Patent GB-823181-A (GB)
Title: Epoxy-substituted aromatic compounds and process for preparing these compounds
IPC: C08G59/02
Filed: 1957-11-18
Abstract: New polyepoxide compounds, which are aromatic hydrocarbons or halogen,-substituted aromatic hydrocarbons substituted on at least one ring carbon atom with an epoxyhydrocarbon radical in which the epoxy group is at least one carbon atom removed from the ring carbon atom and substituted on at least one other ring carbon atom with the same or different epoxy-hydrocarbon radical, may be used as additives for vinyl polymers, such as polyvinyl halide and may be used to react with compounds having two hydrogen atoms capable of reacting with the epoxy groups to form high molecular weight products which may be cured with hardening agents to form hard cross-linked insoluble products.  Suitable compounds for reacting with the epoxy compounds are for example, resorcinol, 2,2-bis-(4-hydroxyphenyl) propane, catechol, hydroquinone, methyl resorcinol and 2,2-bis-(4-hydroxyphenyl) butane.  The polyepoxide compounds of the invention may also be copolymerized with other polyepoxide compounds such as glycidyl polyethers of polyhydric phenols or alcohols, polymers prepared from ethylenically unsaturated epoxides, such as glycidyl ether, alone or with other ethylenically unsaturated monomers, and polyepoxide polyethers obtained by reacting a polyhydric alcohol or polyhydric phenol with poly-epoxides.  Suitable curing agents for effecting the above homo- and copolymerization are carboxylic acids or anhydrides, such as formic acid, oxalic acid or phthalic anhydride.  Friedel-Crafts metal halides, such as aluminium chloride, zinc chloride, ferric chloride or boron fluoride or complexes of these with ethers, amines, acid anhydrides, ketones and diazonium salts; phosphoric acid and its partial esters such as n-butyl orthophosphate, diethyl orthophosphate and hexaethyl tetraphosphate; amino compounds such as triethylamine, ethylene diamine, diethylamine, diethylene triamine, triethylene tetramine, dicyandiamide and melamine; and salts of inorganic acids such as zinc fluoborate, potassium persulphate, nickel fluoborate and magnesium perchlorate.  The amount of curing agent used may vary from 1 to 200% by weight of the polyepoxide. Preferably the curing is effected by mixing the curing agent with the polyepoxide and heating to a temperature up to 100 DEG  C.  To prepare improved coating compositions the epoxy material and curing agent with the desired solvents and, if desired, other film-forming materials such as tung oil, linseed oil, dehydrated castor oil and soya bean oil; cellulose nitrate, cellulose acetate, cellulose acetate butyrate, cellulose propionate and ethyl cellulose; and polymers of vinyl chloride, vinylidine chloride, methyl methacrylate and diallyl phthalate, are combined and applied to the surface to be coated.  The new polyepoxides and their polymers may also be used for stabilizing various halogen-containing polymers, particularly the vinyl halide polymers, alone or in combination with other stabilizing agents such as ureas and cadmium salts.  In the examples: (a) 1,4 - bis - (2,3 - epoxypropyl)-benzene is heated with m-phenylene diamine to give an insoluble casting which has excellent heat resistance; similar casting is obtained by heating the same epoxy compound with the diglycidyl ether of 2,2-bis-(4-hydroxy-phenyl)-propane and m-phenylene diamine; (b) 1,4-bis - (2,3 - epoxypropyl - 2,3,5,6 - tetramethyl benzene is heated with m-phenylene diamine to give a hard insoluble casting; similar castings are obtained if the m-phenylenediamine is replaced with diaminodiphenyl sulphone, adduct of m-phenylene diamine and phenylglycidyl ether, diaminopyridine and 1,4-diaminocyclohexane; (c) 1,4 - bis - (2,3 - epoxybutyl)-benzene is heated with m-phenylenediamine to give a hard insoluble casting; a similar casting is obtained by heating the 1,4 - bis - (2,3 - epoxybutyl) benzene with diglycidyl ether of 2,3-bis-(4-hydroxyphenyl) propane and m-phenylene diamine; (d) 1,4-bis-(epoxycyclohexyl) benzene is heated with m-phenylenediamine to give a hard insoluble casting; a similar casting is obtained by heating 1,4-bis-(epoxycyclohexyl) benzene with phthalic anhydride and benzyldimethylamine; (e) a hard casting is obtained by heating 1-epoxyethyl - 4 - (2,3 - epoxypropyl) benzene with m-phenylene diamine; and (f) a heat-resistant casting is obtained by heating bis-(2,3 - epoxypropyl) chlorobenzene with m-phenylene diamine.ALSO:The invention comprises new polyepoxide compounds which are aromatic hydrocarbons or halogen-substituted aromatic hydrocarbons substituted on at least one ring carbon atom with an epoxyhydrocarbon radical in which the epoxy group is at least one carbon atom removed from the ring carbon atom and substituted on at least one other ring carbon atom with the same or different epoxyhydrocarbon radical.  