Patent GB-812735-A (GB)
Title: Process for curing compounds having internal epoxy groups
IPC: C08G59/32
Filed: 1956-11-15
Abstract: Compounds having a plurality of internal i.e. non-terminal epoxy groups are hardened to give coating compositions, e.g. enamels, paints, potting compositions, castings, laminates, by admixture with a polybasic acid anhydride in presence of an accelerator consisting of an amine, amine salt, or quaternary ammonium compound.  Curing is effected at from 50-110 DEG  C. but temperatures up to 200 DEG  C. may be used.  Types of "internally" epoxidized compounds used are: (1) epoxidized esters of polyethylenically unsaturated monocarboxylic acids especially epoxidized triglycerides, e.g. epoxidized linseed, soyabean, &c., vegetable oils, alkyl substituted fatty acids, e.g. methyl linoleate; (2) epoxidized esters of unsaturated monohydric alcohols and polycarboxylic acids, e.g. di-(2,3-epoxybutyl) adipate, di-(2,3-epoxy-butyl) phthalate di-(5,6-epoxyoctyl) cyclohexane - 1,3 - dicarboxylate; (3) epoxidized esters of unsaturated alcohols and unsaturated acids, e.g. 2,3 - epoxybutyl, 3,4 - epoxypentanoate, 3,4 - epoxycyclohexyl, 4,5 - epoxy octanoate; (4) epoxidized derivatives of polyethylenically unsaturated polycarboxylic acids, e.g. dimethyl 8,9,12,13-diepoxy eicosanedioate; (5) epoxidized polyesters obtained by reacting a saturated polyhydric alcohol with an unsaturated polycarboxylic acid, e.g. the polyester obtained by reacting 8,9,12,13-eicosadienedioic acid with ethylene glycol; (6) epoxidized polymers and copolymers of diolefines, e.g. butadiene. The epoxy compounds are obtained by reacting the unsaturated compounds with epoxidizing agents, e.g. organic peroxides.  The anhydrides used as curing agents may be aliphatic, cycloaliphatic or aromatic and their chlorinated derivatives, e.g. 3,4,5,6,7,7 - hexachloro - 3,6 - endomethylene 1,2,3,6 - tetrahydrophthalic anhydride (chlorendic anhydride).  Tertiary amines are preferably used as accelerators, e.g. pyridine, dimethyl aniline, dimethyl ethanolamine, morpholine, dimethylaminopropylamine, stearyldimethylamine, tri - n - butyl amine, phenylene diamine or their hydrochloride, sulphate, or acetate salts may be used; quaternary ammonium salts specified are benzyltrimethylammonium chloride, cyclohexyltributylammonium sulphate and those having the general formula <FORM:0812735/IV (a)/1> where R is alkyl, aryl or arylalkyl.  The amount of curing agents may range from 1.1 to 1.5:1 by weight of the epoxy compound while the activator may vary in weight from 0.1-4 per cent of the resin.  Solvents are preferably added to the mixture to give fluidity, e.g. ketones, esters, ether alcohols, chlorinated hydrocarbons mixed with aromatic hydrocarbons; solvents which will remain in the cured products may be used, e.g. dibutyl phthalate; liquid monoepoxy compounds, e.g. glycidyl allyl ether; cyanosubstituted hydrocarbons, e.g. acetonitrile.  Epoxides having terminal epoxide groups may also be present.  Tables are given showing the curing time of an epoxidized soyabean oil mixed with chlorendic anhydride and p,p-bis-(dimethylaminophenyl) methane as compared with mixtures with other primary amines, acids and boron fluoride-amine complexes. Other examples are given illustrating the curing of epoxidized oils with (2) phthalic anhydride; (3) chlorendic anhydride and pyridine; (4) chloromaleic anhydride and pyridine; (6) mixtures of chlorendic anhydride, chlorphthalic anhydride and hexahydrophthalic anhydride and benzyltrimethylammonium chloride; (11) curing epoxidized esters of ethylene glycol and tetrahydrophthalic acid with hexahydrophthalic anhydride and methyldiethanolamine; (12) epoxidized dicrotyl adipate and hexahydrophthalic anhydride and benzyldimethylamine; (16) epoxidized dicyclohexenyl propane and chlorendic anhydride and benzyldimethyl amine; (17) epoxidized cyclohexenyl cyclohexenecarboxylate and hexahydrophthalic anhydride and p.p1 - bis - (dimethylaminophenyl) methane; (18) epoxidized Hycar rubber and hexahydrophthalic acid anhydride and dimethyl ethanolamine; (1) epoxidized dicrotyl terephthalate and hexahydrophthalic acid anhydride and dimethyl ethanolamine; (25) epoxidized dimethallyl 8,12 - eicosadienedioate-1,2 and hexahydrophthalic acid anhydride and dimethyl ethanolamine. Specifications 783,740 and 786,116 are referred to.