy-3-methoxy)propyl-2-citraconimidobenzene 1-[3-(2,2,4-trimethylpent-2-yl)-3-methoxy)]propyl-2-citraconimidobenzene
2-t-butylperoxy-2-methoxy-4-citraconimidobutane
2-t-amylperoxy-2-methoxy-4-citraconimidobutane
2-t-hexylperoxy-2-methoxy-4-citraconimidobutane 2-α-cumylperoxy-2-methoxy-4-citraconimidobutane
2-pinanylperoxy-2-methoxy-4-citraconimidobutane
2-p-menthylperoxy-2-methoxy-4-citraconimidobutane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methoxy-4-citraconimidobutane
2-t-butylperoxy-2-methoxy-5-citraconimidopentane
2-t-amylperoxy-2-methoxy-5-citraconimidopentane
2-t-hexylperoxy-2-methoxy-5-citraconimidopentane
2-α-cumylperoxy-2-methoxy-5-citraconimidopentane
2-pinanylperoxy-2-methoxy-5-citraconimidopentane
2-p-menthylperoxy-2-methoxy-5-citraconimidopentane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methoxy-5-citraconimidopentane
1-t-butylperoxy-1-methoxy-2-maleimidoethane
1-t-amylperoxy-1-methoxy-2-maleimidoethane
1-t-hexylperoxy-1-methoxy-2-maleimidoethane
1-α-cumylperoxy-1-methoxy-2-maleimidoethane
1-pinanylperoxy-1-methoxy-2-maleimidoethane
1-p-menthylperoxy-1-methoxy-2-maleimidoethane
1-(2,2,4-trimethylpent-2-yl)peroxy-1-methoxy-2-maleimidoethane 1-t-butylperoxy-1-methoxy-3-maleimidopropane
1-t-amylperoxy-1-methoxy-3-maleimidopropane
1-t-hexylperoxy-1-methoxy-3-maleimidopropane
1-α-cumylperoxy-1-methoxy-3-maleimidopropane
1-pinanylperoxy-1-methoxy-3-maleimidopropane
1-p-menthylperoxy-1-methoxy-3-maleimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1-methoxy-3-maleimidopropane 1-t-butylperoxy-1-methoxy-2-maleimidopropane
1-t-amylperoxy-1-methoxy-2-maleimidopropane
1-t-hexylperoxy-1-methoxy-2-maleimidopropane
1-α-cumylperoxy-1-methoxy-2-maleimidopropane
1-pinanylperoxy-1-methoxy-2-maleimidopropane
1-p-menthylperoxy-1-methoxy-2-maleimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1-methoxy-2-maleimidopropane 1-(1-t-butylperoxy-1-methoxy)ethyl-4-maleimidobenzene
1-(1-t-amylperoxy-1-methoxy)ethyl-4-maleimidobenzene
1-(1-t-hexylperoxy-1-methoxy)ethyl-4-maleimidobenzene 1-(1-α-cumylperoxy-1-methoxy)ethyl-4-maleimidobenzene
1-(1-pinanylperoxy-1-methoxy)ethyl-4-maleimidobenzene
1-(1-p-menthylperoxy-1-methoxy)ethyl-4-maleimidobenzene
1-[1-(2,2,4-trimethylpent-2-yl)-1-methoxy)]ethyl-4-maleimidobenzene
1-(2-t-butylperoxy-2-methoxy)ethyl-2-maleimidobenzene
1-(2-t-amylperoxy-2-methoxy)ethyl-2-maleimidobenzene
1-(2-t-hexylperoxy-2-methoxy)ethyl-2-maleimidobenzene
1-(2-α-cumylperoxy-2-methoxy)ethyl-2-maleimidobenzene
1-(2-pinanylperoxy-2-methoxy)ethyl-2-maleimidobenzene
1-(2-p-menthylperoxy-2-methoxy)ethyl-2-maleimidobenzene
1-[2-(2,2,4-trimethylpent-2-yl)-2-methoxy)]ethyl-2-maleimidobenzene
1-(3-t-butylperoxy-3-methoxy)propyl-2-maleimidobenzene
1-(3-t-amylperoxy-3-methoxy)propyl-2-maleimidobenzene
1-(3-t-hexylperoxy-3-methoxy)propyl-2-maleimidobenzene
1-(3-α-cumylperoxy-3-methoxy)propyl-2-maleimidobenzene
1-(3-pinanylperoxy-3-methoxy)propyl-2-maleimidobenzene
1-(3-p-menthylperoxy-3-methoxy)propyl-2-maleimidobenzene
1-[3-(2,2,4-trimethylpent-2-yl)-3-methoxy)]propyl-2-maleimidobenzene
2-t-butylperoxy-2-methoxy-4-maleimidobutane
2-t-amylperoxy-2-methoxy-4-maleimidobutane
2-t-hexylperoxy-2-methoxy-4-maleimidobutane
2-α-cumylperoxy-2-methoxy-4-maleimidobutane
2-pinanylperoxy-2-methoxy-4-maleimidobutane
2-p-menthylperoxy-2-methoxy-4-maleimidobutane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methoxy-4-maleimidobutane 2-t-butylperoxy-2-methoxy-5-maleimidopentane
2-t-amylperoxy-2-methoxy-5-maleimidopentane
2-t-hexylperoxy-2-methoxy-5-maleimidopentane
2-α-cumylperoxy-2-methoxy-5-maleimidopentane
2-pinanylperoxy-2-methoxy-5-maleimidopentane
2-p-menthylperoxy-2-methoxy-5-maleimidopentane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methoxy-5-maleimidopentane 1-t-butylperoxy-1-methoxy-2-dimethylmaleimidoethane
1-t-amylperoxy-1-methoxy-2-dimethylmaleimidoethane 1-t-hexylperoxy-1-methoxy-2-dimethylmaleimidoethane
1-α-cumylperoxy-1-methoxy-2-dimethylmaleimidoethane
1-pinanylperoxy-1-methoxy-2-dimethylmaleimidoethane
1-p-menthylperoxy-1-methoxy-2-dimethylmaleimidoethane
1-(2,2,4-trimethylpent-2-yl)peroxy-1-methoxy-2-dimethylmaleimidoethane
1-t-butylperoxy-1-methoxy-3-dimethylmaleimidopropane
1-t-amylperoxy-1-methoxy-3-dimethylmaleimidopropane
1-t-hexylperoxy-1-methoxy-3-dimethylmaleimidopropane
1-α-cumylperoxy-1-methoxy-3-dimethylmaleimidopropane
1-pinanylperoxy-1-methoxy-3-dimethylmaleimidopropane
1-p-menthylperoxy-1-methoxy-3-dimethylmaleimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1-methoxy-3-dimethylmaleimidopropane
1-t-butylperoxy-1-methoxy-2-dimethylmaleimidopropane
1-t-amylperoxy-1-methoxy-2-dimethylmaleimidopropane
1-t-hexylperoxy-1-methoxy-2-dimethylmaleimidopropane
1-α-cumylperoxy-1-methoxy-2-dimethylmaleimidopropane
1-pinanylperoxy-1-methoxy-2-dimethylmaleimidopropane
1-p-menthylperoxy-1-methoxy-2-dimethylmaleimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1-methoxy-2-dimethylmaleimidopropane
1-(1-t-butylperoxy-1-methoxy)ethyl-4-dimethylmaleimidobenzene 1-(1-t-amylperoxy-1-methoxy)ethyl-4-dimethylmaleimidobenzene 1-(1-t-hexylperoxy-1-methoxy)ethyl-4-dimethylmaleimidobenzene 1-(1-α-cumylperoxy-1-methoxy)ethyl-4-dimethylmaleimidobenzene 1-(1-pinanylperoxy-1-methoxy)ethyl-4-dimethylmaleimidobenzene 1-(1-p-menthylperoxy-1-methoxy)ethyl-4-dimethylmaleimidobenzene 1-[1-(2,2,4-trimethylpent-2-yl)-1-methoxy)]ethyl-4-dimethylmaleimidobenzene
1-(2-t-butylperoxy-2-methoxy)ethyl-2-dimethylmaleimidobenzene 1-(2-t-amylperoxy-2-methoxy)ethyl-2-dimethylmaleimidobenzene 1-(2-t-hexylperoxy-2-methoxy)ethyl-2-dimethylmaleimidobenzene 1-(2-α-cumylperoxy-2-methoxy)ethyl-2-dimethylmaleimidobenzene 1-(2-pinanylperoxy-2-methoxy)ethyl-2-dimethylmaleimidobenzene 1-(2-p-menthylperoxy-2-methoxy)ethyl-2-dimethylmaleimidobenzene 1-[2-(2,2,4-trimethylpent-2-yl)-2-methoxy)]ethyl-2-dimethyl maleimidobenzene
1-(3-t-butylperoxy-3-methoxy)propyl-2-dimethylmaleimidobenzene 1-(3-t-amylperoxy-3-methoxy)propyl-2-dimethylmaleimidobenzene 1-(3-t-hexylperoxy-3-methoxy)propyl-2-dimethylmaleimidobenzene 1-(3-α-cumylperoxy-3-methoxy)propyl-2-dimethylmaleimidobenzene 1-(3-pinanylperoxy-3-methoxy)propyl-2-dimethylmaleimidobenzene 1-(3-p-menthylperoxy-3-methoxy)propyl-2-dimethylmaleimidobenzene
1-[3-(2,2,4-trimethylpent-2-yl)-3-methoxy)]propyl-2-dimethylmaleimidobenzene
2-t-butylperoxy-2-methoxy-4-dimethylmaleimidobutane
2-t-amylperoxy-2-methoxy-4-dimethylmaleimidobutane
2-t-hexylperoxy-2-methoxy-4-dimethylmaleimidobutane
2-α-cumylperoxy-2-methoxy-4-dimethylmaleimidobutane
2-pinanylperoxy-2-methoxy-4-dimethylmaleimidobutane
