Patent GB-770795-A (GB)
Title: Epoxy esters of aromatic polycarboxylic acids and acid esters and polymers thereof
IPC: C08G59/22
Filed: 1955-02-09
Abstract: Esters of epoxy-substituted monohydric alcohols and acid components which may be aromatic polycarboxylic acids or acid esters produced by esterifying polyhydric compounds with such proportions of aromatic carboxylic acids that the acid esters possess at least two free carboxyl groups, in particular esters wherein the acid component is a polycarboxylic acid having at least two benzene nuclei joined by a bivalent aliphatic hydrocarbon radical and at least two carboxyl groups joined to separate nuclei (see Group IV (b)), are used as (1) stabilizers for halogen-containing polymers, e.g. polyvinyl chloride; (2) plasticisers for vinyl polymers and synthetic rubbers, or (3) they may be polymerized alone or with other polyepoxide materials. The esters may be used as stabilizers under (1) either alone or together with other stabilizers such as urea, thiourea, metal salts, organic or inorganic acids, and as plasticisers under (2) they may be used singly or as a mixture or with other conventional plasticisers to plasticise polymers of styrene, a -methylstyrene, vinyl naphthalene, vinyl phenol, acrylic esters such as methyl, propyl, and butyl acrylates, methyl, lauryl, and hexyl methacrylates, vinylidene chloride, vinyl chloride, acrylonitrile, methacrylonitrile, vinyl acetate, benzoate, or caproate, diallyl phthalate or succinate, vinyl ethyl or butyl ether, vinyl ketones, and vinyl pyridine.  As regards (3), they may be copolymerized with ethylene or propylene oxide, isobutylene epoxide, epichlorhydrin, vinyl cyclohexane dioxide, butadiene mono- or dioxide, epoxidized tri- and di-glyceride, diglycidyl ether, glycidyl ethers of polyhydric phenols, polyepoxy polyethers, and other polyepoxy esters such as di-(2.3-epoxypropyl) adipate.  The polymerization may be effected in presence of an epoxy-curing catalyst, e.g. triethylamine, ethylene diamine, 2.4.6-tris-(dimethylaminomethyl) phenol, melamine, phthalic anhydride, boron trifluoride and its ether complexes.ALSO:An ester of an epoxy-substituted monohydric alcohol and an acid component which is either an aromatic polycarboxylic acid or an acid ester produced by esterifying a polyhydric compound with such a proportion of an aromatic polycarboxylic acid that the acid ester possesses at least two free carboxyl groups, by a process comprising reacting a halogen-substituted epoxy compound corresponding to the monohydric alcohol, with the acid component or its salt.  The product first obtained, viz. the halohydrin ester of the acid component, may be converted to the desired ester by dehydrohalogenation.  The products are stabilizers for halogen-containing polymers, such as polyvinyl chloride and plasticisers for vinyl polymers and synthetic rubbers (see Group IV (a)), and act as lubricants for textiles or impart crease- or shrink-resistance when cured within the fibres of the fabrics.  In examples: (1) epichlorhydrin is reacted in presence of tributylamine with phthalic acid, terephthalic acid, or p,p1-stilbene dicarboxylic acid, and the di-(hydroxychloropropyl) esters so obtained are dehydrochlorinated with caustic soda in ethylene dichloride to give di-(2,3-epoxypropyl) phthalate, terephthalate, and p,p1-stilbene dicarboxylate; (2) pentanediol - 1,5 - bis - (hydrogen phthalate), prepared from 1 mol. pentanediol-1,5 and 2 mols. phthalic anhydride, is similarly reacted with epichlorhydrin to give 1,5-pentanediol bis (hydroxychloropropyl) phthalate which is similarly dehydrochlorinated to give the pentanediol - 1,5 - bis - (2,3 - epoxypropyl phthalate), and the pentanediol-1,5 may be replaced by 2,4-dimethyl-4-methoxypentanediol-1,5, hexanediol-1,6, and pentaethylene glycol.  Other epoxy esters specified are di-(2,3-epoxypropyl) isophthalate, di-(3,4-epoxybutyl) terephthalate, di - (3,4 - epoxypentyl) chlorophthalate, di - (epoxypropoxypropyl) terephthalate, di - (2,3 - epoxypropyl) o,m1-stilbene dicarboxylate, di-(3,4-epoxyhexyl)-4-butyl-phthalate, di-(carboepoxypropoxy)-di-benzyldibenzene or -diphenylmethane or phenyltolymethane, di - (3,4 - epoxyhexyl) diphenylthioether - 4,41 - dicarboxylate, di - (2,3 - epoxypropyl) diphenoxybenzene - 4,41 - dicarboxylate, diethyleneglycol bis - (2,3 - epoxyhexyl isophthalate), glycerol tri (2,3 - epoxyhexyl chlorophthalate), tetrahydropyran - 2,3 - dipropanol - bis - (epoxypropoxyethyl terephthalate), pentaerythritol bis - (2,3 - epoxyoctyl) terephthalate, 1,5-pentanediol bis-(2,3-epoxypropyl stilbene or diphenoxybenzene dicarboxylate), diethylene glycol bis-(2,3-epoxypropyl diphenylthioether - 4,41 - dicarboxylate, and the ester formed from 2,2-bis - (4 - hydroxyphenyl) propane and 2,3-epoxypropyl terephthalic acid.  Lists of epoxy alcohols and acid components are given. Specification 763,559 is referred to.