Patent GB-775892-A (GB)
Title: Method of producing shaped articles from acrylonitrile polymerisation products
IPC: D01F6/18
Filed: 1954-09-16
Abstract: Shaped articles having a major dimension (such as filaments and films) are produced from acrylonitrile homo-, co- and ter-polymers by dissolving the polymer in a solvent, extruding the solution into a coagulating medium, stretching along a major dimension the extruded article so produced to orient the polymer molecules at a temperature at which, during the period of stretching, no substantial crystallization will take place, e.g. at 100 DEG  C. for not over 15 seconds or at 80 DEG  C. for not over 30 minutes, relaxing the extruded article and then crystallizing the polymer by heating the article, for example, to a temperature of 100-120 DEG  C. for a period of 15 seconds.  The polymers contain at least 80 per cent by weight of polymerized or copolymerized acrylonitrile or they may be a blend comprising polyacrylonitrile and copolymers of acrylonitrile with 2-50 per cent of another polymeric material, the blend containing at least 80 per cent of polymerized acrylonitrile. Solvent may be extracted from the shaped article at any stage after coagulation, provided that the temperature of the liquid extraction medium used does not exceed that of the next operation.  Relaxation need not take place immediately after stretching.  Preferably, the stretching temperature and time do not exceed 100 DEG  C. and 15 seconds and the article is washed at below 80 DEG  C. and then heated at low tension to a temperature sufficient to cause the relaxed article to shrink at least 15 to 30 per cent along the major dimension along which it has been stretched.  While thus relaxed the article is washed or dried at a temperature sufficiently high and for a time sufficiently long to result in the article being dimensionally stabilized and to render the micro-structure of the article highly crystalline.  In the case of filaments, they may be crimped and/or cut into staple fibres before or after drying.  The starting material may be a copolymer of 80-98 per cent acrylonitrile and 2-20 per cent of another polymerizable monomer, e.g. acrylic, alpha-chloroacrylic or methacrylic acid, vinyl chloride, fluoride or bromide, vinylidene chloride, 1-chlor-1-bromoethylene, methacrylonitrile, acrylamide, methacrylamide or alpha-chloroacrylamide or a mono-alkyl substitution product thereof, methyl vinyl ketone, a vinyl carboxylate such as vinyl acetate, chloracetate, propionate or stearate, an N-vinylimide, such as N-vinylphthalimide or N-vinylsuccinimide, a methylene malonic ester, itaconic acid or an itaconic ester, N-vinylcarbazole, vinyl furane, an alkyl vinyl ether, vinyl sulphonic acid, an ethylene alpha, beta-dicarboxylic acid or an anhydride or derivative thereof, such as diethyl fumarate, diethyl maleate, diethyl citraconate or diethyl mesaconate, styrene, vinyl naphthalene, a vinylsubstituted tertiary heterocyclic amine, such as a vinyl-pyridine or an alkyl-substituted vinyl pyridine, e.g. 2-vinyl- or 4-vinyl-pyridine or 5 - methyl - 2 - vinylpyridine, or 1 - vinylimid - azole or an alkyl-substituted 1-vinylimidazole, such as 2-, 4- or 5-methyl-1-vinylimidazole.  The polymer may also be an interpolymer such as may be obtained by the interpolymerization of acrylonitrile and two or more of any of the above monomers. Suitable interpolymers comprise 80-97 per cent of acrylonitrile, 1-10 per cent of a vinylpyridine (or a 1-vinylimidazole), and 1-18 per cent of methacrylonitrile (or vinyl chloride).  The polymer may also be a blend of polyacrylonitrile, or of a copolymer of 80-99 per cent acrylonitrile and 1-20 per cent of at least one other substance containing an ethylenic bond, with 2-50 per cent, on the weight of the blend, of a copolymer of 10-70 per cent of acrylonitrile and 30-90 per cent of at least one other ethylenically unsaturated polymerizable monomer, the blend having an overall polymerized acrylonitrile content of at least 80 per cent.  A suitable blend consists of a copolymer of 90-98 per cent acrylonitrile and 2-10 per cent of another mono-olefinic monomer, such as vinyl acetate, which is not receptive to dyestuffs, blended with a sufficient proportion of a copolymer of 10-70 per cent acrylonitrile and 30-90 per cent of a vinylsubstituted tertiary heterocyclic amine, such as a vinylpyridine or 1-vinyl-imidazole, to give a dyeable blend having an overall vinyl-substituted tertiary heterocyclic amine content of 2-10 per cent.  In an example, a spinning solution of 13 per cent concentration is prepared from a blend of a copolymer of 97 per cent acrylonitrile and 3 per cent vinyl acetate with a 50/50 acrylonitrile-vinyl pyridine copolymer in such proportions that the blend contains 6 per cent of vinyl pyridine, the solvent being N,N-dimethylacetamide.  The solution is spun at 25 DEG  C. into an aqueous coagulating bath containing 60 per cent of dimethylacetamide, and the bundle of filaments thus formed is passed from the coagulating bath into a stretch bath of 80 per cent aqueous dimethylacetamide at 100 DEG  C., the length of immersion being 2 inches and the rate of travel 24 feet per minute.  The filaments are then passed through a wash bath of boiling water, the immersion time being less than 15 seconds, and are then removed from the wash bath at a rate of 148 ft. per min., passed through a second boiling water bath in a relaxed condition, the immersion time being 2 seconds, and dried at 100 DEG  C. for over 15 seconds to complete the crystallization of the filaments.