Patent GB-1082365-A (GB)
Title: Fibre-forming acrylonitrile polymers
Inventor: MAYER RUDI
IPC: C08F28/00
Filed: 1964-08-18
Abstract: Acrylonitrile copolymers are prepared by polymerizing a monomer mixture comprising at least 70% by weight of acrylonitrile and 0.1 to 10% by weight of a thiosulphate compound of the formula R-S-SO3X1, wherein R is an alkyl or aryl group substituted by an ethylenically unsaturated radical and X1 is an alkali metal or an ammonium or substituted ammonium radical, the thiosulphate compound being converted to the free acid form, i.e. X1 is replaced by H, when the reaction is conducted in an acid medium.  The polymerizable mixture may contain an additional monomer, for example in an amount of 1 to 25% by weight of the total monomers; additional compounds specified are vinyl chloride, vinylidene chloride, vinyl acetate, N-vinylpyridine, methyl acrylate, methyl methacrylate, acrylamide, methacrylamide and methacrylonitrile.  The R moiety of the thiosulphate monomer may include, for example, a vinyl, vinyl ester, vinyl ether, acrylic ester, methacrylic ester, acrylamide or methacrylamide group.  Polymerization can be effected in bulk, solution, dispersion or emulsion, the latter method employing emulsifiers such as fatty acid salts, alkyl- or arylsulphonates and polyalkylene oxides.  Suitable catalysts include hydrogen peroxide, persulphates, hydroperoxides, peroxides and azo compounds, e.g. azodiisobutyronitrile, and redox systems such as combinations of persulphates with sulphur compounds containing sulphur in a lower valency state, optionally together with small amounts of iron, copper, cobalt or nickel ions.  Some of the -S-SO3X1 groups (or -S-SO3H groups) can be converted, by known methods, to -SX and/or -SO2X groups during or after polymerization, X being H or X1 as defined above.  Examples illustrate the polymerization in aqueous dispersion at an acid pH of (1) acrylonitrile and sodium allyl thiosulphate, (2) acrylonitrile, methyl acrylate and sodium allyl thiosulphate, (3) acrylonitrile, methyl acrylate and N-(b -methacryloyloxyethyl)-N1-(b  - sodium thiosulphatoethyl) - urea and (4) acrylonitrile, methyl acrylate and sodium vinyloxycarbonylmethylthiosulphate.  The copolymers can be cross-linked by treatment with alkalis, hydrogen peroxide or alkali metal sulphides, disulphide linkages being formed. They are particularly suitable for forming shaped articles, e.g. foils, films, filaments and fibres having excellent dyeability with basic dyestuffs.ALSO:Sodium allyl thiosulphate is prepared by heating sodium thiosulphate with allyl chloride in aqueous medium.  The product is recovered by evaporating, extracting with methanol, evaporating again, and recrystallizing from ethanol.ALSO:Copolymers comprising at least 70% by weight of polymerised acrylonitrile and 0.1 to 10% by weight of a copolymerised thiosulphuric compound of the formula R-S-SO3X, wherein R is alkyl or aryl substituted by an ethylenically unsaturated group and X is hydrogen, alkali metal, ammonium or substituted ammonium, are suitable for forming into shaped articles, e.g. foils, films, filaments and fibres, having excellent affinity for basic dyestuffs.  Examples illustrate the dyeing of films of acrylonitrile - allyl thiosulphuric acid and acrylonitrile - methyl acrylate - allyl thiosulphuric acid copolymers with an aqueous solution of the blue dyestuff of Example 1 of Specification 807,241.