Patent GB-896971-A (GB)
Title: Epoxide-containing esters, their preparation and resinous compositions containing them
IPC: C08G59/14
Filed: 1960-01-06
Abstract: A curable composition comprises a partial ester of an aliphatic monocarboxylic acid and a polyepoxide containing at least two cyclohexene oxide groups, the ester having an oxirane oxygen content of at least 0,3 milliequivalents per gram of the ester, and a polymerization catalyst or a hardening agent.  Preferred monocarboxylic acids from which the esters are derived are the saturated and unsaturated acids containing between 3 and 22 carbon atoms.  The preferred classes of polyepoxide are 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylates, bis(3,4-epoxycyclohexylmethyl) dicarboxylates, dihydric alcohol bis(3,4-epoxycyclohexanecarboxylates), trihydric alcohol tris(3,4-epoxycyclohexanecarboxylates) and tetraol tetrakis(3,4-epoxycyclohexanecarboxylates), 3,4-epoxycyclohexylmethyl carbonate, 3,4-epoxycyclohexylmethyl ethers of alkylene glycols and polyalkylene glycols, and derivatives such as 1,2-bis(3,4-epoxy-1-chlorocyclohexyl) ethane and 1,4-bis(3,4-epoxycyclohexylmethyl) benzene.  The esters are formed by opening up one of the epoxide rings of the polyepoxide (for preparation see Group IV(b)).  Suitable polymerization catalysts are acids, alkyl titanates, metal halide Lewis acids, boron trifluoride etherates, boron trifluoride-amine complexes, metal fluoborates; bases such as sodium hydroxide, alkali metal alcoholates and tertiary amines.  The quantity of catalyst may vary between 0,005 and 15 weight per cent based on the total weight of polymerizable material. The composition may be obtained by mixing the components at room temperature, if desired using a solution of catalyst in solvent. Curing occurs with or without solvent at a temperature between 25 DEG and 200 DEG C.  Suitable hardening agents include polyepoxides, polycarboxylic acids and esters, polycarboxylic acid anhydrides, polycarboxylic acid halides, polyhydric alcohols and phenols, polythiols, polyisocyanates, polyfunctional amines, polyamides, urea-formaldehyde adducts, melamineformaldehyde adducts, and phenol-formaldehyde adducts.  Lists of suitable examples of polymerization catalysts and hardening agents are given.  The compositions in which the fatty acid moiety of the epoxy ester is olefinically unsaturated are drying compositions.  Suitable driers for addition to such compositions are salts of heavy metals, such as cobalt naphthenate and lead octanoate.  Maleic anhydride and dicyclopentadiene are suitable bodying agents.  The polymerization of the polymerizable compositions may also be accomplished simultaneously with the preparation of the epoxy-fatty acid ester.ALSO:The invention comprises an ester of an aliphatic monocarboxylic acid and a polyepoxide containing at least two cyclohexene oxide groups which may be made by interacting at a temperature between 25 DEG C. and 250 DEG C. a polyepoxide containing at least two cyclohexene oxide groups with a sufficient amount of an aliphatic monocarboxylic acid to provide between 0.3 and 0.7 carboxylic equivalents per epoxy equivalent of said polyepoxide. The esters are formed by opening up one of the epoxide rings of the polyepoxide.  Preferred classes are 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane-carboxylates, bis (3,4-epoxycyclohexylmethyl) dicarboxylates, dihydric alcohol bis(3,4-epoxycyclohexanecarboxylates), trihydric alcohol tris (3,4-epoxycyclohexanecarboxylates) and tetraol tetrakis (3,4-epoxycyclohexanecarboxylates), 3,4-epoxycyclohexylmethyl carbonate, 3,4 - epoxycyclohexylmethyl ethers of alkylene glycols and polyalkylene glycols, and derivatives such as 1,2-bis-(3,4-epoxy - 1 - chlorocyclohexyl)ethane and 1,4-bis(3,4 - epoxycyclohexylmethyl) benzene.  Aliphatic monocarboxylic acids preferred are the saturated and unsaturated acids containing between 3 and 22 carbon atoms.  It is advantageous to employ mixtures of acids particularly those derived from vegetable oils. Suitable esterification catalysts are sulphuric acid, sulphonic acids, phosphoric and polyphosphoric acid, and dimethyldihydrogen pyrophosphate, bases such as sodium hydroxide and sodium alcoholates, quaternary ammonium compounds and tertiary amines. If desired solvents such as aromatic hydrocarbons, aliphatic p  hydrocarbons, terpenes, esters, ketones and ethers may be used. The epoxy-ester products may be polymerized to form resins (see Group IV(a)).