Patent GB-771813-A (GB)
Title: Esters of epoxy-substituted polycarboxylic acids and epoxy-substituted alcohols and their polymers
Inventor: PAYNE GEORGE BERNSON
IPC: C07D303/44
Filed: 1955-02-11
Abstract: Esters of polycarboxylic acids possessing at least one epoxy group in the acid radical and at least one epoxy group in an alcohol radical (but which may also contain ethylenic unsaturation in the acid and/or alcohol radicals) may be polymerized either by themselves or with other epoxy compounds such as ethylene oxide, propylene oxide, isobutylene epoxide, epichlorohydrin, vinyl cyclohexane dioxide, butadiene mono- or dioxide, epoxidized tri- and diglycerides, epoxy ethers, polyepoxy polyethers and other polyepoxide esters.  The polymerization may be effected by heating the materials in the presence of a catalyst capable of promoting polymerization through an epoxy group, e.g. an amine, such as triethylamine, ethylenediamine and 2,4,6-(trimethylaminomethyl) phenol, melamine and boron trifluoride.  The esters which also possess an unsaturated linkage may also be polymerized or copolymerized through the unsaturated linkage alone or through the unsaturated linkage and the epoxy groups.  They may be copolymerized with vinyl monomers such as vinyl chloride, acrylonitrile, methyl methacrylate, vinyl acetate, vinyl pyridine, allyl acetate, styrene and a -methyl styrene. Polymerization may be effected by heating in the presence of a free radical-yielding catalyst, e.g. a peroxide, such as benzoyl peroxide and t.-butyl peroxide in an amount of 0.5 to 5 wt. per cent.  The polymers may be used in the preparation of pottings, castings and rigid plastic articles and coating and impregnating compositions. Many examples of the monomers are given, typical of which are: di-(2,3-epoxypropyl) 4,5-epoxycyclohexane-1,2-dicarboxylate, di - (4,5 - epoxycyclohexyl) - 4 - epoxycyclohexane - 1,2 - dicarboxylate, 2,3 - (epoxypropyl) - 1,2,3,4 - diepoxycyclohexane - 1,2 - dioxylate, 2,3 - epoxypropylallyl - 4 - epoxycyclohexane - 1,2 - dicarboxylate, 3,4 - epoxyhexyl methallyl - 8,9,10,13 - diepoxyeicosandioate and 3,4 - epoxycyclohexyl - chloroallyl - 8 - epoxyethyl-10,11-eicosanedioate.  (For preparation see Group IV (b)). In detailed examples: (1) an epoxy ester produced by epoxidizing diallyl 4 - cyclohexene - 1,2 - dicarboxylate when heated with 2,4,6 - tri-(dimethylaminomethyl) phenol forms a solid resin; (2) the product of epoxidizing the acid radical and one allyl radical of diallyl-8,12-eicosadienedioate is heated with a polyglycidyl polyether of bis-phenol in the presence of 2,4,6 - tri - (dimethylaminomethyl) phenol to form a resin; (3) the product of epoxidizing the acid radical and one allyl radical of di(allyloxyethyl) 4-cyclohexene-1,2-dicarboxylic acid is heated with methyl methacrylate in the presence of benzoyl peroxide giving a solid resin; (4) the product of epoxidizing one double bond in both the acid and allyl radicals of the diallyl ester of dimerized linoleic acid is heated with 2,4,6-tri-(dimethylaminomethyl) phenol to form a solid resin.  The above-described epoxy ester monomers may be used as plasticisers and stabilizers for vinyl polymers and copolymers of monomers such as styrene, a -methyl styrene, vinyl naphthalene, vinyl phenol, acrylic acid esters, vinylidene chloride, vinyl chloride, acrylonitrile, methacrylonitrile, vinyl esters, diallyl phthalate or succinate, vinyl ethers, vinyl ketones and vinyl pyridine. When used as plasticisers, from 20-150, preferably 40-75 parts of epoxyester per 100 parts by weight of resin are suitable. When used as stabilizers, from 0.1 to 5 per cent by weight based on the polymer is effective.  If other stabilizers such as urea, thiourea, metal salts or organic and inorganic acids are used in combination with the novel esters, amounts of ester such as 0.01 to 2 per cent by weight, based on the polymer, are sufficient. Examples describe the use of the epoxidized ester monomers described in Examples (1) and (3) above as plasticisers for polyvinyl chloride and copolymers of vinyl chloride and vinyl acetate.  Specifications 762,340 and 770,481 are referred to.ALSO:The invention comprises an ester of a polycarboxylic acid possessing at least one epoxy group in the acid radical and at least one epoxy group in an alcohol radical. The epoxy-substituted polycarboxylic acids may possess 2, 3, 4 or more carboxyl groups and are derived from mono- and polyethylenically unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic acids, preferably containing not more than 26, more preferably not more than 22, carbon atoms per molecule.  