2-p-menthylperoxy-2-methoxy-4-dimethylmaleimidobutane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methoxy-4-dimethylmaleimidobutane
2-t-butylperoxy-2-methoxy-5-dimethylmaleimidopentane
2-t-amylperoxy-2-methoxy-5-dimethylmaleimidopentane
2-t-hexylperoxy-2-methoxy-5-dimethylmaleimidopentane
2-α-cumylperoxy-2-methoxy-5-dimethylmaleimidopentane
2-pinanylperoxy-2-methoxy-5-dimethylmaleimidopentane
2-p-menthylperoxy-2-methoxy-5-dimethylmaleimidopentane
2-(2,2,4-trimethylpent-2-yl)peroxy-2-methoxy-5-dimethylmaleimidopentane.
Examples of preferred peroxides of this sub-class are:
1-t-butylperoxy-1-methoxy-2-citraconimidoethane
1-t-butylperoxy-1-methoxy-2-dimethylmaleimidoethane
1-t-butylperoxy-1-methoxy-2-maleimidoethane
1-t-butylperoxy-1-methoxy-2-citraconimidopropane
1-t-butylperoxy-1-methoxy-2-dimethylmaleimidopropane
1-t-butylperoxy-1-methoxy-2-maleimidopropane
A further sub-class of the compounds of formula I in accordance with the present invention is constituted by the imidoperortho esters, in which X is C(OR8,OR9) and n, Y and R1-30 are as defined above. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following:
1-t-butylperoxy-1,1-dimethoxy-2-citraconimidoethane
1-t-amylperoxy-1,1-dimethoxy-2-citraconimidoethane
1-t-hexylperoxy-1,1-dimethoxy-2-citraconimidoethane
1-α-cumylperoxy-1,1-dimethoxy-2-citraconimidoethane
1-pinanylperoxy-1,1-dimethoxy-2-citraconimidoethane
1-p-menthylperoxy-1,1-dimethoxy-2-citraconimidoethane
1-(2,2,4-trimethylpent-2-yl)peroxy-1,1-dimethoxy-2-citraconimidoethane
1-t-butylperoxy-1,1-dimethoxy-3-citraconimidopropane
1-t-amylperoxy-1,1-dimethoxy-3-citraconimidopropane
1-t-hexylperoxy-1,1-dimethoxy-3-citraconimidopropane
1-α-cumylperoxy-1,1-dimethoxy-3-citraconimidopropane
1-pinanylperoxy-1,1-dimethoxy-3-citraconimidopropane
1-p-menthylperoxy-1,1-dimethoxy-3-citraconimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1,1-dimethoxy-3-citraconimidopropane
1-t-butylperoxy-1,1-diethoxy-3-citraconimidopropane
1-t-amylperoxy-1,1-diethoxy-3-citraconimidopropane
1-t-hexylperoxy-l,1-diethoxy-3-citraconimidopropane
1-α-cumylperoxy-1,1-diethoxy-3-citraconimidopropane
1-pinanylperoxy-1,1-diethoxy-3-citraconimidopropane
1-p-menthylperoxy-1,1-diethoxy-3-citraconimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1,1-diethoxy-3-citraconimidopropane
1-t-butylperoxy-1,1-dimethoxy-2-maleimidoethane
1-t-amylperoxy-1,1-dimethoxy-2-maleimidoethane
1-t-hexylperoxy-1,1-dimethoxy-2-maleimidoethane
1-α-cumylperoxy-1,1-dimethoxy-2-maleimidoethane
1-pinanylperoxy-1,1-dimethoxy-2-maleimidoethane
1-p-menthylperoxy-1,1-dimethoxy-2-maleimidoethane
1-(2,2,4-trimethylpent-2-yl)peroxy-1,1-dimethoxy-2-maleimido ethane
1-t-butylperoxy-1,1-dimethoxy-3-maleimidopropane
1-t-amylperoxy-1,1-dimethoxy-3-maleimidopropane
1-t-hexylperoxy-1,1-dimethoxy-3-maleimidopropane
1-α-cumylperoxy-1,1-dimethoxy-3-maleimidopropane
1-pinanylperoxy-1,1-dimethoxy-3-maleimidopropane
1-p-menthylperoxy-1,1-dimethoxy-3-maleimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1,1-dimethoxy-3-maleimidopropane
1-t-butylperoxy-1,1-diethoxy-3-maleimidopropane
1-t-amylperoxy-1,1-diethoxy-3-maleimidopropane
1-t-hexylperoxy-1,1-diethoxy-3-maleimidopropane
1-α-cumylperoxy-1,1-diethoxy-3-maleimidopropane
1-pinanylperoxy-1,1-diethoxy-3-maleimidopropane
1-p-menthylperoxy-1,1-diethoxy-3-maleimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1,1-diethoxy-3-maleimidopropane
1-t-butylperoxy-1,1-dimethoxy-2-dimethylmaleimidoethane
1-t-amylperoxy-1,1-dimethoxy-2-dimethylmaleimidoethane
1-t-hexylperoxy-1,1-dimethoxy-2-dimethylmaleimidoethane
1-α-cumylperoxy-1,1-dimethoxy-2-dimethylmaleimidoethane
1-pinanylperoxy-1,1-dimethoxy-2-dimethylmaleimidoethane
1-p-menthylperoxy-1,1-dimethoxy-2-dimethylmaleimidoethane 1-(2,2,4-trimethylpent-2-yl)peroxy-1,1-dimethoxy-2-dimethylmaleimidoethane
1-t-butylperoxy-1,1-dimethoxy-3-dimethylmaleimidopropane 1-t-amylperoxy-1,1-dimethoxy-3-dimethylmaleimidopropane
1-t-hexylperoxy-1,1-dimethoxy-3-dimethylmaleimidopropane 1-α-cumylperoxy-1,1-dimethoxy-3-dimethylmaleimidopropane 1-pinanylperoxy-1,1-dimethoxy-3-dimethylmaleimidopropane 1-p-menthylperoxy-1,1-dimethoxy-3-dimethylmaleimidopropane 1-(2,2,4-trimethylpent-2-yl)peroxy-1,1-dimethoxy-3-dimethylmaleimidopropane
1-t-butylperoxy-1,1-diethoxy-3-dimethylmaleimidopropane 1-t-amylperoxy-1,1-diethoxy-3-dimethylmaleimidopropane
1-t-hexylperoxy-1,1-diethoxy-3-dimethylmaleimidopropane 1-α-cumylperoxy-1,1-diethoxy-3-dimethylmaleimidopropane 1-pinanylperoxy-1,1-diethoxy-3-dimethylmaleimidopropane
1-p-menthylperoxy-1,1-diethoxy-3-dimethylmaleimidopropane
1-(2,2,4-trimethylpent-2-yl)peroxy-1,1-diethoxy-3-dimethylmaleimidopropane
Still a further sub-class of the compounds of formula I in accordance with the present invention is constituted by the imidodiperoxyketals, in which X is C (R10, OOR11) and n, Y and R1-30 are as defined above. More specific examples of some of the imido peroxide compounds according to this sub-class which are useful in the present invention include, but are not limited to, the following: 1,1-di(t-butylperoxy)-2-citraconimidoethane
1,1-di(t-amylperoxy)-2-citraconimidoethane
1,1-di(t-hexylperoxy)-2-citraconimidoethane
1,1-di(α-cumylperoxy)-2-citraconimidoethane
1,1-di(pinanylperoxy)-2-citraconimidoethane
1,1-di(p-menthylperoxy)-2-citraconimidoethane
1,1-di[(2,2,4-trimethylpent-2-yl)peroxy]-2-citraconimidoethane 1,1-di(t-butylperoxy)-3-citraconimidopropane
1,1-di(t-amylperoxy)-3-citraconimidopropane
1,1-di(t-hexylperoxy)-3-citraconimidopropane
1,1-di(a-cumylperoxy)-3-citraconimidopropane
1,1-di(pinanylperoxy)-3-citraconimidopropane
1,1-di(p-menthylperoxy)-3-citraconimidopropane
1,1-[(2,2,4-trimethylpent-2-yl)peroxy]-3-citraconimidopropane 2,2-di(t-butylperoxy)-4-citraconimidobutane
2,2-di(t-amylperoxy)-4-citraconimidobutane
2,2-di(t-hexylperoxy)-4-citraconimidobutane
2,2-di(α-cumylperoxy)-4-citraconimidobutane
2,2-di(pinanylperoxy)-4-citraconimidobutane
2,2-di(p-menthylperoxy)-4-citraconimidobutane
2,2-di[(2,2,4-trimethylpent-2-yl)peroxy]-4-citraconimidobutane 2,2-di(t-butylperoxy)-5-citraconimidopentane
2,2-di(t-amylperoxy)-5-citraconimidopentane
2,2-di(t-hexylperoxy)-5-citraconimidopentane 2,2-di(α-cumylperoxy)-5-citraconimidopentane
2,2-di(pinanylperoxy)-5-citraconimidopentane
2,2-di(p-menthylperoxy)-5-citraconimidopentane
2,2-di[(2,2,4-trimethylpent-2-yl)peroxy]-5-citraconimidopentane
1,1-di(t-butylperoxy)-2-maleimidoethane
1,1-di(t-amylperoxy)-2-maleimidoethane
1,1-di(t-hexylperoxy)-2-maleimidoethane
1,1-di(α-cumylperoxy)-2-maleimidoethane
1,1-di(pinanylperoxy)-2-maleimidoethane
1,1-di(p-menthylperoxy)-2-maleimidoethane
1,1-di[(2,2,4-trimethylpent-2-yl)peroxy]-2-maleimidoethane
