Patent GB-814067-A (GB)
Title: Vinyl acetate polymerization
IPC: C08F18/08
Filed: 1955-10-20
Abstract: Vinyl acetate is polymerized in aqueous emulsion in the presence of decahydronaphthalene and, optionally, a small amount of a chelating sequestering agent containing amine and carboxylic acid groups or an alkali metal salt thereof.  The vinyl acetate and decahydronaphthalene may be gradually added to an aqueous medium containing a dispersing agent and a water-soluble peroxidic initiator, preferably at such a rate that the concentration of monomer does not exceed 25 parts per 100 of water.  Copolymers with ethylenic monomers may be obtained and specified are methyl acrylate and methacrylate, ethyl crotonate; acrylic, methacrylic and crotonic acids; acrylamide, N-alkyl- and N,N-dialkyl-acrylamides; acrylonitrile, fumaronitrile, maleic anhydride, dimethyl maleate, vinyl butyrate, vinyl chloride, N-vinyl pyrrolidone, methyl vinyl sulphone, vinyl benzene sulphonic acid and its salts, vinyl benzene sulphonamide, and sodium and ethyl vinyl-sulphonates.  Initiators disclosed are potassium and ammonium persulphates, hydrogen peroxide, unspecified bromates and mixtures of these with iron salts, zinc formaldehyde sulphoxylate, titanous salts and sodium bisulphite. The dispersing agent is preferably a mixture of a hydrophilic colloid and a surface-tension depressant and listed compounds are polyvinyl alcohols, partially hydrolysed polyvinyl acetates, gum arabic; hydroxyethyl, methyl and carboxymethyl celluloses; starch, glue, gelatine, sodium alginate, agar; sterols, e.g. cholesterol; cationic and anionic wetting agents, such as alkyl aryl sulphonates, e.g. isobutyl, diisobutyl and ceryl naphthalene sulphonic acids and their sodium salts, sodium lauryl sulphate, sodium dioctyl sulphosuccinate and formaldehyde-naphthalene sulphonic acid condensation products; non-ionic depressants such as the polyglycol ethers, esters and amides obtained from polyethylene glycols with fatty acids; and mixtures thereof.  The sequestering agents used and which aid polymerization in the presence of an inhibitor such as hydroquinone, are iminotriacetic and ethylene diamine tetra-acetic acids and alkali metal salts thereof.  The polymerization is preferably carried out at pH from 3 to 8 with the aid of acids and bases such as formic acid, sodium bicarbonate, sodium acetate and/or sodium phosphate, and may be effected in two stages as illustrated by the examples wherein most of the monomer is added gradually in the second stage.  The polymer particles in the emulsion are substantially all of diameter less than 2 microns and the products are useful as emulsions in the production of paints.  Pigments and plasticisers which are used in producing paints are titanium dioxide, manganese dioxide, lithopone, antimony oxide, barytes, diatomaceous silica, talc, clays, mica, iron oxides, maroon oxides, metallic browns, cadmium red, toluidine red, para red, lithol toner, cadmium yellow, "Hansa" (Registered Trade Mark) yellow, benzidine yellow, dinitraniline orange, chromium oxide green, phthalocyanine green and blue, lampblack, carbon black, mineral black, aluminium and copper flakes, luminous pigments and "Monastral" (Registered Trade Mark) blue; dibutyl- and dioctylphthalates, dioctyl-sebacate and -adipate, tricresyl phosphate, alkyd resin polyesters, chlorinated diphenyls and substituted biphenyls.  In examples other ingredients specified are ammonia, deionized water and tetra-alkyl quaternary ammonium halide.  Example 8 compares the result obtained by polymerization in the presence of p-xylene. Specification 814,068 is referred to.