They may be further substituted by chorine atoms or ether radicals. The epoxysubstituted alcohols from which the esters are derived comprise mono- or polyhydric alcohols having at least one epoxy group.  The alcohols may be aliphatic, cycloaliphatic, aromatic or heterocyclic, saturated or unsaturated, and may have other substituents such as halogen atoms or ether radicals.  Preferred alcohols are the aliphatic or cycloaliphatic monohydric alcohols containing 3 to 15 carbon atoms, and dihydric alcohols containing 4 to 15 carbon atoms.  In the novel esters, any carboxyl groups which are not esterified with epoxy alcohols may remain free or may be esterified with saturated or unsaturated aliphatic or cycloaliphatic alcohols or phenols, preferably with b ,g -monoethylenically unsaturated monohydric alcohols containing from 3 to 10 carbon atoms, e.g. allyl, methallyl or crotyl alcohol, 2-chloro-3-butenol or 2-octenol.  Many examples of the novel esters are given and preferred esters include di-(4,5-epoxycyclohexyl) - 4 - epoxycyclohexane - 1,2 - dicarboxylate, di - (2,3 - epoxypropoxypropyl)-8,9,12,13 - diepoxyeicosanedioate, di - (3,4 - epoxyhexyl) - 4 - epoxycyclohexane - 1,2 - di-carboxylate, di - (3,4 - epoxydecyl) - 8 - epoxyethyl - 10,11 - eicosanedioate, 2,3 - epoxypropyl allyl 4 - epoxycyclohexane - 1,2 - dicarboxylate,3,4-epoxyhexylmethallyl-8,9,10, 13-diepoxyeicosanedioate, 3,4 - epoxycyclohexyl chlorallyl - 8 - epoxyethyl - 10,11 - eicosanedioate and 2,3 - epoxypropyl - 4,5 - epoxycyclohexane - 1,2 - dicarboxylate.  The novel esters may be prepared by reacting the epoxysubstituted alcohol with an acid halide of the epoxy-substituted polycarboxylic acid, by reacting the epoxy-substituted alcohol with an acid halide of an unsaturated polycarboxylic acid and epoxidizing the resultant ester, by reacting the unsaturated alcohol with the epoxidized polycarboxylic acid and epoxidizing the resultant ester, or by reacting an unsaturated alcohol with an unsaturated polycarboxylic acid or acid halide and epoxidizing the resultant ester.  The reaction of an alcohol and an acid halide may be effected at 0 DEG  to 30 DEG  C. in the presence of an inert solvent such as toluene or benzene and a hydrogen halide absorbing agent such as a weak inorganic base or triethylamine, triamylamine or pyridine.  The reaction of unsaturated acid and alcohol may be effected by a known process such as in the presence of p-toluene sulphonic acid.  The epoxidation of unsaturated acids, alcohols or esters thereof may be effected by means of an epoxidizing agent such as peracetic, perbenzoic or monoperphthalic acid, preferably in a solvent such as chloroform, ethyl ether, dichloromethane, benzene or ethyl acetate at temperatures between - 20 DEG  and 60 DEG  C., more preferably 10 DEG  and 40 DEG  C. Suitable unsaturated polycarboxylic acids for use in forming the novel esters are those obtained by condensing maleic acid with a compound having a conjugated system of double bonds; those obtained by condensing a chloromaleic acid with a compound having a conjugated system of double bonds and dehydrohalogenating the product; acids obtained by reacting maleic acid with a halogenated olefinic compound and dehydrohalogenating the product; acids obtained by reacting maleic acid with an olefinic compound; dimerized polyethylenically unsaturated fatty acids; and acids obtained by treating a cyclic peroxide with a compound having a conjugated system of double bonds in the presence of a heavy metal as described in Specification 762,340.  In examples: (1) dially 4-cyclohexene-1,2-dicarboxylate (obtained by condensing butadiene and diallyl maleate); (2) diallyl 8,12-eicosadienedioate (obtained by reacting 8,12-eicosadienedioic acid with allyl alcohol); (3) di-(allyloxyethyl) 4 - cyclohexene - 1,2 - dicarboxylate (obtained by condensing butadiene with di(allyloxyethyl) maleate); and (4) diallyl ester of dimerized linoleic acid, are epoxidized by treating with peracetic acid while in chloroform solution.  A similar treatment of the dimethallyl, di-(4-hexenyl-4,5-dimethyl, di-(allyloxypropyl) - 5 - butyl, di - (methyallyoxypropyl) and di - (allyloxypropyl) - 1,2,5,6 - tetrachloro derivatives of 4-cyclohexene-1,2-dicarboxylic acid is also mentioned.  The novel esters are useful as stabilizers and plasticizers and as monomers for the preparation of synthetic resins (see Group IV (a)). Specification 770,481 also is referred to.