Patent GB-897985-A (GB)
Title: A process for the manufacture of hardened artificial resin materials and compositions therefor
IPC: C08F20/62
Filed: 1958-08-25
Abstract: In a method for hardening epoxy resins which are substantially free from carboxyl groups and contain n epoxide groups calculated on the average molecular weight, where n is a whole or fractional number greater than 1, the hardening is effected in an anhydrous medium and there is used as hardening agent a polymerization product or copolymerization product obtained from 60 to 0% by weight of at least one polymerizable compound free from basic amino groups and 40 to 100% by weight of at least one polymerizable compound containing at least one tertiary amino group of the formula -NR1R2 wherein R1 and R2 each represent a hydrocarbon radical of 1 to 6 carbon atoms which may be substituted or may be linked together to form with the nitrogen atom a heterocyclic ring, the polymerizable compounds containing at least one polymerizable carbon-to-carbon double bond. Preferred starting materials containing a basic tertiary amino group are compounds of the general formula <FORM:0897985/IV (a)/1> in which k, m, n, p, and q each is a whole number not exceeding 2; A stands for a hydrocarbon residue containing m to 8-m carbon atoms; and R1 and R2 are hydrocarbon residues which contain 1 to 6 carbon atoms and may be substituted or linked together to form a heterocyclic ring. Specified compounds are the g -diethylaminopropyl-, g -di-(hydroxyethyl)aminopropyl-, b -diethylaminoethyl-, 4-dimethylaminophenyl-, b - N-morpholinoethyl- and b -pyrrolidinoethyl-amides of acrylic acid; the dimethylaminocyclohexyl-, dimethylaminopropyl-and diethylaminoethyl-amides of methacrylic acid; b -dimethyl or diethylaminoethyl-, di-(2-cyanoethyl)aminopropyl-, di-n-butylaminopropyl-, diphenylaminopropyl-, 4-diethylaminophenyl-esters of acrylic acid and methacrylic acid g -diethylaminopropyl ester, b -diethylaminoethyl-, b -di-butylaminoethyl-, b -morpholinoethyl- and 4-dimethylaminophenylmethyl-vinyl ethers; 2- or 4-dimethylamino-, 2-diethylamino, 3-diisopropylamino-, 4-(N:N-dimethylaminomethyl)-styrenes, 4-dimethylamino- 3-methyl-styrene, 2:4-bis-(dimethylamino)-5-methyl-styrene and p 3-(dimethylamino)-a -methyl-styrene; N,N-dimethyl- or diethylallylamines; basic amides and esters of unsaturated dicarboxylic acids such as maleic, itaconic and fumaric. Copolymerization components specified are vinyl esters or halides, vinylalkyl-ketones, vinylidene chlorides, vinylaryl compounds, acrylic and methacrylic esters, amides or nitriles and analagous derivatives of a -chloracrylic, crotonic, itaconic, maleic or fumaric acids or acrylic acid itself; isobutylene, butadiene or 2-chlorobutadiene.  Suitable polyepoxides are di- or polyglycidyl ethers of polyalcohols or polyphenols; polyglycidyl esters of polycarboxylic acids; polyglycidyl ethers or esters obtained by polymerizing unsaturated glycidyl esters or ethers; polyglycidyl thioethers of polythiols; reaction products of polyphenols with butadiene dioxide or diglycidyl ether; amine polyepoxides; epoxidation products of unsaturated compounds, such as unsaturated fatty acids or polyesters, unsaturated copolymers and unsaturated olefin homopolymers such as di- or tricyclopentadiene.  Together with the polymeric hardening agent there may be used known hardeners such as triethylene tetramine, N:N-diethylpropylenediamine, phthalic anhydride, tetra- or hexa-hydrophthalic anhydride, methyl endomethylenetetrahydro phthalic anhydride and hexachloroendomethylenetetrahydrophthalic anhydride.  Modifiers mentioned are 1:2-epoxydodecane, 1:2-epoxyhexadecane, 1:2-epoxyoctadecane and epoxidized fatty acids and fatty acid esters.  In examples (1) N-diethylaminopropyl methacrylamide and ethyl acrylate are copolymerized in alcohol in the presence of benzoyl peroxide. The copolymer obtained is used in various proportions to harden portions of an epoxy resin, used as an impregnant, adhesive or (with quartz filler) as a putty.  An epoxy resin from terephthalic acid and epichlorhydrin is also hardened with this polymer.  In other examples the hardeners are variously polymers of N-dimethylaminopropyl crotonic acid amide and butyl acrylate; diethylaminoethyl acrylamide and styrene; diethylaminoethyl acrylamide alone; ethyl acrylate and di-[N-dimethylaminopropyl]-fumaric acid amide; N-diethylaminoethyl acrylamide, vinylidene chloride and ethyl acrylate; dimethylaminophenyl acrylamide, tertiary butyl acrylamide and 2-ethylbutyl acrylate; isobutyl acrylate and acrylic acid g -diethylamino propylamide; acrylic acid g -dimethylaminopropyl acrylamide, isobutyl acrylate and methacrylic acid b -hydroxyethyl ester.  Epoxy resins from epichlorhydrin and aniline or a novolak are employed in some cases.