1,1-di(t-butylperoxy)-3-maleimidopropane
1,1-di(t-amylperoxy)-3-maleimidopropane
1 1-di(t-hexylperoxy)-3-maleimidopropane
1,1-di(α-cumylperoxy)-3-maleimidopropane
1,1-di(pinanylperoxy)-3-maleimidopropane
1,1-di(p-menthylperoxy)-3-maleimidopropane
1,1- [(2,2,4-trimethylpent-2-yl)peroxy]-3-maleimidopropane
2,2-di(t-butylperoxy)-4-maleimidobutane
2,2-di(t-amylperoxy)-4-maleimidobutane
2,2-di(t-hexylperoxy)-4-maleimidobutane
2,2-di(α-cumylperoxy)-4-maleimidobutane
2,2-di(pinanylperoxy)-4-maleimidobutane
2,2-di(p-menthylperoxy)-4-maleimidobutane
2,2-di[(2,2,4-trimethylpent-2-yl)peroxy]-4-maleimidobutane
2,2-di(t-butylperoxy)-5-maleimidopentane
2,2-di(t-amylperoxy)-5-maleimidopentane
2,2-di(t-hexylperoxy)-5-maleimidopentane
2,2-di(α-cumylperoxy)-5-maleimidopentane
2,2-di(pinanylperoxy)-5-maleimidopentane
2,2-di(p-menthylperoxy)-5-maleimidopentane
2,2-di[(2,2,4-trimethylpent-2-yl)peroxy]-5-maleimidopentane
1,1-di(t-butylperoxy)-2-dimethylmaleimidoethane
1,1-di(t-amylperoxy)-2-dimethylmaleimidoethane
1,1-di(t-hexylperoxy)-2-dimethylmaleimidoethane
1,1-di(α-cumylperoxy)-2-dimethylmaleimidoethane
1,1-di(pinanylperoxy)-2-dimethylmaleimidoethane 1,1-di(p-menthylperoxy)-2-dimethylmaleimidoethane
1,1-di[(2,2,4-trimethylpent-2-yl)peroxy]-2-dimethylmaleimidoethane
1,1-di(t-butylperoxy)-3-dimethylmaleimidopropane
1,1-di(t-amylperoxy)-3-dimethylmaleimidopropane
1,1-di(t-hexylperoxy)-3-dimethylmaleimidopropane
1,1-di(α-cumylperoxy)-3-dimethylmaleimidopropane
1,1-di(pinanylperoxy)-3-dimethylmaleimidopropane
1,1-di(p-menthylperoxy)-3-dimethylmaleimidopropane
1,1-[(2,2,4-trimethylpent-2-yl)peroxy]-3-dimethylmaleimidopropane
2,2-di(t-butylperoxy)-4-dimethylmaleimidobutane
2,2-di(t-amylperoxy)-4-dimethylmaleimidobutane
2,2-di(t-hexylperoxy)-4-dimethylmaleimidobutane
2,2-di(α-cumylperoxy)-4-dimethylmaleimidobutane
2,2-di(pinanylperoxy)-4-dimethylmaleimidobutane
2,2-di(p-menthylperoxy)-4-dimethylmaleimidobutane
2,2-di((2,2,4-trimethylpent-2-yl)peroxy]-4-dimethylmaleimidobutane
2,2-di(t-butylperoxy)-5-dimethylmaleimidopentane
2,2-di(t-amylperoxy)-5-dimethylmaleimidopentane
2,2-di(t-hexylperoxy)-5-dimethylmaleimidopentane
2,2-di(α-cumylperoxy)-5-dimethylmaleimidopentane
2,2-di(pinanylperoxy)-5-dimethylmaleimidopentane
2,2-di(p-menthylperoxy)-5-dimethylmaleimidopentane
2,2-di[(2,2,4-trimethylpent-2-yl)peroxy]-5-dimethylmaleimidopentane.
The word "(co) polymer" as used in this application should be interpreted to mean "polymers and copolymers".
The imido peroxides of the formula I are prepared in conventional manner, for example by methods which are known in the art for the preparation of analogous compounds. Thus, in a typical procedure the imidodialkylperoxides according to the invention are prepared by reacting an imido tert alkyl alcohol with a hydroperoxide under acidic conditions in a suitable solvent, essentially according to the following reaction scheme:
Figure imgf000022_0001
wherein R1 to R5 and Y are as defined above. Suitable solvents include chlorohydrocarbons, e.g. dichloromethane; alkanes, in particular n-hexane and n-heptane, and phlegmatizing agents.
Suitable acids are, for example, sulfuric acid, perchloric acid and p-toluenesulfonic acid. Generally, the temperature at which the reaction is conducted is in the range of from about 0°C to about 50°C, depending upon the reactivity of the agents used.
The reaction time is usually from about 2 to about 20 hours.
The isolation and recovery of the desired are also performed in conventional manner for isolating and recovering solids.
In another typical procedure the imidopercarbonates of formula (I) are prepared by reacting an imido chloroformate with a hydroperoxide under alkaline conditions in a suitable solvent, essentially according to the following reaction scheme:
Figure imgf000022_0002
wherein R1 to R3 and Y are as defined above. A suitable base is, for example, pyridine, triethylamine, Li, Na or KOH, etc. Preferably, the reaction is carried out under phase transfer conditions. The chloroformate precursor is conveniently made by reacting a primary, secondary or tert. alchol with phosgene in the presence of a suitable base at a temperature in the range of about -20 to +50°C.
The imidoperacetals of formula (I) can be suitably prepared by reacting an acetal in a suitable solvent, e.g. dichloromethane, with an acid, e.g. sulfuric acid, perchloric acid or p-toluenesulfonic acid. To this solution is added the hydroperoxide of choice. The reaction conditions again depend on the reactiviy of the agents used. Usually the reaction time is between about two to about 72 hours and the reaction temperature between ambient temperature up to about 50°C. The imidoperoxyorthoesters and the imidodiperoxyketals are conveniently prepared in a similar way as the imidoperacetals.
The starting materials for the preparation of the imidoperoxides according to the present invention are either commercially available or they can be prepared in a manner known per se, e.g. for the preparation of analogous compounds.
The peroxides can be prepared, transported, stored and applied as such or in the form of, e.g., powders, granules, pellets, pastilles, flakes, slabs, solid masterbatches, solutions, suspensions, emulsions and pastes. These formulations may optionally be phlegmatized, as necessary, depending on the particular peroxide and its concentration in the formulation. Which of these forms is to be preferred partly depends on the application for which it will be used and partly on the manner that it will be mixed.
Also, considerations of safety may play a role to the extent that phlegmatizers may have to be incorporated in certain compositions to ensure their safety. As examples of suitable phlegmatizers may be mentioned solid carrier materials such as inert plasticizers, solvents and inert diluents such as silicone oils, white oils, high boiling hydrocarbons such as isododecane, and water.
The present peroxides are well suited for use as initiators for polymer production, in particular the preparation of acrylic
(co) polymers, styrene (co) polymers, ethylene (co) polymers and vinylchloride (co) polymers, for use in the modification of polymers, in particular the degradation of polyolefins such as polypropylene and copolymers thereof, the crosslinking of polyolefins such as ethylene/propylene/diene polymers, polyethylene and copolymers thereof, the crosslinking of rubbers and elastomers, such as EPDM rubber, the dynamic crosslinking of blends of elastomers and thermoplastic polymers, the grafting of monomers onto polymers such as polyethers, polyolefins and elastomers, and the functionalization of polyolefins, as well as in the curing of unsaturated polyester resins (by processes such as SMC, BMC, pulltrusion, RTM and continuous laminating, etc).
