Patent GB-980268-A (GB)
Title: Improvements in and relating to the curing of polyepoxides
IPC: C08L63/00
Filed: 1962-06-19
Abstract: An adduct of a polyglycol diamine comprises the reaction product of a diepoxide having 2 oxirane epoxy groups per molecule and a polyglycol diamine of the formula H2N-(CH2)3-O-(CnH2nO-)n -(CH2)3-NH2 where n is 2 to 5 inclusive and x is 1 to 85 inclusive, said adduct having six aminohydrogen atoms per molecule.  The adducts are made by reacting the diepoxide with at least 2 mols. per mol. of diepoxide of the polyglycol diamine. The polyglycol diamines are made by cyanoalkylating a glycol of the formula HO(CnH2nO)xH with acrylonitrile with subsequent hydrogenation of the product, specified glycols being ethylene, diethylene, 1 : 2- and 1 : 3-propylene and 1 : 4-butylene glycol, poly(ethylene glycol) and poly(propylene glycol) The specified diepoxides include the diglycidyl ethers of resorcinol, catechol, hydroquinone, methyl resorcinol, bis-(p-hydroxyphenyl)-methane, 1 : 1 - bis - (p - hydroxyphenyl)propane, 2 : 2 - bis - (p - hydroxyphenyl)propane, 2 : 2 - bis - (p - hydroxyphenyl)butane, ethylene glycol, propane diols and butane diols; 1 : 2 : 3 : 6-diepoxydimethylcyclo-octane, bis - (2 : 3 - epoxycyclopentyl)ether, vinylcyclohexene dioxide, dicyclopentadiene dioxide, 1 : 2-bis -(2 : 3-epoxy-2-methylpropoxy)ethane, diglycidyl acetal, divinyl benzene dioxide, dipentene dioxide, glycidyl - 2 : 3 - epoxycyclopentylether, 3 : 9-bis - (1 : 2 - epoxy - 1 - methylethyl) spiro bi-(m-dioxane), glycidyl-2: 3-epoxybutyl ether, bis-(2:3 -epoxy - 2 - methylpropyl)ether, 1 : 1 - bis-2: 3 - epoxy - 2 - methylpropoxyl)ethane, di-(6 - methyl - 3: 4 - epoxycyclohexylmethyl)-ether and 6 - (methyl - 3: 4 - epoxycyclohexyl - methyl)ether. Monoepoxides, e.g. butyl, allyl and phenyl glycidyl ether, may be included in the reaction mixtures.  Examples (1) to (4) describe the preparation of adducts from the diglycidyl ether of 2: 2 - bis - (p - hydroxyphenyl)propane and the di-(3-aminopropyl)ether of diethylene glycol, and, in Examples (2) and (3), butyl glycidyl ether.  Specifications 865,314 and 880,446 also are referred to.ALSO:An adduct of a polyglycol diamine comprises the reaction product of a diepoxide having 2 oxirane epoxy groups per molecule and a polyglycol diamine of the formula H2N-(CH2)3-O-(CnH2nO-)x -(CH2)3-NH2 where n is 2 to 5 inclusive and x is 1 to 85 inclusive, said adduct having six aminohydrogen atoms per molecule.  The adducts are made by reacting the diepoxide with at least 2 moles, per mole of diepoxide of the polyglycol diamine. The polyglycol diamines are made by cyanoalkylating a glycol of the formula HO (CnH2n))xH with acrylonitrile, with subsequent hydrogenation of the product, specified glycols being ethylene, diethylene, 1 :2 and 1 :3 propylene and 1 :4 butylene glycol, poly(ethylene glycol) and poly(propylene glycol). Specified diepoxides are the diglycidyl ethers of resorcinol, catechol, hydroquinone, methyl resorcinol, tribromo resorcinol, bis-(p - hydroxyphenyl) - methane, 1 :1 - bis-(p - hydroxyphenyl) - propane, 2:2 - bis - (p - hydroxyphenyl) - propane, 2:2 - bis - (p - hydroxyphenyl)-butane, ethylene glycol, propane diols and butane diols; the diglycidyl esters of adipic and phthalic acid; the diglycidyl reaction products of epichlorohydrin with aromatic amines e.g. 2:6-dimethyl aniline, aniline, p-toluidine, m-chloraniline and p-aminodiphenyl; 1:2:5:6-diepoxydimethyl cyclooctane, 3:4-epoxy-6-methylcyclohexylmethyl-3:4-epoxy-6-methylcyclohexane carboxylate, 2-ethyl - 1:3 - hexanediol bis - (3:4 - epoxycyclohexane carboxylate), bis - (2:3 - epoxycyclopentyl)-ether, vinylcyclohexene dioxide, dicyclopentadiene dioxide, diethylene glycol bis-(3:4-epoxy-6-methylcyclohexane carboxylate), 3:4 : epoxycyclohexylmethyl - 3:4 - epoxycyclohexane carboxylate, 3:4-epoxy-1 methylcyclohexyl - methyl - 3:4 - epoxy - 1 - methylcyclohexane carboxylate, 1:6 - hexanediol bis - (3:4 - epoxycyclohexane carboxylate) bis - 3:4 - epoxycyclohexylmethyl)-oxalate, 3:4 - epoxy - 6 - methylcyclohexylmethyl 9:10 - epoxystearate, 1:2 : bis - (2:3 - epoxy - 2 - methylpropoxy)-ethane, 4:5-epoxypentyl-4:5 - epoxy pentanoate, bis - (3:4 - epoxy - 6 - methylcyclohexylmethyl)-sebacate, diglycidyl acetal, divinyl benzene dioxide, dipentene dioxide, bis - (3:4 - epoxy - 6 - methylcyclohexylmethyl) adipate, glycidyl-2:3-epoxycyclopentylether, 3:9 - bis - (1:2 - epoxy - 1 - methylethyl spiro bi - (m - dioxane), bis - (3:4 - epoxycyclohexyl)-sulphone, glycidyl 2:3 - epoxybutyl ether, bis - (2:3 - epoxy - 2 - methylpropyl)-ether, 1:1 - bis - (2:3 - epoxy - 2 - methyl-propoxy)-ethane, di - (6 - methyl - 3:4 - epoxy - cyclohexylmethyl) - ether and (6 - methyl - 3:4 - epoxycyclohexylmethyl) - ether.  Monoepoxides may be included in the reaction mixtures, e.g. butyl, allyl and phenyl clycidyl ether.  The adducts may be used for curing epoxides having an epoxy equivalency of greater than one.  Examples (1) to (4) describe the preparation of adducts from the diglycidyl ether of 2:2 - bis - (p - hydroxyphenyl) - propane and di - (3 - aminopropyl) - ether of diethylene glycol and in examples (2) and (3) butyl glycidyl ether.  The remaining examples describe the use of these adducts for curing the diclycidyl ether of 2:2 - bis - (p - hydroxyphenyl) - propane, additional additives being triphenyl phosphite, methyl ethyl ketone, xylene, butanol and titanium dioxide.  Specifications 865,314 and 880,446 also are referred to.