Patent GB-766534-A (GB)
Title: New copolymers of acrylonitrile and process of preparing them
IPC: C08F20/62
Filed: 1952-10-29
Abstract: Acrylonitrile and alpha-substituted acrylonitriles are copolymerized, if desired, in the presence of another copolymerizable compound, with a derivative of an alpha, beta-unsaturated carboxylic acid which contains as a substituent in the carboxyl group a group containing quaternary nitrogen, such as quaternary esters, amides and imides of acrylic, methacrylic, chloroacrylic, phenylacrylic, beta-cyanacrylic, itaconic, fumaric and maleic acids of which many are specified, the preferred being the quaternization products of beta-dimethylaminoethyl acrylate and methacrylate, beta-diethylaminoethyl acrylate and acrylamide, betabromethylacrylamide, 1 : 3 - bis - (diethylamino) - 2 - propyl acrylate, bis - (beta - pyrrolidinoethyl) fumarate, bis - (beta - dimethylaminoethyl) itaconate, and beta-N-pyrollidinoethyl acrylamide.  Optional copolymerizable monomers specified are N-vinyl imidazole, N- or C-vinyl benzimidazole, vinyl pyrrolidone, vinyl - beta - dimethylaminoethyl ether, vinyl - beta - morpholinoethyl ether, vinyl butyl ether, vinyl pyridine and its quaternary derivatives, acrylic acid, acrylamide, N-methyl and N - beta - hydroxyethyl acrylamides, dimethyl methacrylamide, itaconic diamide, maleic acid monomethylamide, bisdimethyl itaconamide, bis-di-gamma-hydroxypropylitaconamide, vinyl formate, acetate and chloracetate, methyl vinylsulphone, N-vinylbenzenesulphonamide, vinyl chloride and styrene.  Polymerization may be carried out in solution in a solvent such as dioxane or isopropanol, or in aqueous emulsion in the presence or absence of an emulsifier such as sodium cetyl sulphate, sodium isododecyl benzenesulphonate, sodium octadecyl sulphate and alkali metal or ammonium salts of condensation products of naphthalene sulphonic acids with formaldehyde.  Specified polymerization catalysts are azodiisobutyronitrile, hydrogen peroxide and alkali metal persulphates or perborates.  The oxidizing catalysts may be activated by reducing agents such as sulphites, hyposulphites, pyrosulphites and mercaptans, e.g. dodecyl mercaptan, which latter also function as chain terminators.  The pH of the aqueous polymerization media is preferably kept within the weakly acid to weakly alkaline range.  During the course of polymerization further quantities of monomer and catalyst may be added gradually to the reaction mixture.  The copolymers produced are soluble in dimethyl formamide, a mixture of dimethyl formamide and cyclohexanone, cyclotetramethylene sulphone, butyrolactone, ethylene cyanhydrin, ethylene carbonate, alpha-chlorobeta-hydroxypropyl cyanide, and, in the case of copolymers containing lesser amounts of acrylonitrile, acetone and cyclohexanone; from solutions thus formed may be produced films and fibres which may be stretched and dyed.  In an Example (6) a dimethylformamide solution of a copolymer of acrylonitrile and betadimethylaminoethyl acrylate methosulphate is wet spun into a coagulating bath consisting of fatty acids containing 7 to 11 carbon atoms.  In addition, copolymers derived from quaternary monomers containing more than one ethylenic linkage, e.g. the reaction product of methyl bromide with di-N-methyl-bis-betahydroxy ethylamine acrylate, may be used as anion-exchangers.ALSO:Derivatives of alpha, beta-unsaturated carboxylic acids which contain as a substituent in the carboxyl group a group containing quaternary nitrogen are prepared either by treating with an alkylating agent a derivative of the acid having an ester or amide group containing a tertiary amino group, or by treating with a tertiary amine a derivative of the acid containing a halogen atom in an alkyl radical of the ester or amide group.  In examples: (1) betadiethylaminoethyl acrylate is quaternized with dimethyl sulphate; (2) beta-dimethylaminoethyl methacrylate is quaternized with methyl bromide; (3) beta-diethylaminoethyl acrylamide is quaternized with dimethyl sulphate; (4) trimethylamine is quaternized with betabromethyl acrylamide; (5) 1 : 3 - bis - (diethylamino)-2-propyl acrylate is quaternized with dimethyl sulphate; (6) beta-dimethylaminoethyl acrylate is quaternized with dimethyl sulphate; (7) beta-dimethylaminoethyl acrylate is quaternized with ethyl monochloracetate; (9) bis - (beta - dimethylaminoethyl) itaconate is quaternized with dimethyl sulphate; (10) bis-(beta-pyrollidinoethyl) fumarate is quaternized with dimethyl sulphate; and (12) beta-N-pyrrolidinoethyl acrylamide is quaternized with dimethyl sulphate.  Other quaternizing agents and derivatives of unsaturated acids are listed.