Patent GB-896134-A (GB)
Title: Method of manufacturing synthetic fibres of polyvinyl alcohol
IPC: C08L39/08
Filed: 1959-11-25
Abstract: Polyvinyl alcohol filaments are made by dry-or wet-spinning a spinning solution comprising a polymerized emulsion obtained by copolymerizing in water a hydrophilic vinyl monomer containing quaternary nitrogen with a monomer which forms a water-insoluble polymer, mixed with and dispersed in an aqueous solution of polyvinyl alcohol, the spinning solution containing 0,5-50% of polymer emulsion, by weight, based on the weight of the polyvinyl alcohol, and the resulting filament containing 0,1-2% of its dry weight of nitrogen.  Specified vinyl monomers containing quaternary nitrogen include 4-vinyl-pyridinium methyl chloride, 4-vinyl-pyridinium benzyl chloride, 2-vinyl-pyridinium ethyl chloride, 3-vinyl-pyridinium methyl iodide, 4-vinyl-pyridine betaine, 2-methyl-5-vinyl-pyridinium ethyl bromide, 5-ethyl-2-vinyl-pyridinium butyl bromide, 2-methyl-5-vinyl-pyridinium dodecylbromide, 2-methyl-5-vinyl-pyridinium benzyl chloride, p 2-methyl-5-vinyl-pyridinium methyl-methyl sulphate, di(2-methyl-5-vinyl-pyridinium methyl) sulphate, 2-methyl-5-vinyl-pyridinium methyl-p-toluene sulphonate, 4-vinyl-pyridinium-b -hydroxyethyl chloride, 2-vinyl-quinolinium ethyl bromide, N-triethyl-N-(2-methacryloxy-ethyl) ammonium iodide, allyltriethyl ammonium chloride, and allyl-pyridinium bromide. Specified monomers forming water-insoluble polymers include 2-, 3-, or 4-vinyl-pyridine, 2-methyl-5-vinyl-pyridine, vinyl-quinoline, styrene, divinylbenzene, ethyl-vinyl-benzene, 2-vinyl-naphthalene, vinyl-carbazole, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl benzoate, acrylonitrile, vinylidene cyanide, methyl acrylate, methyl methacrylate, butyl methacrylate, methyl vinyl ketone, diallyl phthalate, allyl chloride, allyl acetate, N.N-diethylamino-ethyl methacrylate.  The spinning solution may also contain other water-soluble polymers, e.g. starch, polyvinyl pyrrolidone, polyacrylamide or partially cyanoethylated polyvinyl alcohol, pigments, e.g. titanium oxide, anionic, cationic, or non-ionic surface active agents, acids, alkalis and Glauber's salt.  The spinning solution may be wet-spun into a conventional Glauber's salt coagulating bath, or may be dry-spun.  Filaments so obtained may be heat-treated, hot-stretched or insolubilized in conventional manner, as by acetalization with formaldehyde, acetaldehyde, chloroacetaldehyde, butylacetaldehyde, nonylaldehyde, benzaldehyde, monochlorobenzaldehyde, 1-naphthaldehyde, or other aldehydes, or by titanation or chroming.  Filaments so made exhibit enhanced transparency, cross-sectional shape and dyeability compared to conventional polyvinyl alcohol filaments.ALSO:Polyvinyl alcohol filaments of enhanced dye-ability towards direct cotton and acid wool dyestuffs are made by dry- or wet-spinning a spinning solution comprising a polymerized emulsion obtained by copolymerizing in water a hydrophilic vinyl monomer containing quaternary nitrogen with a monomer which forms a water-insoluble polymer, mixed with and dispersed in an aqueous solution of polyvinyl alcohol, the spinning solution containing 0.5%-50% of polymer emulsion, by weight, based on the weight of the polyvinyl alcohol, and the resulting filament containing 0.1%-2% of its dryweight of nitrogen.  Specified vinyl monomers containing quaternary nitrogen include 4-vinyl-pyridine methyl chloride, 4-vinyl-pyridinium benzyl chloride, 2-vinyl-pyridinium ethyl chloride, 3-vinyl-pyridinium methyl iodide, 4-vinyl-pyridinium betaine, 2-methyl-5-vinyl-pyridinium ethyl bromide, 5-ethyl-2-vinyl-pyridinium butyl bromide, 2-methyl-5-vinyl-pyridinium dodecylbromide, 2-methyl-5-vinyl-pyridinium benzyl chloride, 2-methyl - 5 - vinyl - pyridinium methyl - methyl sulphate, di (2 - methyl - 5 - vinyl - pyridinium methyl) sulphate, 2-methyl-5-vinyl-pyridinium methyl - p - toluene sulphonate, 4 - vinyl - pyridinium - b  - hydroxyethyl chloride, 2 - vinyl - quinolinium ethyl bromide, N-triethyl-N-(2-methacryloxyethyl) ammonium iodide, allytriethyl ammonium chloride, and allyl-pyridinium bromide.  Specified monomers forming water-insoluble polymers include 2-, 3- or 4-vinyl-pyridine, 2 - methyl, 5 - vinyl - pyridine, vinyl - quinoline, styrene, divinylbenzene, ethyl-vinylbenzene, 2-vinyl-naphthalene, vinyl-carbazole, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl benzoate, acrylonitrile, vinylidene cyanide, methyl acrylate, methyl methacrylate, butyl methacrylate, methyl vinyl ketone, diallyl phthalate, allyl chloride, allyl acetate, N,N-diethylamino-ethyl methacrylate.  The spinning solution may also contain other water-soluble polymers, e.g. starch, polyvinyl pyrrolidone, polyacrylamide or partially cyanoethylated polyvinyl alcohol, pigments, e.g. titanium oxide, anionic, cationic, or non-ionic surface active agents, acids, alkalis and Glauber's salt.  The spinning solution may be wet-spun into a conventional Glauber's salt coagulating bath, or may be dry-spun.  Filaments so obtained may be heat-treated, hot-stretched or insolubilized in conventional manner, as by acetalization with formaldehyde, acetaldehyde, chloroacetaldehyde, butylacetaldehyde, nonylaldehyde, benzaldehyde, monochlorobenzaldehyde, 1-naphthaldehyde, or other aldehydes, or by titanation or chroming.  In examples, filaments so made are dyed with Acid Brilliant Scarlet, and Nippon Fast Violet BB.