Improvements in or relating to the manufacture of copolymers of acrylonitrile

摘要

Copolymers of acrylonitrile with a halogencontaining ester of vinyl phosphonic acid are subjected to amination and/or hydrolysis, the ester preferably being one of the general formula or in which X represents an aliphatic radical containing 1 to 4 carbon atoms, Y represents a halogen atom and Z represents a halogen atom or a hydrogenation, e.g. vinyl-bis-(beta-chlorethyl)-phosphonate. Amination may be carried out with methylamine, dimethylamine, trimethylamine, morpholine, pyridine, piperidine, piperazine, ethanolamine, diethanolamine, triethanolamine, dimethylamino-ethanol, ethylene diamine, hexamethylene diamine, ethyleneimino-propionitrile and compounds which react as bases, such as thiourea, methyl-, ethyleneand butylethylene-thioureas, benzimidazolethiol and 2-mercaptobenzthiazole. After amination the basic groups in the copolymers may be reacted with acids such as sulphuric, phosphoric, hypophosphorous and hydrofluoboric acids. Hydrolysis may be effected with solutions of alkali carbonates, alkali hydroxides, alkaline earth hydroxides or dilute acids. In addition to the acrylonitrile and vinyl phosphonic ester the copolymer may contain in copolymerized form other monomers, e.g. betadimethylaminoethyl, beta - diethylaminoethyl, beta-pyrrolidinoethyl and beta-morpholinoethyl acrylates and methacrylates, the betadimethylaminoethyl and gamma - dimethylaminopropyl amides of acrylic and methacrylic acids, vinyl pyridine, N-vinyl-imidazole, N-vinyl-benzimidazole, N-vinyl oxazole, acrylic, methacrylic, crotonic, maleic, fumaric and vinyl-sulphonic acids, vinyl formate and acetate, allyl and methallyl alcohols and beta-oxyethylacrylamide. The amination process is preferably carried out on the copolymers in solution in a solvent such as dimethyl formamide or tetramethylene sulphone and the hydrolysis process carried out when the product is in shaped, e.g. film or fibre, form. The polymeric products may be dyes with acid and/or basic dyestuff, the choice of dyestuff depending on the groups present in the copolymer.