In styrene bulk (co) polymerization, when using the peroxides of the present invention, high molecular weight polymers can be produced at high polymerization rate. Accordingly, in one aspect the present invention comprises a process for the preparation of acrylic (co) polymers, ethylenic (co) polymers, styrenic (co) polymers and the curing of unsaturated polyesters, using the peroxides represented in formula I.
In the present invention, polymerization is conducted by any conventional process, except that a specified radical polymerization initiator (or composition) is used. The polymerization processes may be carried out in the usual manner, for example in bulk, suspension, emulsion or solution. In the case of production of ethylene (co) polymers the reaction is usually carried out under high pressure, e.g. about 1000 to about 3500 bar. For the application of the peroxides of the present invention in the modification of polymers, the peroxide may be brought into contact with the (co) polymer in various ways, depending upon the particular object of the modification process. The peroxide is generally mixed with the material to be modified, which material may be in any physical form including finely divided particles (flake), pellets, sheet, in the melt, in solution, or, in the case of an elastomer, in a plastic state, and the like .
The amount of the initiator, which may vary depending on the application and, more in particular, on the polymerization temperature, the capacity for removing the heat of polymerization, and, when applicable, the kind of monomer to be used and the applied pressure, should be an amount effective to achieve polymerization. Usually, from 0.001-25% weight of peroxide, based on the weight of the (co) polymer, should be employed. Preferably, from 0.001-10% weight and most preferably from 0.001-5% weight of peroxide is employed.
The temperature for most reactions within the present invention is usually from about 0°C to about 450°C, preferably from about ambient temperature (20°C) and more preferably from about 50°C to about 350°C. When the temperature exceeds 450°C, the peroxide is spent in the initial stage of the reaction, making it difficult to attain a high conversion. For curing of unsaturated polyester resins at a temperature between ambient and 50°C the peroxide is preferably used in combination with an accelerator. Often a combination of two or more peroxides with different properties is used, for example peroxides with a higher and lower decomposition temperature (dual cure system). In order to reduce the amount of unreacted monomer, it is also possible to conduct polymerization using a temperature profile, e.g. to perform the initial polymerization at about 90°C and then elevate the temperature above 115°C to complete the polymerization. These variations are all known to the man skilled in the art, who will have no difficulty in selecting the reaction conditions of choice, depending on the particular process and the specific peroxide according to the invention to be used. An important criterion in selecting a suitable peroxide in accordance with the present invention is the half-life of the peroxide under application conditions. During (co) polymerization, crosslinking or modification, the formulations may also contain the usual additives and fillers. As examples of such additives may be mentioned: stabilizers such as inhibitors of oxidative, thermal or ultraviolet degradation, lubricants, extender oils, pH controlling substances such as calcium carbonate, release agents, colorants, reinforcing or non-reinforcing fillers such as silica, clay, chalk, carbon black and fibrous materials such as glass fibers, plasticizers, diluents, chain transfer agents, accelerators and other types of peroxides. These additives may be employed in the usual amounts.
Suitable monomers for polymerization using the peroxides according to the present invention are olefinic or ethylenically unsaturated monomers, for example substituted or unsubstituted vinyl aromatic monomers, including styrene, α-methylstyrene, p-methylstyrene and halogenated styrenes, divinylbenzene, β-pinene, ethylvinylbenzene and vinylnaphthalene; ethylene; ethylenically unsaturated carboxylic acids and derivatives thereof such as (meth) acrylic acids,
(meth) acrylic esters, for example 2-ethylhexyl acrylate, 2- ethylhexyl methacrylate, glycidyl methacrylate and hydroxyethyl methacrylate; di, tri and tetra (meth) acrylates; ethylenically unsaturated nitriles and amides such as acrylonitrile, methacrylonitrile and acrylamide; substituted or unsubstituted ethylenically unsaturated monomers such as butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate and vinyl propionate; ethylenically unsaturated dicarboxylic acids and their derivatives including mono- and diesters, anhydrides and imides, such as maleic anhydride, citraconic (= methylmaleic) anhydride, citraconic acid, itaconic acid, nadic anhydride, maleic acid, fumaric acid, aryl, alkyl and aralkyl citraconimides and maleimides; vinyl halides such as vinyl chloride and vinylidene chloride; vinylethers such as methylvinylether and n-butylvinylether; olefins such as isobutene and 4-methylpentene; allyl compounds such as (di) allyl esters, for example diallyl phthalates, (di) allyl carbonates, and triallyl (iso) cyanurate.
Unsaturated polyester resins that can be cured by the imidoperoxides according to the present invention usually include an unsaturated polyester and one or more ethylenically unsaturated monomers. Suitable polymerizable monomers include styrene, α-methylstyrene, p-methylstyrene, chlorostyrenes, bromostyrenes, β-pinene, vinylbenzyl chloride, divinylbenzene, diallyl maleate, dibutyl fumarate, triallyl phosphate, triallyl cyanurate, diallylphthalate, diallyl fumarate, methyl
