Patent GB-810412-A (GB)
Title: Epoxy polymerizable and polymerized compositions and a process for their preparation
IPC: C08G59/24
Filed: 1957-05-31
Abstract: Epoxide resins which are heat hardenable and thus suitable for use in moulding compositions and as adhesives, coating compositions &c. are obtained by condensing in presence of acids bis-(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxylate compounds having the general formula <FORM:0810412/IV (a)/1> wherein R is a divalent hydrocarbon group having 0-10 C atoms and R1-R6 are H or alkyl groups having 1-4 C atoms.  The group <FORM:0810412/IV (a)/2> comprises the residues of aliphatic dicarboxylic acids, e.g. oxalic, maleic, pimelic or aromatic dicarboxylic acids, e.g. phthalic, isophthalic or terephthalic acids or cycloaliphatic dicarboxylic acids, e.g. hexahydrophthalic acids, R2-R5 are preferably H and R1 and R6 alkyl groups having 1-4 C atoms.  The epoxy compounds are prepared by epoxidization, with e.g. acetaldehyde, monoperacetate, or peracetic acid, bis-(3,4-cyclohexenylmethyl) hydrocarbon dicarboxylates (see Group IV (b)).  Acid-type catalysts, e.g. metal halides including borontrifluoride stannic chloride, aluminium chloride, ferric chloride; inorganic acids, e.g. sulphuric, phosphoric, polyphosphoric perchloric and aromatic sulphonic acids in amount from 0.01-10 per cent by weight of the epoxide can be used. Solvents for the reaction are diethyl ether, dipropyl ether, acetone, methylisobutylketone cyclohexanone, methanol, 2-ethyl-i-propanol, cyclohexanol propylene glycol.  In examples: (9) 8 gs. bis-(3,4-epoxy-6-methylcyclohexylmethyl) succinate and 0.2 g. piperidine boron fluoride complex were heated to 60 DEG  C. for 1 minute until a melt was formed and were then heated to 120 DEG  C. for 4 minutes when a gel formed.  Further heating at 120 DEG  C. for 3.6 hours and at 160 DEG  C. for 6 hours converted the gel into a hard resin.  (10 and (11) describe similar reactions with bis-(3,4-epoxycyclohexylmethyl) oxalates and 3,4 - epoxy - 6 - methylcyclohexylmethyl) sebacates.  The diepoxy carboxylates may be copolymerized with polyfunctional compounds containing at least two groups capable of reacting with epoxy groups, e.g. polycarboxylic acid, and their anhydrides, amines, amides, polyamides, polyhydric compounds, imines, polythiols and other polyespoxides.ALSO:Bis - (3,4 - epoxycyclohexylmethyl) hydrocarbon dicarboxylates the formula <FORM:0810412/IV (b)/1> where R is a divalent hydrocarbon group of 0-10 C. atoms and R1-R6 are H or alkyl groups of 1-4 C atoms, are prepared in the following steps:  (1) Butadiene or homologues thereof are reacted with a ,b -unsaturated aldehydes to give 3-cyclohexenylcarboxaldehydes;  (2) The carboxaldehydes are converted by known reduction processes to 3-cyclohexenyl methanols;  (3) The cyclohexenylmethanols are reacted with dicarboxylic acids to give bis-(3,4-cyclohexenylmethyl) dicarboxylates, preferably in the presence of sulphuric acid as a catalyst and in an azeotroping solvent such as benzene or toluene;  (4) The bis - (3,4 - cyclohexenyl) dicarboxylates are epoxidized by reaction with an epoxidizing agent, e.g. octaldehyde monoperacetate or per acetic acid.  There are specified as reactants in the various stages:  (1) Butadienes-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-butadiene; Unsaturated aldehydes-crolein, methacrolein, crotonaldehyde;  (2) 3 - Cyclohexenylcarboxyaldehydes-2,4-dimethyl-, 3,4-dimethyl-, 3 or 4-methyl-, 2-methyl-, 2,2,5,5-tetramethyl-, 2,2-dimethyl-5-methyl -, 2,2 - dimethyl -, 4 - methyl -, 3 or 4 - methyl - 6,6 - dimethyl -, 3 or 4 - methyl-6 - methyl -, 3 or 4 - methyl - 6 - ethyl -, 2,2,6 - trimethyl -, 2,4,6 - trimethyl -, 2,5,6-trimethyl-, 2,2,4-trimethyl-, 2,2,5-trimethyl-, 3 or 4,6,6-trimethyl-, 2,2,5,5,6-pentamethyl-, 2,2,5,6 - tetramethyl -, 1,2,5,5 - tetramethyl -, 2,2,4,6 - tetramethyl -, 1,3,5,5 - tetramethyl - 3-cyclohexenecarboxaldehyde;  (3) Dicarboxylic acids-oxalic, malonic, glutaric, succinic, alkenyl substituted succinic acids, adipic, pimelic, suberic, azelaic, sebacic, maleic, itaconic; hexahydrophthalic acids; phthalic, isophthalic, terephthalic acids;  In examples: (1) 3-cyclohexenyl-methyl alcohol, pyridine and ethyl ether were refluxed together with the gradual addition of oxalic acid over a period of two hours; the ether layer was extracted with water, dried and distilled to give bis-(3-cyclohexenylmethyl) oxalate; 0.626 mols. of the oxalate thus obtained were reacted with 1.69 mols. peracetic acid at 25-40 DEG C., the reaction products were added to a still containing ethyl benzene and, after distilling off acetone, peracetic acid, acetic acid and ethyl benzene, a residue of bis-(3,4-epoxy cyclohexylmethyl) oxalate was obtained.  In a similar manner, (3) bis-(6-methyl-3-cyclohexenylmethyl) sebacate, and (5) bis-(6-methyl-3-cyclohexenylmethyl) maleate, (7) bis-(3-cyclohexenylmethyl) terephthalate were prepared and converted to the corresponding epoxy compounds.  The epoxy compounds may be polymerized in presence of acids and acid chlorides to heat hardenable epoxy resins (see Group IV (a)).