They are preferably prepared by heating the corresponding aromatic hydrocarbon or halo-substituted aromatic hydrocarbon substituted with ethylenically unsaturated side chains with epoxidizing agents, such as peracetic acid, perbenzoic acid and monoperphthalic acid, e.g. 1.4-bis-(2.3-epoxy-propyl) benzene is obtained by treating 1.4-diallylbenzene with peracetic acid. Alternatively, they may be prepared by treating the ethylenically unsaturated compound with HOCl and dehydrochlorinating the product. The aromatic compounds may be mononuclear or polynuclear, which may be fused rings or rings joined through aliphatic or cycloaliphatic radicals.  The rings may be further substituted with hydrocarbon groups such as aliphatic and cycloaliphatic radicals preferably containing up to 12 carbon atoms, such as methyl, butyl, crotyl, cyclohexyl, octyl, decyl, dodecyl and cyclopentyl.  Chlorine and bromine are the preferred halogens.  Suitable starting materials are, for example, 1.4-diallylbenzene, 1.4-dicyclohexenylbenzene, 1.4-dicrotylbenzene, 4-allylcrotylbenzene, 4.41 - diallyl - diphenyl, 2.2-bis-(4 - allylphenyl) propane, 2.2 - bis - (4 - allyl - phenyl) pentane, 1.1.2.2 - tetrakis - (4 - allyl - phenyl) ethane, 1.1.2.2 - tetrakis - (4 - crotyl - phenyl) butane, a .a .a 1.a 1 - tetrakis - (4 - ally - phenyl) - 1.4 - diethylbenzene, 1.3 - diallyl - benzene, 1.3 - diisobutenyl - benzene, 1.3-diallyl - naphthalene, 4 - allylvinylbenzene, 1.3-diallyl - 4 - chlorobenzene, 1.4 - dicrotyl - 2 - chlorobenzene and 1.4 - dicyclohexenyl - 3 - bromobenzene.  One mole. of the epoxidizing agent should be used for every ethylenic group to be oxidized.  Preferably, the epoxidation is carried out in a suitable solvent for the reactants and product.  Suitable solvents are, for example, chloroform, ethyl ether, dichloroethane, benzene and ethyl acetate.  It is desirable to carry out the epoxidation at a temperature between - 20 DEG  C. and 100 DEG  C., preferably between 10 DEG  C. and 60 DEG  C.  The products may be converted to copolymers and homopolymers (Group IV (a)).  In the examples: (a) 1.4-diallylbenzene is dissolved in chloroform and treated with peracetic acid to give 1.4-di-(2.3-epoxy propyl) benzene; (b) 1.4-diallyl-2.3.5.6-tetramethylbenzene is similarly reacted with peracetic acid to give 1.4-bis-(2.3-epoxypropyl)-2.3.5.6-tetramethylbenzene; (c) 1.4-dicrotyl-benzene is similarly reacted with peracetic acid to give 1.4-bis-(2.3-epoxybutyl) benzene; (d) 1.4 - bis - (cyclohexenyl) benzene is reacted with peracetic acid to give 1.4 - bis - (cyclohexenyl) - benzene; (e) 1 - vinyl - 4 - allylbenzene is reacted with peracetic acid to give 1 - epoxyethyl - 4 - (2.3 - epoxypropyl) benzene and (f) 1.4-diallyl-2-chlorobenzene is reacted with peracetic acid to give bis-(2.3-epoxypropyl) chlorobenzene.  Other new compounds which are referred to are 1.3-di-(epoxypropyl) benzene, 1.4 - bis - (2.3 - epoxyhexyl) benzene, 1 - (3.4 - epoxypentyl) - 4 - (2.3 - epoxypropyl) benzene, 1.2 - di - (2.3 - epoxypropylbenzene, 4.41 - bis - (2.3 - epoxypropyl) diphenyl, 1.5 - bis - (2.3 - epoxypropyl) naphthalene, 2.6 - di - (2.3 - epoxypropyl) naphthalene, 1.4 - bis - (2.3 - epoxypropyl) - 3.5 - diisopropyl benzene, 1.4 - bis - (3.4 - epoxybutyl) - 3,5 - di - butyl benzene, 1.2.3 - tri - (2.3 - epoxypropyl) benzene, 1.2.3 - tri - (2.3 - epoxybutyl) benzene, 1.2.3.5 - tetra - (2.3 - epoxypropyl benzene, 1.2-bis - (2.3 - epoxypropyl - 6 - allyl benzene, 1.4-bis - (2.3 - epoxypropyl) - 3 - cyclohexyl benzene, 2.2 - bis - [4 - (2.3 - epoxypropyl) - phenyl] - propane, 2.2 - bis - [4 - (3.4 - epoxybutyl)phenyl] butane, 1.1.2.2 - tetra - [4 - (2.3 - epoxypropyl) phenyl] ethane, 1.1.2.2-tetra - [4 - 2.3 - epoxybutyl) - phenyl] butane, a .a .a 1.a 1 - tetra - [4-(2.3 - epoxypropyl) - phenyl] - 1.4 - diethyl butane, 1.3 - bis - (2.3 - epoxypropyl) - 4 - chlorobenzene, 1.4 - bis - (2.3 - epoxypentyl) - 3.5 - dibromobenzene, 1.4 - bis - (2.3 - epoxycyclopentyl) - 5 - bromobenzene and 1-(2.3-epoxypropyl)-4-epoxyethyl benzene.