Patent GB-954096-A (GB)
Title: Improvements in and relating to polymers
IPC: C08F214/06
Filed: 1961-12-13
Abstract: Acryloxyalkoxyaryl sulphonic acid compounds of formula: <FORM:0954096/C2/1> where R is hydrogen or methyl, Ar is a substituted or unsubstituted phenylene or naphthylene radical, M is hydrogen, ammonium or an alkali metal, b is 1, 2 or 3, c is 1 or 2 and d is 1 or 2 may be prepared by sulphonation with concentrated sulphuric acid of the corresponding acrylic or methacrylic esters, optionally in the presence of an inert organic liquid diluent, followed by neutralisation if desired with the corresponding bases. Experiments describe the preparation of (I) acryloxyethoxy benzene sulphonic acid by the sulphonation of phenoxyethyl acrylate, (II) potassium acryloxyethoxy nitrobenzene sulphonate by the sulphonation of nitrophenoxyethyl acrylate and treatment of the product with potassium acetate, (III) potassium acryloxyethoxy-p-t. butylbenzene sulphonate by the sulphonation of p-t. butylphenoxyethyl acrylate and treatment of the product with potassium acetate, and (IV) sodium methacryloxy ethoxybenzene sulphonate by the sulphonation of phenoxyethyl methacrylate and treatment of the product with sodium hydroxide.ALSO:Solid polymers containing 35 to 75% by weight of polymerized acrylonitrile, 10 to 60% of polymerized vinyl chloride and 0.5 to 10% of a polymerized acryloxyalkoxyarylsulphonic acid compound of formula: <FORM:0954096/C3/1> where R is hydrogen or methyl; Ar is a substituted or unsubstituted phenylene or naphthylene radical; M is hydrogen, ammonium or an alkali metal; b is 1, 2 or 3; c is 1 or 2 and d is 1 or 2; and if desired 5 to 20% of polymerized vinylidene chloride, the sum of all the copolymerized monomers being 100%, may be prepared by copolymerizing the monomers at 25 to 70 DEG C. Polymerization may be effected in the presence of catalysts, e.g. alkali metal persulphates and peroxides, optionally together with alkali metal bisulphites, sulphur dioxide or ferrous sulphate, and azo compounds; and chain terminators, e.g. t dodecyl mercaptan, 2-mercaptoethanol and thiourea; in bulk; in aqueous emulsion or dispersion in the presence of emulsifying and dispersing agents, e.g. potassium stearate, potassium palmitate, potassium laurate, amine soaps, sulphonates of alkanes, alkylbenzenes, naphthalenes and succinic esters, and salts of formaldehyde condensed alkyl aryl sulphonic acids; or in solution, e.g. in acetone, acetonitrile, N,N-dimethylformamide N,N-dimethylacetamide and dimethyl sulphoxide. The polymers may be mixed with pigments and stabilizers, e.g. dibutyl tin maleate, dioctyl tin maleate, the diglycidyl ether of Bisphenol-A, propylene oxide, pyridine borane, trioctyl phosphite and diphenyl pentaerythritol diphosphite; and may be dissolved in solvents, e.g. acetone, acetonitrile, N N-dimethylformamide, N,N-dimethylacetamide, gammabutyrolactone, ethylene carbonate, ethylene carbamate and N-methyl-2-pyrrolidone, and spun into fibres or cast into films which may readily be dyed.  Examples describe the copolymerization in aqueous emulsion in the presence of redox catalyst systems, sodium di(2-ethylhexyl) sulphosuccinate and 2-mercaptoethanol, and with controlled addition of catalyst components and monomers, of acrylonitrile and vinyl chloride with (1) 2-acryloxy-ethoxybenzene sulphonic acid, 3-acryloxypropoxy benzene sulphonic acid, acryloxyethoxyethoxybenzene sulphonic acid, acryloxypropoxyethoxybenzene sulphonic acid, acryloxyethoxypropoxybenzene sulphonic acid and acryloxypropoxypropoxybenzene sulphonic acid; (2) potassium and lithium acryloxy-ethoxybenzene sulphonates; (3) sodium and ammonium acryloxyethoxy benzene sulphonates; (4) methacryloxyethoxybenzene sulphonic acid, methacyloxypropoxybenzene sulphonic acid, methacryloxyethoxy ethoxybenzene sulphonic acid, methacryloxypropoxyethoxybenzene sulphonic acid, methacryloxyethoxypropoxybenzene sulphonic acid and methacryloxypropoxypropoxybenzene sulphonic acid; (5) sodium, ammonium, lithium and potassium methacryloxyethoxybenzene sulphonates; (6) potassium methacryloxyethoxy-naphthalenesulphonate, acryloxyethoxynaphthalene sulphonic acid, acryloxypropoxynaphthalene sulphonic acid, methacryloxypropoxyethoxynaphthalene sulphonic acid, acryloxy ethoxypropoxynaphthalene sulphonic acid, methacryloxypropoxypropoxynaphthalene sulphonic acid and the sodium, potassium and ammonium salts of these acids; (7) potassium methacryloxynaphthalene disulphonate, acryloxymethoxy-naphthalene disulphonic acid, methacryloxypropoxynaphthalene disulphonic acid, acryloxyethoxyethoxynaphthalene disulphonic acid, methacryloxyethoxypropoxynaphthalene disulphonic acid, acryloxypropoxypropoxynaphthalene disulphonic acid and the sodium, potassium, lithium and ammonium salts of these acids; and (10) sodium methacryloxyethoxy benzene sulphonate; and of acrylonitrile, vinyl chloride and vinylidene chloride with (8) potassium acryloxyethoxybenzene sulphonate, methacryloxypropoxybenzene sulphonic acid, methacryloxyethoxyethoxybenzene sulphonic acid, methacryloxypropoxyethoxybenzene sulphonic acid, methacryloxyethoxypropoxybenzene sulphonic acid, acryloxyethoxynaphthalene sulphonic acid, methacryloxyethoxynaphthalene disulphonic acid, methacryloxypropoxynaphthalene sulphonic acid, acryloxyethoxyethoxynaphthalene disulphonic acid, acryloxyethoxypropoxybenzene sulphonic acid, acryloxypropoxypropoxynaphthalene disulphonic acid and the salts of these acids and (9) sodium acryloxyethoxybenzene sulphonate.