Patent GB-932814-A (GB)
Title: Improving physical properties of cellulosic articles
IPC: D21H17/44
Filed: 1961-01-30
Abstract: Polymers or copolymers containing the recurring group: <FORM:0932814/IV(a)/1> where R1 is hydrogen or an alkyl radical containing from 1 to 6 carbon atoms, X is an organic sulphonium radical of a kind resulting from an increase in the valency of the sulphur atom of an organic sulphide of the general formula: R11-S-R111, where R11 and R111 either each represent one of the following: (a) an alkyl radical, (b) a haloalkyl radical, (c) a hydroxyalkyl radical, (d) -(CH2)nCHNH2-COOH, (e) -(CH2)n1CH(OH)COOH, (f) -(CH2CH2O-)mCH2CH2OH, (g) -Cm1H2m1COOH, (h) <FORM:0932814/IV(a)/2> (i) -Cm1H2m1COO-alkali metal, or (j) -Cm1H2m1CONH2, where n, n1, m and m1 are integers and the total number of carbon atoms in each substituent does not exceed 6, or together represent a bivalent organic radical forming with the sulphur atom a ring containing 4 or 5 carbon atoms and one sulphur atom, and Y represents a carbonate, oxalate, phthalate, succinate, dihydrogen phosphate, fluoride, benzoate, chloride, nitrate, acetate, sulphate, bromide or iodide anion are made by:  (1) polymerizing a monomer:  <FORM:0932814/IV(a)/3> (2) copolymerizing two or more such monomers,  (3) copolymerizing such a monomer with a minor proportion of one or more ethylenically unsaturated monomers,  (4) mixing two or more of the polymeric materials of (1), (2) and (3) above,  (5) introducing a halomethyl group into an aromatic polymer substrate and thereafter reacting with a thioether, or  (6) polymerizing the vinyl-benzyl halide and reacting with the sulphur-containing compound.  Examples of cyclic sulphides of the formula R11-S-R111 are tetrahydrothiophene, halosubstituted tetrahydrothiophene, alkyl-substituted tetrahydrothiophene in which the alkyl group contains one to five carbon atoms, thiacyclohexane and 1-oxa-4-thiacyclohexane.  Suitable comonomers are acrylamide, olefines, acrylic acid, vinyl-aromatic compounds, acrylates, methacrylates, acrylonitrile and ar-vinyl-benzyltrimethylammonium chloride.  The polymerization may be carried out in an emulsion or solution in the presence of a catalyst such as ultra-violet light, gamma radiation, "azo" catalysts or peroxides.  The homopolymers and copolymers may be lightly cross-linked by such agents as divinylbenzene, the divinyl ether of diethylene glycol, ethylene glycol diacrylate, ethylene glycol dimethacrylate, glycerol trimethacrylate, diallyl itaconate, diallyl maleate, diallyl fumarate, diisopropenyl-diphenyl, and their homologues and mixtures. Homopolymers referred to are those of vinylbenzyl-bis-(2-hydroxyethyl)-sulphonium chloride, vinylbenzyl-methylthetine, vinylbenzyl-2-hydroxyethanolthetine, vinylbenzylmethyl-(3-carboxy-3-hydroxy-propyl)-sulphonium hydroxide as an inner salt, vinylbenzyl-bis-(2-carboxyethyl)-sulphonium hydroxide as an inner salt, vinylbenzyl-methyl-2-hydroxyethyl-sulphonium chloride, dimethyl-ar-vinylbenzenesulphonium chloride, vinylbenzylmethyl-2,3-dihydroxypropylsulphonium chloride, vinylbenzyl - 2 - hydroxyethyl - 2 - carbamoylethylsulphonium chloride, vinylbenzyl-methyl-2-carbamoylethylsulphonium chloride, vinylbenzylmethyl-2-hydroxyethylsulphonium chloride, vinylbenzyl-methyl-carbamoylmethyl-sulphonium chloride, vinylbenzyl-ethanolthetin, vinylbenzyl-methionium chloride, vinylbenzyl-bis(2-hydroxyethyl)-sulphonium bicarbonate, the acetate, dihydrogen phosphate, sulphate, bromide, fluoride, nitrate, benzoate, phthalate, carbonate, succinate, oxalate and maleate of the last-named base, ar-vinylbenzyl-tetrahydrothiophenium chloride, and ar-vinylbenzyl-(2(2-(2(2(2-hydroxyethoxy) ethoxy) ethoxy) ethoxy) ethyl)-sulphonium chloride.  Copolymers referred to are of dimethyl-ar-vinylbenzyl-sulphonium chloride and divinylbenzene, styrene, acrylonitrile or methyl methacrylate, of dimethyl-ar-vinylbenzyl-sulphonium chloride, divinylbenzene and acrylic acid or acrylamide, of bis-2-hydroxyethyl)-ar-vinylbenzyl-sulphonium chloride and trimethyl-(ar-vinylbenzyl)-ammonium chloride, or dimethyl-(ar-vinylbenzyl)-sulphonium chloride, or acrylamide, or acrylic acid, and of bis - (2 - hydroxyethyl) - ar - vinylbenzyl - sulphonium chloride, trimethyl-(ar-vinylbenzyl)-ammonium chloride and divinylbenzene.  Another specific substance referred to is obtained by dissolving polystyrene in chloromethyl ether with a catalyst, killing the reaction with methanol, isolating the product and reacting it with dimethyl sulphide.ALSO:Monomers, which are polymerisable (see Group IV(a)), of the formula: <FORM:0932814/IV(a)/1> where R1 is hydrogen or an alkyl radical containing from 1 to 6 carbon atoms, X is an organic sulphonium radical of a kind resulting from an increase in the valency of the sulphur atom of an organic sulphide of the general formula: R11-S-R111, where R11 and R111 either each represent one of the following: (a) an alkyl radical, (b) a haloalkyl radical, (c) a hydroxyalkyl radical, (d) -(CH2)nCHNH2-COOH, (e) -(CH2)n1CH(OH)COOH, (f) -(CH2CH2O-)mCH2CH2OH, (g) -Cm1H2m1COOH (h) Cm1H2m1COOCm1H2m1+1 (i) -Cm1H2m1COO-alkali metal, or (j) -Cm1H2m1CONH2, where n, n1, m and m1 are integers and the total number of carbon atoms in each substituent does not exceed 6, or together represent a bivalent organic radical forming with the sulphur atom a ring containing 4 or 5 carbon atoms and one sulphur atom, and Y represents a carbonate, oxalate, phthalate, succinate, dihydrogen phosphate, fluoride, benzoate, chloride, nitrate, acetate, sulphate, bromide or iodide anion are made by contacting a vinyl benzyl halide with a compound of the formula R11-S-R111 in the presence or absence of a solvent or non-solvent liquid medium.  Examples of cyclic sulphides of the formula R11-S-R111 are tetrahydrothiophene, halo-substituted tetrahydrothiophene, alkylsubstituted tetrahydrothiophene in which the alkyl group contains one to five carbon atoms, thiacyclohexane and 1-oxa-4-thiacyclohexane.  An excess of the sulphide promotes the formation of the vinylbenzylsulphonium compound.  Solvents such as water, nitromethane, methanol, ethanol and acetonitrile may be used, or may be dispensed with if the reactants are liquid.  The resulting materials have a halide anion.  If desired this can be converted to carbonate, nitrate, sulphate and acetate by passing a solution of the monomer into contact with an anion-exchange resin in the form of its appropriate salt.