(meth)acrylate, n-butyl (meth) acrylate, ethyl acrylate, and mixtures thereof, which are copolymerizable with the unsaturated polyesters. The unsaturated polyesters are, for example, polyesters as they are obtained by esterifying at least one ethylenically unsaturated di- or polycarboxylic acid, anhydride or acid halide, such as maleic acid, fumaric acid, glutaconic acid, itaconic acid, mesaconic acid, citraconic acid, allylmalonic acid, tetrahydrophthalic acid, and others, with saturated and unsaturated di- or polyols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediols, 1,2-, 1,3- and 1,4-butanediols, 2,2-dimethyl-1, 3-propanediols, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2- buten-1,4-diol, 2-butyn-l, 4-diol, 2, 4,4-trimethyl-1,3-pentanediol, glycerol, pentaerythritol, mannitol, and others. The di- or polycarboxylic acids may be partially replaced by saturated di- or polycarboxylic acids, such as adipic acid, succinic acid and others, and/or by aromatic di- or polycarboxylic acids, such as phthalic acid, trimellitic acid, pyromellitic acid, isophthalic acid and terephthalic acid. The acids used may be substituted by groups such as halogen. Suitable halogenated acids include, for example, tetrachlorophthalic acid and tetrabromophthalic acid.
In the case of unsaturated polyester ("UP") resins, the application of the peroxides according to the invention is confined to temperatures >0°C. Usually, a temperature of about
20-250°C and more preferably about 50-200°C, is employed. The heating time is generally between 0.1 and 30 minutes and, more preferably, between 0.5 and 5 minutes. The reaction is most preferably carried out in a moulding press or pulltrusion die. Due to the crosslinkable imido group the use of the imido¬peroxides according to the present invention in UP applications will result in reduced amounts of volatiles and the absence of benzene.
In general, any (co)polymer comprising abstractable hydrogen atoms can be modified by the present process. For instance, polymers which tend to degrade include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, alkylene/ propylene copolymers such as ethylene/propylene random and block copolymers; propylene/diene monomer copolymers, propylene/styrene copolymers, poly(butene-1), poly (butene-2), polyisobutene, isoprene/isobutylene copolymers, chlorinated isoprene/isobutylene copolymers, poly(methylpentene), polyvinyl alcohol, polystyrene, poly (α-methyl)styrene, 2, 6-dimethyl polyphenylene oxide and mixtures or blends of these polymers with one another and/or with other non-degradable polymers.
The imidoperoxides according to the present invention may also be employed in the crosslinking of polymers such as low, medium and high density polyethylene, ethylene/alkene copolymers, ethylene/propylene/diene monomer ter-polymers, chlorosulphonated polyethylene, chlorinated polyethylene, ethylene/ vinyl acetate copolymers, ethylene/propylene copolymers, propylene/diene monomer copolymers, brominated isoprene/ isobutylene copolymers, partially hydrogenated butadiene/ acrylonitrile copolymers, polyisoprene, polychloroprene, poly- (cyclopentadiene), poly (methylcyclopentadiene), polynorbornene, isoprene/styrene copolymers, butadiene/styrene copolymers, butadiene/acrylonitrile copolymers, acrylonitrile/butadiene/ styrene terpolymers, polyacrylamides, polymethacrylamides, polyurethanes, polysulfides, polyethylene terephthalate, polybutylene terephthalate, copolyether esters, polyamides, silicone rubbers, fluor rubbers such as polyfluoralkoxy- phosphazenes; allylglycidylether/epichlorohydrin copolymers and mixtures or blends thereof.
The (co) polymer modification process of the present invention is also useful for the grafting of monomers onto polymers or for the production of graft-copolymers. Examples of suitable (co) polymers which according to the present invention can be grafted by means of the imidoperoxides are copolymers and block copolymers of conjugated 1,3-dienes, and one or more copolymerizable monoethylenically unsaturated monomers such as aromatic monovinylidene hydrocarbons, halogenated aromatic monovinylidene hydrocarbons, (meth) acrylonitrile, alkyl (meth)- acrylates, acrylamides, unsaturated ketones, vinyl esters, vinylidenes and vinyl halides; ethylene/propylene copolymers and ethylene/propylene copolymers with other (poly) unsaturated compounds such as hexadiene-1,4, dicyclopentadiene and 5-ethylidenenorbornene; polyolefins such as polyethylene, polypropylene and copolymers thereof; and polyols including polyols which are essentially free of ethylenic unsaturation. Such polyols include polyalkylene polyether polyols having from 2-6 carbon atoms per monomeric unit and an Mn of 400-2000, polyhydroxyl containing polyesters, hydroxy-terminated polyesters and aliphatic polyols. Suitable monomers for grafting onto the above-mentioned polymers using the imidoperoxides of the present invention are olefinic or ethylenically unsaturated monomers such as: substituted or unsubstituted vinyl aromatic monomers including styrene and of-methylstyrene; ethylenically unsaturated carboxylic acids and derivatives thereof such as (meth) acrylic acids, (meth) acrylic esters and glycidyl methacrylate; ethylenically unsaturated nitriles and amides such as acrylonitrile, methacrylonitrile and acrylamide; substituted or unsubstituted ethylenically unsaturated monomers such as butadiene; vinyl esters such as vinyl acetate and vinyl propionate; ethylenically unsaturated dicarboxylic acids and their derivatives including mono- and diesters, anhydrides and imides, such as maleic anhydride, citraconic anhydride, citraconic acid, itaconic acid, nadic anhydride, maleic acid, aryl, alkyl and aralkyl citraconimides and maleimides; vinyl halogenides such as vinyl chloride and vinylidene chloride; olefins such as isobutene and 4-methylpentene; and epoxides.
Finally, in another aspect, the present invention provides a polymerization process which can be employed to introduce functional groups into (co) polymers. This may be accomplished by employing an imidoperoxide of the formula I which contains one or more functional "R" groups attached thereto. These functional groups will remain intact in the free radicals formed by the peroxides and thus are introduced into the (co) polymer. Conventional polymerization conditions and equipment may be used to achieve this object of the invention.
The invention is further illustrated by the following examples which are not to be construed as limiting the invention in any way. The scope of the invention is to be determined from the claims appended hereto.
Experimental Synthesis examples Preparation of acetal citraconimides and dimethylmaleimides General procedures
A. A mixture of 0.5 mole of amino acetal and 0.51 mole of anhydride in 500 ml acetic acid, is refluxed for 2 hrs. The water/acetic acid azeotrope is distilled off. The crude product is purified by distillation under reduced pressure.
B. A mixture of 0.5 mole aminoacetal, 0.51 mole anhydride and 1.5 g CF3COOH in 500 ml. Q 5911 (bp. 140-165°C, ex. Shell) is refluxed using a Dean Stark trap until the theoretical amount of water is distilled off. The solvent is evaporated, and the crude product is purified by distillation under reduced pressure.
