Patent GB-804294-A (GB)
Title: Improvements in or relating to the preparation of curing agents for polyepoxides
IPC: C08G59/64
Filed: 1956-04-26
Abstract: Monomeric and polymeric polyepoxides are cured by means of an adduct prepared by reacting an aromatic polyamine with a monoepoxide having a terminal epoxy group in a molar ratio of more than 2 : 1, preferably more than 2.2 : 1, to give a permanently liquid complex adduct, soluble in organic solvents (see Group IV (b)).  Preferably at least two of the amino groups are primary and, preferably also, the amino groups are attached to the same aromatic nucleus. Particularly preferred amines include those of the formul  X(NH2)n and (NH2)mX-R-X(NH2)m wherein X is a polyvalent, preferably C6-12, aromatic hydrocarbon radical, R is a bivalent aliphatic, preferably C1-6, hydrocarbon radical, n is an integer, at least 2, preferably 2-4 and m is an integer, at least 1, preferably 1-3.  The amines preferably contain no group reactive with the epoxy group other than the amino groups.  Examples of suitable amines are: the phenylenediamines, 4 : 4 - diaminodiphenylmethane; p,p - diaminodiphenylsulphone; triaminobenzene; 2,4 - diaminotoluene; 3,3 - diaminodiphenyl; 1,3 - diamino - 4 - isopropylbenzene; 1,3 - diamino-4,5 - diethylbenzene and diaminostilbene.  m-Phenylenediamine is especially preferred.  The monoepoxides may be aliphatic, cycloaliphatic, aromatic or heterocyclic, saturated or unsaturated and may be substituted with substituents which are non-reactive under the reaction conditions, e.g. ether and ester radicals, halogen atoms.  Preferred are monoepoxy-substituted hydrocarbons containing no more than 12 carbon atoms; mono-epoxy-alkyl ethers of monohydric alcohols or phenols containing no more than 12 carbon atoms; mono-epoxy-alkyl esters of monocarboxylic acids or of polycarboxylic acids where the other carboxyl groups are esterified with alkanols; alkyl and alkenyl esters of 1,2-epoxy monocarboxylic acids; epoxyalkyl ethers of polyhydric alcohols wherein the other hydroxy groups are esterified or etherified and monoesters of polyhydric alcohols and 1,2-epoxymonocarboxylic acids wherein the other OH groups are esterified or etherified.  Especially preferred are the glycidyl monoethers of phenols or aliphatic alcohols containing no more than 8 carbon atoms and monoepoxy-substituted hydrocarbons containing no more than 10 carbon atoms.  Amongst many epoxides mentioned are styrene oxide, allyl glycidyl ether, alkyl glycidyl ethers, aryl glycidyl ethers, chlorophenyl glycidyl ether, esters of the monoglycidyl ether of glycerol, 1,2-alkylene oxides, epichlorhydrin, glycidyl esters, and 1,2-epoxy propionates.  The polyepoxide may be cured by merely mixing in the adduct.  The curing reaction occurs slowly at 20 DEG  C., but a temperature between 50 DEG  and about 280 DEG  C. is desirable.  It is possible to arrest the curing at an intermediate stage by, for example, cooling below 40 DEG  C., giving a resinous product which remains readily fusible and acetone-soluble for some weeks when kept at about 20-25 DEG  C. Amounts of adducts used can range from about 5 to 40, preferably 10-30, parts per 100 parts of polyepoxide.  It is desirable to have the polyepoxide in a liquid condition when the adduct is added to facilitate mixing.  This may be effected by heat or by solvents which may either be volatile and evaporate before or during the curing reaction, e.g. ketones, esters, alcohols or chlorinated hydrocarbons or mixtures of these active solvents with aromatic hydrocarbons or alcohols, or may remain in the cured composition, e.g. dibutyl phthalate, or acetonitrile.  The polyepoxides may be saturated or unsaturated. aliphatic, alicyclic, aromatic or heterocyclic and may be substituted, for example, chlorine, hydroxyl or the ether radical. Suitable types of which numerous examples are given are: (1) polyepoxides which are single compounds such as butadiene dioxide or diglycidylether; (2) glycidylpolyethers of polyhydric phenols such as bis-phenol-[2,2-bis-(4-hydroxyphenyl)-propane] and novolac resins; (3) polepoxypolyethers from polyhydric alcohols, for example, glycerol triglycidyl ether; (4) polyepoxy polyesters such as the diglycidyl ester of adipic acid; (5) polymers and copolymers of epoxy - containing monomers possessing at least one polymerizable linkage, e.g. polyallyl glycidyl ethers and copolymers of allyl glycidyl ethers and styrene.  