Patent GB-822638-A (GB)
Title: Process for curing polyepoxides and resulting products
IPC: C08G59/50
Filed: 1956-12-28
Abstract: Polyepoxide compositions which cure to an intermediate soluble and fusible state in which they can be stored for long periods before conversion to the infusible state and are thus suitable for making coating compositions, electrical pottings, castings and laminates consist of a polyepoxide having on the average more than one epoxy group per molecule and a hydrogenated aromatic primary and/or secondary amine having at least two amino hydrogen atoms in the molecule.  Aromatic amines specified are o-, m-, p-phenylene diamine, N-methyl p-phenylene diamine, diamino diphenylmethane, p,p1-methylene dianiline, N-ethyl, p,p1-methylene dianiline, p,p1-diamino diphenyl sulphone, triaminobenzene, 2,4 - diamino toluene, 3,31 - diamino diphenyl, 1,3 - diamino - 4 - isopropylbenzene, 1.31 - diamino - 4.5 - diethylbenzene, N,N1 - diethyl - triaminobenzene, diamino stilbene, N,N1 - diphenylethylethylenediamine, 4,41,411 - triamino - triphenylmethane, 2,6 - diamino - anthraquinone, 1 - hydroxy - 2,4,6 - triaminobenzene. Preferred polyamines are those having the formula X(NHR)n and (RHN)nXR1X(NHR)n wherein X is a polyvalent aromatic hydrocarbon radical which may be hydroxyl substituted, preferably containing from 6-12 carbon atoms, R is H or an aliphatic hydrocarbon radical preferably containing 1-6 carbon atoms, R1 is a bivalent hydrocarbon or -S-, -SO-, or -SO2- containing hydrocarbon radical, n is 2-4 and m is 1-3.  Mixtures of the amines may be used.  The amines are hydrogenated by treatment with hydrogen in the presence of a catalyst to convert at least 50% of the aromatic structures to aliphatic structures and preferably all the aromatic rings to aliphatic rings.  Curing of the compositions may be effected at 20 DEG  C. but temperatures of 50-280 DEG  C. are preferred. Curing can be arrested by cooling to about 40 DEG  C. and the product can be maintained fusible for a number of weeks if maintained at 20-25 DEG C. 5-50 parts of the hydrogenated amine can be used per 100 parts polyepoxide. The fluidity of the mixture can be increased by addition of solvents which may be volatile and removed during curing, e.g. ketones, esters, alcohols, cellosolve acetate, glycols, ethers, chlorinated hydrocarbons (trichloropropane or chloroform).  These may be used in admixture with aromatic solvents, e.g. toluene.  Solvents which remain in the cured composition may also be used, e.g. diethyl phthalate, dibutyl phthalate, monoepoxides, e.g. glycidyl allyl ether, styrene oxide, 1,2-hexylene oxide, glycide, and nitriles. Polyepoxides specified are (1) glycidyl ethers of polyhydric phenols or polyhydric alcohols; (2) glycidyl ethers of novolac resins; (3) glycidyl ethers of polyhydric phenols having two hydroxyaryl groups separated by an aliphatic chain of at least 6 carbon atoms produced by condensing a phenol with a phenol having an aliphatic chain with one or more double bonds, e.g. cardanol.  In examples: (1) m-phenylene diamine dissolved in dioxane containing a little ruthenium dioxide was hydrogenated in a bomb with hydrogen at 100-120 DEG  C. for 8 hours after purification and distillation a liquid identified as diaminocyclohexane was obtained.  15 parts were mixed with 100 parts of a polyether obtained from 2,2-bis-(4-hydroxyphenyl) propane and epichlorhydrin and the mixture heated for 4 hours at 100 DEG  C. and then 2 hours at 150 DEG  C. The resulting product has a barcol hardness of 40 at room temperature and a hardness 42 after immersion in boiling water. In the following examples the following hydrogenated amines were used as curing agents for specified epoxide resins: (3) p,p1-diamino-diphenylmethane; (4) p-phenylene diamine; (5) benzene triamine; (6) p,p1 - diamino - diphenyl sulphone. Specification 791,836 is referred to.  Reference has been directed by the Comptroller to Specification 781,412.