Patent GB-1227410-A (GB)
IPC: C08F289/00
Filed: 1968-09-03
Abstract: 1,227,410. Acrylonitrile copolymer films and filaments. TOYO BOSEKI K.K. 3 Sept., 1968 [2 Sept., 1967; 22 Dec., 1967], No. 41923/68. Heading B5B. [Also in Division C3] Filaments or films are produced by extruding into a coagulating bath an acidic solution of a cross-linkable linear copolymer consisting of units derived from: I, acrylonitrile or a mixture of acrylonitrile and at least one comonomer, the concentration of acrylonitrile in said mixture being at least 70% by weight, II, an ethylenically unsaturated monomer having as substituent a group of formula in which X<SP>1</SP> is a halogen atom and X<SP>2</SP> is a hydrogen or halogen atom or an alkyl, amino, hydroxyl, mercapto or carboxyl group and Z is a nitrogen atom or methine group, III, an ethylenically unsaturated monomer having an amino, imino or hydroxyl group or a group which is convertible into an amino, amino or hydroxyl group or a pyridyl, pyrazinyl or quinolyl group, and/or a protein. Examples are given in which (a) an aqueous zinc chloride solution of (i) a graft polymer of protein, acrylonitrile (AN) and 2-allylamino - 4,6- dichloro - s - triazine (AAT), (ii) a graft polymer of protein, AN, 2 - (para - vinylanilino) - 4,6- dichloropyrimidine (VAP) and methyl methacrylate, (iii) a copolymer of AN, AAT, allylamine (AA) and, in some cases, methyl acrylate (MA), (iv) a copolymer of AN, MA, AAT and allylalcohol (AOM), (v) a copolymer of AN, MA, AAT and 4 - vinylpyridine, (vi) a copolymer of AN, MA, 2 - allylamino - 4,6 - dichloropyrimidine and AA or (vii) a copolymer of AN, acrylamide (AAM), 2 - amino - 4 - allyloxy - 6- chloro - 8 - triazine (AAOT) and AA is extruded into an aqueous zinc chloride solution at -2 to 0 C., the coagulated filaments formed being stretched to 15 times their original length in steam or glycerine at 120 C. or in boiling water: (b) an aqueous zinc chloride-sodium chloride of a graft polymer of protein, AN, AAM and AAOT is extruded into an aqueous zinc chloride-sodium chloride bath and the filaments formed are treated as in (a): (c) an acidic dimethyl sulphoxide solution of (i) a graft polymer of protein, AN and ATT, (ii) a graft polymer of protein, AN, VAP and methyl methacrylate or (iii) a graft polymer of protein, AN, AAOT and vinyl acetate is extruded into aqueous acidic dimethyl sulphoxide, the filaments formed being stretched to 13 times their original length in water at 90 C.: (d) an aqueous nitric acid-zinc nitrate solution of a copolymer of AN, MA, AAT and AA is extruded into aqueous nitric acid at 10 C., the filaments formed being stretched to 7 times their original length in boiling water: (e) an acidic dimethyl sulphoxide solution of a copolymer as in (d) is extruded into aqueous dimethyl sulphoxide at 40 C., the filaments formed being stretched to 7 times their original length in glycerine at 120 C., washed, passed through boiling water under tension and dried: (f) an aqueous ethylene carbonate solution of a copolymer of AN, MA, AAT and AA is extruded into an aqueous acidic bath at 30 C., the filaments formed being stretched to 7 times their original length in boiling water: (g) an acidic dimethyl acetamide solution of a copolymer of AN, MA, AAT and AA is extruded into aqueous dimethyl acetamide at 20 C., the filaments formed being stretched to 6 times their original length in boiling water: (h) an acidic dimethyl formamide solution of a graft polymer of protein, AN and AAT is extruded into a spinning tube at 200 to 250 C., the filaments formed being stretched to 5 times their original length in boiling water: (i) an aqueous zinc chloride solution of a graft polymer of protein, AN and AAT or a copolymer of AN, AAT, MA and AA is extruded into aqueous zinc chloride solution at 0 C. and passed over an inclined flat plate whilst being coagulated, the film formed being stretched to 5 times its original length in one direction in hot water.