Patent GB-914003-A (GB)
Title: Improvements in or relating to polyepoxide compositions
IPC: C08G59/18
Filed: 1958-11-24
Abstract: Polyepoxides are cured with a latent system comprising (i) a curing agent for the polyepoxide, (ii) a molecular sieve carrier for the curing agent, and (iii) a meltable coating material encasing the curing agent-containing molecular sieve, the coating being, at a temperature below its melting point, substantially non-reactive with (i), (ii) and the polyepoxide composition.  The carrier is impregnated with the curing agent in liquid form, in a slurry containing the carrier in, e.g. benzene or toluene: the mixture is then heated and refluxed so that the curing agent is taken up by the carrier, and the hydrocarbon is distilled off.  If the curing agent is a gas, the carrier is impregnated in convntional manner.  The impregnated carrier is coated by being mixed with the molten coating material, e.g. by tumbling or stirring for 10 minutes, and the resultant coated carrier, which may be hot compounded on a differential 2-roll mill and sheeted, is then cooled and granulated. Curing agents (i) specified are (a) "hardeners," e.g. n-butylamine, m-phenylene diamine, 4,41-methylenedianiline, N-(2-hydroxy-2,3,3,-trimethylpentyl) diethylenetriamine, m-xylylenediamine, 2:2-bis(p-hydroxyphenyl)propane, novolak resins, and hexahydrophthalic, chlorendic and methylnadic anhydrides; (b) "catalysts", e.g. -methyl benzyl dimethylamine, p-dimethylamino ethylphenol, methyl-dimethylamine, and triethanolamine.  Molecular sieves (ii) specified are the zeolite sieves, composed of soda, lime, alumina and silica, the zeolite X of Specification 777,233 being preferred.  Coating materials (iii) specified are polyethylene, polyethylene glycol (e.g. Carbowax 6000), linear polyamides and mineral, vegetable or synthetic waxes.  Polyepoxides specified are vinyl cyclohexene dioxide, epoxidized soyabean oil, butadiene dioxide, 1,4-bis(epoxypropoxybenzene) 1,3-bis(2,3-epoxypropoxy)cyclohexane, 4,4-bis-(2-hydroxy-3,4epoxybutoxy)diphenyldimethylmethane, 1,3-bis-(4,5-epoxypentoxy)-5-chloro-benzene, 1,4-bis-(3,4-epoxybutoxy)-2-chlorocyclohexane, 1,3-bis-(2-hydroxy-3,4-epoxybutoxy)benzene, 1,4-bis(2-hydroxy-4,5-epoxypentoxy)-benzene, 1,2,5,6-diepoxy-3-hexyne, 1,2,5,6-diepoxyhexane, 1,2,3,4-tetra-(2-hydroxy-3:4-epoxybutoxy)butane, the diglycidyl ethers of bis(4-hydroxyphenyl)-dimethylmethane and of bis(4-hydroxyphenyl) methane, diglycidyl adipate or phthalate, glycidyl ethers of resorcinol of pyrogallol, of the bisphenols of Specification 666,732, of novolaks (e.g. phenol-formaldehyde and those derived from a phenol and an unsaturated aldehyde such as acrolein in Specification 788,556) of alkyl resorcinols, of tribromoresorcinols and of bis-phenol A, and 3,4-epoxy-6-methylcyclohexylmethyl-3, 4-epoxy-6-methylcyclohexane-carboxylate.  Optional additives include Al, Fe, Ca stearate, silica, alumina, portland cement, SiC, iron oxide, mica and nylon.  In Example (5) an epoxidized novolak is prepared from an ethyl alcohol solution of epichlorhydrin and an oxalic acid catalyzed phenol-formaldehyde novolak.  Reference has been directed by the Comptroller to Specification 884,074.ALSO:Polyepoxides are cured with a latent system comprising (i) a curing agent for the polyepoxide, (ii) a molecular sieve carrier for the curing agent, and (iii) a meltable coating material encasing the curing agent-containing molecular sieve, the coating being, at a temperature below its melting point, substantially non-reactive with (i), (ii) and the polyepoxide composition.  The carrier is impregnated with the curing agent in liquid form, in a slurry containing the carrier in e.g. benzene or toluene: the mixture is then heated and refluxed so that the curing agent is taken up by the carrier, and the hydrocarbon is distilled off.  If the curing agent is a gas, the carrier is impregnated in conventional manner. The impregnated carrier is coated by being mixed with the molten coating material, e.g. by tumbling or stirring for 10 minutes, and the resultant coated carrier, which may be hot compounded on a differential 2 roll mill and sheeted, is then cooled and granulated. Curing agents (i) specified are (a) "hardeners", e.g. n-butylamine, m-phenylene diamine, 4,41-methylenedianiline, N (2-hydroxy-2,3,3-trimethylpentyl) diethylenetriamine, m-xylylenediamine, 2:2-bis (p-hydroxyphenyl) propane, novolak resins, and hexahydrophthalic, chlorendic and methylnadic anhydrides; (b) "catalysts", e.g. a -methyl benzyl dimethylamine, p-dimethylamino ethylphenol, methyldimethylamine, and triethanolamine.  Molecular sieves (ii) specified are the zeolite sieves, composed of soda, lime, alumina and silica, the zeolite X of Specification 777,233 being preferred.  Coating materials (iii) specified are polyethylene, polyethylene glycol (e.g. Carbowax 6000), linear polyamides and mineral, vegetable or synthetic waxes.  Polyepoxides specified are vinyl cyclohexene dioxide, epoxidized soyabean oil, butadiene dioxide, 1,4-bis-(epoxypropoxy benzene) 1,3-bis-(2,3-epoxy propoxy) cyclohexane, 4,4-bis-(2-hydroxy-3,4-epoxy butoxy) diphenyl dimethyl methane, 1,3-bis-(4,5-epoxy pentoxy)-5-chlorobenzene, 1,4-bis-(3,4-epoxy butoxy)-2-chlorocyclohexane, 1,3-bis-(2-hydroxy-4,5-epoxy butoxy) benzene, 1,4-bis-(2-hydroxy-4,5-epoxy pentoxy)-benzene, 1,2,5,6-diepoxy-3-hexyne, 1,2,5,6-diepoxy hexane, 1,2,3,4-tetra-(2-hydroxy-3:4-epoxy butoxy) butane, the diglycidyl ethers of bis-(4-hydroxy phenyl)-dimethyl methane and of bis-(4-hydroxy phenyl) methane, diglycidyl adipate or phthalate, glycidyl ethers of resorcinol, of pyrogallol, of the bisphenols of Specification 666,732, of novolaks (e.g. phenol-formaldehyde and those derived from a phenol and an unsaturated aldehyde such as acrolein in Specification 788,556) of alkyl resorcinols, of tribromoresorcinols and of bisphenol A, and 3,4-epoxy-6-methyl cyclohexylmethyl-3,4-epoxy-6-methyl cyclohexane-carboxylate. Optional additives include Al, Fe, Ca stearate, silica, alumina, portland cement, SiC, iron oxide, mica and nylon.  In Example (5) an epoxidized novolak is prepared from an ethyl alcohol solution of epichlorhydrin and an oxalic acid catalysed phenolformaldehyde novolak.  Reference has been directed by the Comptroller to Specification 884,074.