WO1997003961A1 - Imido-peroxydes servant d'initiateurs de processus de polymerisation - Google Patents

Imido-peroxydes servant d'initiateurs de processus de polymerisation Download PDF

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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
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Prior art keywords
methoxy
tri
groups
substituted
alkylphosphineoxide
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PCT/EP1996/003108
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English (en)
Inventor
Leonie Arina Stigter
Andreas Petrus Van Swieten
Auke Gerardus Talma
John Meijer
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Akzo Nobel N.V.
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Priority to AU66570/96A priority Critical patent/AU6657096A/en
Publication of WO1997003961A1 publication Critical patent/WO1997003961A1/fr

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    • 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.

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Abstract

Nouveau groupe d'imido-péroxydes de formule générale (I), dans laquelle X représente C(R4, R5), OC(O), C(R6, OR7), C(OR8, OR9), C(R10, OOR11); et n est 1, 2 ou 3. Ces composés sont très intéressants pour certaines applications industrielles, telles que l'initiation de processus de polymérisation, la modification et la réticulation des polymères. Ainsi, ils s'avèrent très utiles à la production de (co)polymères polystyrène de masse moléculaire élevée, la réticulation des caoutchoucs et élastomères, et la vulcanisation des polyesters insaturés. Sont également décrites des compositions comportant au moins un imido-péroxyde de formule (I), ainsi que des procédés de préparation de ces péroxydes.
PCT/EP1996/003108 1995-07-14 1996-07-12 Imido-peroxydes servant d'initiateurs de processus de polymerisation WO1997003961A1 (fr)

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AU66570/96A AU6657096A (en) 1995-07-14 1996-07-12 Imido peroxides as initiators of polymerization processes

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EP95201949 1995-07-14
EP95201949.5 1995-07-14

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016094163A1 (fr) 2014-12-09 2016-06-16 Arkema Inc. Compositions et procédés pour la réticulation de polymères en présence d'oxygène atmosphérique
WO2022074237A1 (fr) 2020-10-09 2022-04-14 Arkema France Composition comprenant au moins un peroxyde organique et au moins un composé soufré pour la réticulation de polymères en présence d'oxygène
EP4039733A1 (fr) 2013-03-14 2022-08-10 Arkema, Inc. Procédé de réticulation de compositions polymères en présence d'oxygène atmosphérique
FR3132103A1 (fr) 2022-01-25 2023-07-28 Arkema France Formulations de peroxyde dotées de propriétés anti-grillage
FR3132102A1 (fr) 2022-01-25 2023-07-28 Arkema France Procédé pour le durcissement d’une composition durcissable

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4039733A1 (fr) 2013-03-14 2022-08-10 Arkema, Inc. Procédé de réticulation de compositions polymères en présence d'oxygène atmosphérique
WO2016094163A1 (fr) 2014-12-09 2016-06-16 Arkema Inc. Compositions et procédés pour la réticulation de polymères en présence d'oxygène atmosphérique
WO2022074237A1 (fr) 2020-10-09 2022-04-14 Arkema France Composition comprenant au moins un peroxyde organique et au moins un composé soufré pour la réticulation de polymères en présence d'oxygène
FR3115041A1 (fr) 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
FR3132103A1 (fr) 2022-01-25 2023-07-28 Arkema France Formulations de peroxyde dotées de propriétés anti-grillage
FR3132102A1 (fr) 2022-01-25 2023-07-28 Arkema France Procédé pour le durcissement d’une composition durcissable
WO2023144146A1 (fr) 2022-01-25 2023-08-03 Arkema France Procédé de durcissement d'une composition durcissable
WO2023144147A1 (fr) 2022-01-25 2023-08-03 Arkema France Formulations de peroxyde présentant des propriétés anti-grillage

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