Patent GB-768835-A (GB)
Title: Process for polymerising polymerisable unsaturated compounds by the emulsion polymerisation process
IPC: C08F2/22
Filed: 1953-08-24
Abstract: In emulsion polymerization processes, watersoluble compounds of the general formula <FORM:0768835/IV(a)/1> in which R represents an unbranched alkyl chain containing 8-18 carbon atoms, R1, R2 and R3 each represent hydrogen or a methyl group and Me represents an alkali metal cation, are used as emulsifying agents.  They are prepared by reacting the corresponding sultones with alkali metal alcoholates (see Group IV (b).  Specific emulsifying agents mentioned are sodium salts of a -methyl-g -tetradecoxy-propane sulphonic acid, a -methyl-g -dodecoxy-propane sulphonic acid, a -methyl-g -decoxy-propane sulphonic acid, g -dodecoxy-propane sulphonic acid and a -dimethyl-g -decoxy-propane sulphonic acid. Monomeric starting materials mentioned include vinyl esters of organic acids, e.g. the acetate, formate, butyrate, trifluoroacetate or benzoate; vinyl alkyl ketones, vinyl halides, e.g. the chloride and fluoride, chlorofluoroethylene or vinylidene chloride; vinylaryl compounds, e.g. styrene and substituted styrenes; compounds of the acrylic acid series, e.g. esters with alcohols, or phenols, e.g. ethyl, butyl and dodecyl acrylates, acrylonitrile or acrylic amide and its derivatives substituted at the amide nitrogen atom, analogous derivatives of methacrylic acid, a -chloracrylic acid, crotonic acid, maleic acid or fumaric acid, acrylic or methacrylic acid, polymerizable olefines, e.g. isobutylene, butadiene, 2-chloro-butadiene or heterocyclic compounds containing at least one vinyl group, e.g. N-vinyl pyrrolidone, N-vinyl imidazole, vinyl pyridines or vinyl quinolines, unsaturated hydrocarbons, e.g. camphene or unsaturated ethers such as vinyl ethers or isobornyl ether. Polymerization catalysts may be employed, e.g. organic or inorganic peroxides or per-salts, e.g. peracetic acid, acetyl peroxide, benzoyl peroxide, benzoyl acetyl peroxide, lauryl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, para-methane hydroperoxide, hydrogen peroxide, percarbonates, persulphates or perborates.  Heat and actinic rays may be employed separately or together and with or without the use of catalysts. Polymerization regulators, e.g. mercaptans or terpenes, may be added.  The polymerization is advantageously conducted in the absence of oxygen and in the presence of an inert gas, e.g. nitrogen or carbon dioxide.  Activators may be employed, e.g. inorganic, oxidisable, oxygen-containing sulphur compounds, e.g. sulphur dioxide, sodium bisulphite, sodium sulphite, ammonium bisulphite, sodium hydrosulphite and thiosulphate.  Redox systems using water-soluble aliphatic tertiary amines, e.g. triethanolamine or diethyl-ethanolamine, may be employed.  The action of the polymerization catalysts can be accelerated by the use of a heavy metal compound capable of existing in more than one stage of valency and present in the reduced condition or by the addition of a complex cyanide, e.g. of iron, cobalt, molybdenum, mercury, zinc, copper or silver or a mixture of such complexes. In examples: A mixture of acrylonitrile and 2-ethyl hexyl acetate is emulsified with a mixture of sodium a  - methyl - g  - dodecoxy - propane sulphonate, water, triethanolamine, iso-octyl alcohol and acrylic acid, potassium persulphate is added to the emulsion and one half is heated under nitrogen until polymerization commences when the remainder is added and the polymerization is continued, residual monomer is removed by blowing with nitrogen to obtain an emulsion suitable for dressing textiles and paper; alternatively a  - methyl - g  - tetradecoxy - propane sulphonate or a -methyl-g -decoxy-propane sulphonate may be employed as the emulsifying agent (1); in a similar process an emulsion obtained by emulsifying isobutyl acrylate, acrylonitrile and acrylic acid amide in a solution of sodium-a -methyl-g -tetradecoxy-propane sulphonate in water to which acrylic acid, triethanolamine, iso-octyl alcohol and heptadecanol is polymerized to obtain an emulsion suitable for coating textiles; the emulsifying agent may be replaced by sodium g -dodecoxypropane sulphonate or sodium a -dimethyl-g  decoxy-propane sulphonate.ALSO:Compounds corresponding to the general formula <FORM:0768835/IV(b)/1> in which R represents an unbranched alkyl chain containing 8-18 carbon atoms, R1, R2 and R3 each represents hydrogen or a methyl group and Me represents an alkali metal cation, can be made by reacting sultones of the general formula <FORM:0768835/IV(b)/2> with alkali metal alcoholates of the general formula R-OMe, wherein R, R1, R2, R3 and Me have the above definitions.  Elevated temperature, reduced or elevated pressure and an inert diluent may be employed.  Sultones mentioned include a -dimethyl propane sultone, a  - dimethyl - g  - methyl propane sultone and a -methyl-propane sultone.  The sultones may be obtained by sulphochlorinating with sulphur dioxide and chlorine whilst exposing to light an alkyl chloride of the formula <FORM:0768835/IV(b)/3> hydrolysing the sulphochloride formed, and splitting off hydrogen chloride from the resulting sulphonic acid. Sodium a -methyl-g -tetra-decoxy-propane sulphonate is prepared by reacting a -methyl propane sultone with the product obtained by reacting sodium with tetradecanol in xylene.  Dodecanol may be similarly reacted with propane- and a -methyl propane sultone and decanol with a -methyl-and a -dimethyl propane sultones.  The products are employed as emulsifying agents in emulsion polymerization processes (see Group IV (a)).