Preparation of acetal maleimides
For the preparation of these maleimides a procedure is used similar to the method described in GB 2.018.253 B (1982), which is incorporated herein by reference.
Preparation of peroxyacetal containing maleimides, citraconimides and dimethylmaleimides General Procedure
To a solution of acetal (0.2 mole) in CH2Cl2 (150 ml) is added 1.8 ml of concentrated H2SO4. To this solution is added 0.22 mole TBHP (t-butyl hydroperoxide) at room temperature. The mixture is stirred for 72 hrs at room temperature. To the solution is added K2CO3 to neutralize the acid. The organic layer is washed three times with 50 ml NaOH (0.1 N) and then with H2O to pH 7. The organic layer is dried over MgSO4, filtered and the solvent evaporated under reduced pressure. The peracetal is used as such.
Materials Employed
Monomers:
Styrene (distilled)
n-Butylacrylate (distilled)
Imido peroxides: t-butyl 2-(methylmaleimido)-1-methoxyethyl peroxide
t-butyl 2-(maleimido)-1-methoxyethyl peroxide
t-butyl 2-(dimethylmaleimido)-1-methoxyethyl peroxide
Methods used in the examples
Molecular weight and dispersity of the resins
Molecular weights and dispersity of the resins were determined by Gel Permeation Chromatography using polystyrene standards.
Conversion
Conversion was calculated from residual monomer content. Residual monomer concentrations were determined by gas chromatography on a solution of the polymer in dichloromethane using n-butylbenzene or t-butylbenzene as an internal standard.
Testing of imidoperoxides as polymerization initiators A. Styrene mass polymerization
Example 1
0.188 meq t-butyl 2-(methylmaleimido)-1-methoxyethyl peroxide was added to 100 g of styrene monomer. Mass polymerization of styrene was carried out in 3 ml brown glass ampoules in a thermostatted oil bath at 110°C. Ampoules were removed from the oil bath after 2, 4, 6, 7 and 8 hours. The samples were quenched in a 20 ml solution of dichloromethane containing Topanol® OC (butylated hydroxytoluene) and n-butyl benzene as internal standard. Styrene conversion as a function of time and molecular weight distribution after 8 hrs of polymerization are given in Table 1.
Example 2
As Example 1, but using a concentration of 0.375 meq t-butyl 2- (methylmaleimido)-1-methoxyethyl peroxide in 100 g of styrene monomer.
Example 3
As Example 1, but using a concentration of 0.563 meq t-butyl 2- (methylmaleimido)-1-methoxyethyl peroxide in 100 g of styrene monomer.
Example 4
As Example 1, but using a concentration of 0.750 meq t-butyl 2- (methylmaleimido)-1-methoxyethylperoxide in 100 g of styrene monomer.
Example 5
As Example 4, but polymerization was carried out at 120°C.
Example 6
As Example 2, but using a concentration of 0.375 meq t-butyl 2- (maleimido)-1-methoxyethyl peroxide in 100 g of styrene monomer.
Example 7
As Example 2 , but using a concentration of 0 .375 meq t-butyl 2- (dimethylmaleimido) -1-methoxyethyl peroxide in 100 g of styrene monomer . B. Styrene acrylic copolymerization
Example 8
0.375 meq t-butyl 2-(maleimido)-1-methoxyethyl peroxide was added to a mixture of 80 g of styrene monomer and 20 g of n-butyl acrylate. Mass copolymerization of this mixture was carried out in 3 ml brown glass ampoules in a thermostatted oil bath at 110°C. Ampoules were removed from the oil bath after 2, 4, 6, 8 and 10 hours. The samples were quenched in a 20 ml solution of dichloromethane containing Topanol OC (butylated hydroxytoluene) and n-butyl benzene as internal standard. Monomer conversion as a function of time and molecular weight distribution after 10 hrs of polymerization are given in Table 2.
Example 9
As Example 8, but using a concentration of 0.375 meq t-butyl 2- (methylmaleimido)-1-methoxyethyl peroxide in 100 g of the styrene/ n-butylacrylate (80/20) monomer mixture.
Example 10
As Example 8, but using a concentration of 0.375 meq t-butyl 2- (dimethylmaleimido)-1-methoxyethyl peroxide in 100 g of the styrene/n-butyl acrylate (80/20) monomer mixture.
Figure imgf000035_0001
The application of the imidoperoxides in the curing of unsaturated polyesters has been evaluated for temperatures >100°C. Due to the polymerizable imido group the imidoperoxide will result in reduced amounts of volatiles.
C. Curing of Unsaturated Polyesters
The curing of Unsaturated Polyester (UP) resins at elevated or high temperatures comprises Hot Press Moulding (HPM) such as SMC, BMC, ZMC and TMC, pulltrusion, continuous laminating and sometimes RTM. These techniques are described in "Unsaturated Polyester and Vinyl Ester Resins", Chapter 4 of the Handbook of Thermoset Plastics, ed. S. H. Goodman. Example 11
A BMC formulation was prepared by mixing the ingredients by means of a Z-blade Mixer during 5 minutes. After a thickening period of 7 days, the BMC was pressed at 150°C/75 bar pressure during 150 sec on a SMC-Reactomer (SMC Technologie Aachen) .
The BMC formulation consisted of:
- 100 parts of resin (e.g. Palatal® P18 ex BASF)
- 200 parts of filler Durcal® 5
75 parts of 6 mm chopped glass fibers
- 5 parts zinc stearate
5 parts of styrene
1.5 parts Luvatix® MK35 (thickening agent)
Example 12
Instead of 1.5 parts of t-butyl 2-(methylmaleimido)-1-methoxyethyl peroxide, the same amount of t-butyl 2-(maleimido)-1-methoxyethyl peroxide was used. The results are mentioned in Table 3.
Example 13
Instead of 1.5 parts of t-butyl 2-(methylmaleimido)-1-methoxyethyl peroxide, the same amount of t-butyl 2-(dimethyl-maleimido)-1-methoxyethyl peroxide was used. The results are mentioned in Table 3.
Figure imgf000037_0001
D. Crosslinking of rubbers
Example 14
The crosslinking efficiency of an imidoperoxide according to the present invention, viz. tert-butyl 2-citraconimido-1-methoxyethyl peroxide, was demonstrated in a model EPDM compound. The liquid imidoperoxide was phlegmatized (50% on silica) prior to the RCAL trials. The phlegmatized compound
("Compound A") was checked in three levels of addition. The composition of the three compounds is mentioned in Table 4.
Figure imgf000038_0001
The rheological data of the three compound are shown in Table 5 below.
Figure imgf000038_0002
Finally, the mechanical data of the composition with the highest addition of Compound A are given in Table 6 below.
Figure imgf000038_0003
The foregoing examples were presented for the purpose of illustration and description only and are not to be construed as limiting the invention in any way. The scope of the invention is to be determined from the claims appended hereto.

