Patent GB-819194-A (GB)
Title: Improvements in and relating to the preparation of epoxy compounds and infusible products therefrom
IPC: C07D301/28
Filed: 1957-09-09
Abstract: Compounds still containing free epoxy groups and thus curable to infusible product with the aid of the usual curing catalysts are obtained by reacting a polybasic acid or anhydride with at least 1.5 times the chemical equivalent amount of a poly epoxide containing on the average more than one epoxy group per molecule in the presence of a catalyst comprising a tertiary amine, a quaternary ammonium salt or an organic phosphine.  Polyepoxides specified are (1) monomeric polyepoxides-1,4-bis (2,3-epoxypropoxy) benzene 1,3-bis (2,3-epoxypropoxy) benzene 1,4-bis (2,3-epoxypropoxy) cyclohexane; (2) epoxypolyethers of polyhydric phenols obtained by reacting a halogen containing epoxide with a polyhydric phenol in presence of alkali, e.g. glycidyl polyethers of bis-phenol; (3) polyepoxy polyethers obtained by reacting a polyhydric alcohol with epihalohydrins in presence of acid and treating the product with alkali; (4) epoxyesters of polybasic acids, e.g. diglycidyl phthalate; (5) polyepoxides having internal epoxide groups, e.g. the epoxidized esters of polyethylenically unsaturated monocarboxylic acids, e.g. epoxidized linseed &c. oils; (6) epoxidized esters of unsaturated alcohols, e.g. di(2,3-epoxybutyl) adipate; (7) epoxidized esters of unsaturated alcohols and unsaturated acids, e.g. 2,3-epoxybutyl 3,4-epoxypentanoate; (8) epoxidized esters of unsaturated monocarboxylic acids and polyhydric alcohols; (9) epoxidized derivatives of polyethylenically unsaturated polycarboxylic acids, e.g. dimethyl 8,9,12,13-diepoxyeicosanedioate; (10) epoxidized polyesters obtained by reacting an unsaturated polyhydric alcohol with an unsaturated polycarboxylic acid, e.g. the polyester obtained by reacting 8,9,12,13-eicosanedioic acid with ethylene glycol; (11) epoxidized polymers and copolymers of diolefines such as butadiene, butadiene-acrylonitrile copolymers and butadiene-styrene copolymers; (12) epoxidized hydrocarbons, e.g. 2,2-bis (cyclohexenyl) propane.  Catalysts specified are (a) tertiary amines -trialkyl and triaryl amines, methyl diethanol amine, tricyclohexylamine, pyridine; (b) quaternary ammonium salts-benzyltrimethylammonium-chloride, -sulphate, -nitrate tetraoctyl ammonium chloride; (13) phosphines of general formula P(R)3, where at least one R is an organic radical, e.g. trihydrocarbyl phosphines.  The usual curing agents for epoxide resins are specified.  Surface-coating compositions curing when heated to 60-200 DEG  C. are obtained by dissolving the epoxides in the usual solvents, e.g. ketones, glycol ester and ethers, chlorinated hydrocarbons, aromatic hydrocarbons.  Coal tar resins, tars, oils, may be added to make road coating compositions.  Fillers, e.g. glass fibres, may be added to give moulding and laminating compositions.  In examples: (1) 57 parts of phthalic anhydride were dissolved in 300 parts of a polyether obtained by reacting bis-phenol with epichlorhydrin to give a polymer of molecular weight 350 and average number of epoxy groups per mol. of 1.75; 3.6 parts of methyl diethanolamine were added the temperature rising to 154 DEG  C.: the epoxy product obtained was a brittle hard resin which, dissolved in a 50/50 mixture of methyl isobutyl ketone and xylene and with the addition of 2 parts diethylene triamine, gave a tough coating when cured at 150 DEG  C. for 15 mins.  (2) A C19 acid (prepared from oleic acid by addition of CO and water catalysed by H2SO4) was dissolved in the polyether of (1).  Methyldiethanolamine was added and the mixture was heated to 152 DEG  C. with further additions of acid.  A viscous liquid having an epoxy equivalent of 0.137 was obtained and was mixed with a urea-formaldehyde resin, methylisobutyl ketone, xylene and cellosolve acetate to give a coating composition. In the following examples the reactants employed are (6) epoxidized tetrahydrobenzoate, isophthalic methyldiethanolamine; (7) dimerized octadecadienoic acid, methyldiethanolamine and polyether of (1); (9) polyether, sebacic acid anhydride and triphenyl phosphine; (10) diglycidyl ether, sebacic acid anhydride, and benzyldimethylammonium chloride. Specifications 666,300, 777,255, 777,621 and 781,416 are referred to.