Ingredients such as pigments, fillers, dyes, plasticizers and resins may be mixed with the polyepoxide as subjected to cure with the adducts.  The polyepoxides cured according to the invention may be used in the manufacture of laminates re-inforced with fibrous materials (see Group VIII), or for moulded articles.  Examples illustrate the use of adducts, obtained by reacting phenylene diamines, methylene dianiline, p,p1-diaminodiphenylmethane, 4,41 - diaminodiphenyl, m-toluenediamine or diaminostilbene with styrene oxide, phenyl glycidyl ether, allyl glycidyl ether, glycidyl propionate, glycidyl caproate, allyl glycidyl phthalate or glycidyl acrylate in curing polyepoxy polyethers obtained by reacting bisphenol with epichlorohydrin at elevated temperatures in the presence of sodium hydroxide.ALSO:An aromatic polyamine is reacted with a monoepoxide having a terminal epoxy group in a molar ratio of more than 2 : 1, preferably more than 2.2 : 1, to give a permanently liquid complex adduct, soluble in organic solvents.  Preferably at least two of the amino groups are primary and, preferably also, the amino groups are attached to the same aromatic nucleus. Particularly preferred amines include those of the formul  X(NH2)n and (NH2)mX-R-X(NH2)m\t wherein X is a polyvalent, preferably C6-12, aromatic hydrocarbon radical, R is a bivalent aliphatic, preferably C1-6, hydrocarbon radical, n is an integer, at least 2, preferably 2-4, and m is an integer, at least 1, preferably 1-3. The amines preferably contain no group reactive with the epoxy group other than the amino groups.  Examples of suitable amines are: the phenylenediamines, 4 : 4 - diaminodiphenylmethane; p,p - diaminodiphenylsulphone; triaminobenzene; 2,4 - diaminotoluene; 3,3 - diaminodiphenyl; 1,3 - diamino - 4 - isopropylbenzene; 1,3 - diamino - 4,5 - diethylbenzene and diaminostilbene. m-Phenylenediamine is especially preferred.  The monoepoxides may be aliphatic, cycloaliphatic, aromatic or heterocyclic, saturated or unsaturated and may be substituted with substituents which are non-reactive under the reaction conditions, e.g. ether and ester radicals, halogen atoms.  Preferred are monoepoxy-substituted hydrocarbons containing no more than 12 carbon atoms; mono-epoxy-alkyl ethers of monohydric alcohols or phenols containing no more than 12 carbon atoms; mono-epoxy-alkyl esters of monocarboxylic acids or of polycarboxylic acids, where the other carboxyl groups are esterified with alkanols; alkyl and alkenyl esters of 1,2-epoxy-monocarboxylic acids; epoxyalkyl ethers of polyhydric alcohols wherein the other hydroxy groups are esterified or etherified and monoesters of polyhydric alcohols and 1,2-epoxymonocarboxylic acids wherein the other OH groups are esterified or etherified.  Especially preferred are the glycidyl monoethers of phenols or aliphatic alcohols containing no more than 8 carbon atoms and monoepoxy-substituted hydrocarbons containing no more than 10 carbon atoms.  Amongst many epoxides mentioned are styrene oxide, allyl glycidyl ether, alkyl glycidyl ethers, aryl glycidyl ethers, chlorophenyl glycidyl ether, esters of the monoglycidyl ether of glycerol, 1,2-alkylene oxides, epichlorhydrin, glycidyl esters, and 1,2-epoxy propionates.  The adducts are prepared by heating the reactants, preferably above 50 DEG  C., more preferably at 80-200 DEG  C., for a short period and then allowing to stand.  Pressure is usually atmospheric but may be higher.  The amount of polyamine should preferably not exceed 10, and more preferably 5, mols. per mol. of monoepoxide.  It is preferred to add the epoxide to the amine.  The reaction may be effected in an inert solvent, e.g. dioxane or diethyl ether.  The adducts are used for curing epoxide resins (see Groups IV (a) and VIII).  In examples, adducts are formed by reacting m-phenylenediamine, a mixture of m-phenylenediamine and 4,41-diamino-diphenylmethane, a eutectic mixture of o- and m-phenylenediamines, 4,41-diaminodiphenylmethane, 4,41 - diamino-diphenyl, m-toluylenediamine or diaminostilbene with styrene oxide, phenyl glycidyl ether, allyl glycidyl ether, glycidyl propionate, glycidyl caproate, allyl glycidyl phthalate or glycidyl acrylate.