Claims

Claims
A compound of the general formula:
Figure imgf000040_0001
wherein: X is C(R4,R5) , OC(O) , C(R6,OR7) , C(OR8,OR9) , C(R10,OOR11) n is 1, 2 or 3; and, if n is 1,
Y is H, C(R12,R13,R14) , C(O)R15, C(0)OR16, C (R17, R18, OR19) ,
C ( R20 , OR21, OR22 ) , or C ( R23 , R24 , OOR25) ; if n is 2,
Y is C7-22 alkylene having a tertiary structure at both ends, C7_22 alkenylene having a tertiary structure at both ends, C8-22 alkynylene having a tertiary structure at both ends, a group of the general formula: -C (CH3)2-C6H4-q-(R26) q-C (CH3)2- wherein q is 0 or 1 and R26 is isopropyl, isopropenyl or 2-hydroxyisopropyl,
A[C(O)] wherein A is a covalent bond, C1-22 alkylene, C2-22 alkenylene, C2-22 alkynylene, C6-22 arylene, C7-22 alkarylene, C7-22 arylalkylene, or C3-22 cycloalkylene, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di(C1-20)-alkylphosphonate, tri (C1-20)alkylsilane and tri (C1-20) alkoxysilane; D[OC(O)]2, wherein D is C1-22 alkylene, C6-22 arylene, C7-22 alkarylene, C7-22 arylalkylene, or C3_22 cycloalkylene, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)-alkoxysilane; C(R27,R28) or C(R29,OR30); if n is 3,
Y is 1,2,4-triisopropylbenzene-α,α',α"-triyl, 1,3,5-triisopropylbenzene-α,α',α"-triyl, E[C(O)]3, wherein E is selected from C1-22 alkatriyl, C2-22 alkenetriyl, C2-22 alkyntriyl, C6-22 aryltriyl, C7-22 alkaryltriyl, C7-22 arylalkatriyl, or C3-22 cycloalkatriyl, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)alkoxysilane; or G[OC(O)]3, wherein G is selected from C1-22 alkatriyl, C6-22 aryltriyl, C7-22 alkaryltriyl, C7-22 arylalkatriyl, or C3-22 cycloalkatriyl, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)-alkoxysilane;
R1 and R2 are independently selected from H, C1- 22 alkyl, C2-22 alkenyl, C2-22 alkynyl, C6-22 aryl, C7-22 aralkyl and C7-22 alkaryl, which groups may be linear or branched and be substituted with one or more functional groups selected from hydroxy, halogen, ester, carboxy, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20)alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)alkoxysilane;
R3 is a covalent bond, C1-22 alkylene, C2-22 alkenylene, C2-22 alkynylene, C6 22 arylene, C7-22 alkarylene, C7-22 arylalkylene, C3-22 cycloalkylene, which groups may be branched or linear and be substituted with one or more groups selected from hydroxy, halogen, ester, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di(C1-20 )alkylphosphineoxide, di(C1-20)alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)alkoxysilane, maleimido, citraconimido (= methylmaleimido) and dimethylmaleimido;
R4, R5, R6, R10, R12, R13, R14, R15, R16, R17, R18, R20, R23, R24, R27, R28 and R29 are independently selected from C1-22 alkyl, C2-22 alkenyl, C2-22 alkynyl, C6-22 aryl, C7-22 aralkyl, and C7-22 alkaryl, which groups may be linear or branched and be substituted with one or more functional groups selected from hydroxy, halogen, ester, acid, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di (C1-20)-alkylphosphineoxide, di(C1-20) alkylphosphonate, tri(C1-20)alkylsilane and tri(C1-20)alkoxysilane;
R7, R8, R9, R19, R21, R22 and R30 are independently selected from C1-22 alkyl, C6-22 aryl, C7-22 aralkyl, and C7-22 alkaryl, which groups may be linear or branched and be substituted with one or more functional groups selected from hydroxy, halogen, ester, acid, amido, C1-20 alkoxy, C6-20 aryloxy, ketone, nitrile, C1-20 alkylcarbonate, C1-20 alkylsulfoxide, C1-20 alkylsulfone, di (C1-20) - alkylphosphineoxide, di (C1-20)alkylphosphonate, tri (C1-20) alkylsilane and tri(C1-20)alkoxysilane; or R4/R5, R6/OR7, OR8/OR9, R12/R13, R17/R18, Rι7/OR19, R20/OR21, OR21/OR22, R23/R24 may individually, together with the carbon atom to which they are attached, form a ring up to 20 atoms, optionally substituted;
R11 and R25 are independently selected from C4-22 tertiary alkyl, tertiary cycloalkyl, tertiary alkenyl and tertiary alkynyl, and a group of the general formula: -C(CH3)2C-C6H5-p-(R26)p, wherein p is 0,1 or 2 and R26 has the above defined meaning.
2. The compound of Claim 1, wherein R1 and R2 are independently hydrogen or C1-6 alkyl and n is 1.
3. The compound of Claim 1 or 2, wherein the imido group is maleimido, citraconimido or dimethylmaleimido.
4. The compound of any one of Claims 1 to 3 as represented in figure (I), wherein X is C(R6,OR7) and R6 and R7 are as defined in Claim 1.
5. A stable peroxide composition comprising at least one organic peroxide selected from the compounds represented by formula I as defined in claim 1; and 10-99% by weight of one or more diluents selected from the group consisting of liquid phlegmatizers for the imido peroxides, plasticizers, solid polymeric carriers, inorganic supports, organic peroxides and mixtures thereof.
6. A process for the preparation of an imidoperoxide of formula I, wherein X, Y, n and R1-30 are as defined in Claim 1, in a manner known in the art for the preparation of analogous compounds.
7. Use of an imidoperoxide of formula I, wherein X, Y, n and R1-30 are as defined in Claim 1, as an initiator of polymerization processes, in polymer modification, in the crosslinking of rubbers and elastomers, or in the curing of unsaturated polyesters.
PCT/EP1996/003108 1995-07-14 1996-07-12 Imido peroxides as initiators of polymerization processes WO1997003961A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU66570/96A AU6657096A (en) 1995-07-14 1996-07-12 Imido peroxides as initiators of polymerization processes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP95201949 1995-07-14
EP95201949.5 1995-07-14

