Patent GB-806447-A (GB)
Title: Epoxy polymerizable and polymerized compositions and a process for their preparation
IPC: C08G59/24
Filed: 1957-05-31
Abstract: Hardenable epoxy resins suitable for use in granulated or powdered form as a constituent of a moulding powder or as adhesives, films, coating, &c. are obtained by polymerizing an organic diol bis-(3,4-epoxycyclohexanecarboxylate) of the general formula <FORM:0806447/IV (a)/1> wherein R is a divalent aliphatic or divalent oxa-aliphatic group and R1, R2, R3 R4, R5, R6 are H or an alkyl group having 1-4 C. atoms in presence of an acid catalyst at from 0-25 DEG C.  The preparation of the organic diol carboxylates is described in Specification 788,541, [Group IV (b)].  Catalysts specified are metal halides, e.g. boron trifluoride stannic chloride, zinc chloride, aluminium chloride, ferric chloride and their etherates and amine complexes, e.g. piperidine boron fluoride and monoethylamine boron trifluoride; or mineral acids, e.g. sulphuric, phosphoric, perchloric, polyphosphoric, and aromatic sulphonic acids.  The reaction may be carried out in presence of solvents, e.g. organic ethers and esters, ketones and alcohols.  Typical Typical organic diol bis-(3,4-epoxycyclohexane-carboxylates) which may be polymerized are those of diethylene glycol, 2-ethyl hexane, 3-methyl pentane-1,5-diol, triethylene glycol, pentane - 1,5 - diol, 2 - methoxymethyl - 2,4 - dimethylpentane - 1,5 - diol, ethylene glycol, 2,2 - diethylpropane - 1,3 - diol, 1,6 - hexane - diol, while other diols are diethylene glycol bis-(1 - methyl - 3,4 - epoxycyclohexanecarboxylate), diethylene glycol bis-(6-methyl-3,4-epoxycyclohexanecarboxylate), ethylene glycol bis-(6 - methyl - 3,4 - epoxycyclohexanecarboxylate, 3 - methylpentane - 1,5 - diol - bis (2 - methyl - 3,4 - epoxycyclohexanecarboxylate), 3 - methyl-pentane - 1,5 - diol bis - (3 - methyl - 3,4 - epoxycyclohexanecarboxylate), 3 - methylpentane - 1,5 - diol bis - (4 - methyl - 3,4 - epoxycyclohexanecarboxylate and 1,6 - hexandiol bis-(5 - methyl - 3,4 - epoxycyclohexanecarboxylate). In examples: (3) 10 gs. ethylene glycol bis-(3,4-epoxycyclohexanecarboxylate) were mixed with 8 drops of a 25 per cent solution of sulphuric acid and the mixture heated to 120 DEG C. for 10 minutes when a gel was formed. Maintaining the gel at 60 DEG  C. for 1 hour produced an ambercoloured tough product; (4) 1,6-hexane-diol bis-(3,4-epoxycyclohexanecarboxylate) was reacted similarly; (5) piperidine-boron trifluoride complex was employed as catalyst to copolymerize the diols used in (3) and (4).  The diepoxides can be copolymerized with polyfunctional compounds containing at least two groups capable of reacting with epoxy groups, e.g. polycarboxylic acids and anhydrides, polyhydric compounds, primary amines, amides, polyamides, imines, polyimines, imides, polyimides, polythiols and other epoxides.ALSO:The esters of 3,4-epoxycyclohexane carboxylic acids and diols of formula <FORM:0806447/IV (b)/1> where R is a divalent aliphatic or oxa-aliphatic group and R1-R6 are hydrogen or alkyl groups having 1-4 C atoms may be obtained by epoxidizing the ethylenic double bonds of corresponding diol-bis-(3-cyclohexene-carboxylates) with an epoxidizing agent as described in Specification 788,541.  Typical oxa-alkylene groups of the diol components of the general formula -(CH2)mO(CH2)m are 3-oxapentylene (-(CH2)2O(CH2)2-), 3,6 - dioxaoctylene - (-(CH2)2O(CH2)2O(CH2)2), 3,6,9 - trioxaundecylene - (-(CH2)2O(CH2)2O(CH2) 2-O(CH2)2-), 4 - oxaheptylene - (-(CH2)3-O(CH2)3-); 4,8,12 - trioxapentadecylene - <FORM:0806447/IV (b)/2> , 2-methyl-3 - oxapentylene, 2,5 - dimethyl - 3,6 - dioxaoctylene and 2,5,8 - trimethyl - 3,6,9 - trioxaundecylene. Typical organic diol bis-(3,4-epoxycyclohexane carboxylates) which may be prepared by this method are diethylene glycol-, 2 - ethylhexane - 1,3 - diol - bis - (3,4 - epoxycyclohexane carboxylate, diethylene glycol bis-(1 - methyl - 3,4 - epoxycyclohexane carboxylate); 3 - methylpentane - 1,5 - diol -, triethyleneglycol -, pentane - 1,5 - diol -, 2 - methoxymethyl - 2,4 - dimethylpentane - 1,5 - diol -, ethylene glycol -, 2,2 - diethylpropane - 1,3 - diol -, and 1,6 - hexane - diol - (bis - 3,4 - epoxycyclohexanecarboxylate); ethylene glycol bis-(6 - methyl - 3,4 - epoxycyclohexanecarboxylate; 3 - methylpentane - 1,5 - diol bis - (2 - methyl - 3,4 - epoxycyclohexanecarboxylate; 3 - methylpentane - 1,5 - diol bis - (3 - methyl - 3,4 - epoxycyclohexanecarboxylate; 1,6 - hexanediol bis-(5 - methyl - 3,4 - epoxycyclohexanecarboxylate).  The organic diol bis-(3-cyclohexenecarboxylate) compounds used as starting materials may be prepared in known manner by reacting a 3-cyclohexene carboxylic acid and a diol.  Suitable acids are 6-methy.-, 1-methyl-, 2-methyl-, 3-methyl-, 4-methyl-, and 5-methyl-3-cyclohexenecarboxylic acids.  Organic diols specified are ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, dipropylene glycols, polyoxyethylene glycols, 1,2-butylene glycol, 1,4-butylene glycol, 1,5-pentane diol, 2,4 - pentane diol, 2,2 - dimethyl - trimethylene glycol, 1,4-hexane diol, 1,5-hexane diol, 1,6-hexane diol, 2,5-hexane diol, 3-methyl-1,5-pentane diol, 2-methyl-2,5-pentane diol, 2,2-diethyl - 1,3 - propane diol, 2 - ethyl - 1,3 - hexane diol, 2,5-dimethyl-2,5-hexane diol, 1,12-octadecane diol, 1-butene-3,4-diol, 2-butene-1,4-diol, 2-butyne-1,4-diol, 2,5-dimethyl-3-hexyne-2,5-diol.