Publications (1)

Publication Number Publication Date
WO1997003961A1 true WO1997003961A1 (en) 1997-02-06

Family

ID=8220491

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/003108 WO1997003961A1 (en) 1995-07-14 1996-07-12 Imido peroxides as initiators of polymerization processes

Country Status (2)

Country Link
AU (1) AU6657096A (en)
WO (1) WO1997003961A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016094163A1 (en) 2014-12-09 2016-06-16 Arkema Inc. Compositions and methods for crosslinking polymers in the presence of atmospheric oxygen
WO2022074237A1 (en) 2020-10-09 2022-04-14 Arkema France Composition comprising at least one organic peroxide and at least one sulfur-containing compound for crosslinking polymers in the presence of oxygen
EP4039733A1 (en) 2013-03-14 2022-08-10 Arkema, Inc. Methods for crosslinking polymer compositions in the presence of atmospheric oxygen
FR3132102A1 (en) 2022-01-25 2023-07-28 Arkema France Process for curing a curable composition
FR3132103A1 (en) 2022-01-25 2023-07-28 Arkema France Peroxide formulations with anti-scorch properties

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 113, no. 3, 16 July 1990, Columbus, Ohio, US; abstract no. 20222d, S. MATSUGO ET AL. *
CHEMICAL ABSTRACTS, vol. 76, no. 25, 1972, Columbus, Ohio, US; abstract no. 152898f, T.KOENIG ET AL.: "Nitrogen radical initiators" page 389; XP002014089 *
CHEMICAL ABSTRACTS. REGISTRY HANDBOOK - NUMBER SECTION. PRINTED ISSUES, COLUMBUS US, XP002014086 *
H.G. BRÜNKER ET AL.: "Diastereoselective and regioselective singlet oxygen ene oxyfunctionalisation", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 117, no. 14, April 1995 (1995-04-01), WASHINGTON, DC US, pages 3976 - 3982, XP002014087 *
ISAO SAITO ET AL.: "Phthalimide hydroperoxydes as efficient photochemical hydroxyl radical initiators", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 112, no. 2, 1990, WASHINGTON, DC US, pages 883 - 884, XP002014088 *
POLYM. PREPR., AMER. CHEM. SOC., DIV. POLYM. CHEM., vol. 11, no. 2, 1970, pages 826 - 832 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4039733A1 (en) 2013-03-14 2022-08-10 Arkema, Inc. Methods for crosslinking polymer compositions in the presence of atmospheric oxygen
WO2016094163A1 (en) 2014-12-09 2016-06-16 Arkema Inc. Compositions and methods for crosslinking polymers in the presence of atmospheric oxygen
WO2022074237A1 (en) 2020-10-09 2022-04-14 Arkema France Composition comprising at least one organic peroxide and at least one sulfur-containing compound for crosslinking polymers in the presence of oxygen
FR3115041A1 (en) 2020-10-09 2022-04-15 Arkema France Composition comprising at least one organic peroxide and at least one sulfur-containing compound for crosslinking polymers in the presence of oxygen
FR3132102A1 (en) 2022-01-25 2023-07-28 Arkema France Process for curing a curable composition
FR3132103A1 (en) 2022-01-25 2023-07-28 Arkema France Peroxide formulations with anti-scorch properties
WO2023144146A1 (en) 2022-01-25 2023-08-03 Arkema France Method for curing a curable composition
WO2023144147A1 (en) 2022-01-25 2023-08-03 Arkema France Peroxide formulations with anti-scorch properties

Also Published As

Publication number Publication date
AU6657096A (en) 1997-02-18

Similar Documents

Publication Publication Date Title
JP5079751B2 (en) New poly (monoperoxycarbonates)
EP0813550B1 (en) Cyclic ketone peroxides as polymer initiators
US4160759A (en) Elastomer modified polyester molding compound
US6482970B1 (en) Peroxides, their preparation process and use
US4160758A (en) Method of manufacture of elastomer polyester molding compounds
EP1123324B1 (en) Process using dialkylperoxide compounds for initiating a chemical reaction
US6552215B1 (en) Ketone peroxide derivatives, their preparation and use
WO1997003961A1 (en) Imido peroxides as initiators of polymerization processes
US4079074A (en) Unsymmetrical diperoxides and processes of use in polymerizing unsaturated monomers
US6384287B1 (en) Peroxides, their preparation process and use
US4219676A (en) Unsymmetrical diperoxides and processes of use in polymerizing unsaturated monomers
JPH10265455A (en) New oxalic acid peroxide and its use
WO1997003962A1 (en) Imido peresters as initiators of polymerization processes
US5420173A (en) Multi-component ethylenically unsaturate peroxyesters
MXPA01001594A (en) Peroxides, their preparation process and use

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA