Patent GB-580469-A (GB)
Title: Acetylene tetraesters of alpha-methylene monocarboxylic acids and polymers and copolymers thereof
IPC: C08F20/20
Filed: 1944-10-16
Abstract: Acetylene tetraesters of a -methylene monocarboxylic acids are produced by reacting glyoxal or its equivalents, such as its sulphate or polymers, with the acid anhydrides or compounds yielding them under the reaction conditions.  The preferred esters have the formula <FORM:0580469/IV/1> where R is hydrogen, alkyl, aryl or halogen.  The a -methylene monocarboxylic acids include acrylic, a -methacrylic, a -butyl-, a -heptyl-, a -cyclohexyl-, a -phenyl-, and a -chlor-acrylic acids.  The esters polymerize to insoluble, infusible polymers and may first be partially polymerized to a fusible, soluble state. They may be copolymerized with polymerizable ethylenic compounds, especially esters of acrylic and methacrylic acids such as methyl, ethyl, isobutyl and a -phenyl methacrylates, glycol dimethacrylate, polyethylene glycol dimethacrylate, and heptyl acrylate, styrene, vinyl ketones, vinyl esters, chloroprene, butadiene, itaconic esters and vinyl imides such as vinyl phthalimide.  They also copolymerize with compounds not readily polymerizable alone such as a , b unsaturated dicarboxylic acids, esters, and anhydrides, for example diethyl maleate, maleic anhydride, dimethyl fumarate, mesaconic acid and esters, vinyl ethers and allyl and methallyl esters.  Generally 1-10, preferably 2-5, per cent by weight of the copolymer, of the acetylene tetraesters are used.  The tetraesters accelerate the polymerization of the other component and may be added in amounts of .05-5 per cent by weight to, for example, styrene for this purpose. Sheet casting and granular polymerization of such compounds is made possible.  Peroxy compounds and other known polymerization catalysts may be used.  The polymers and copolymers, with plasticisers, fillers, pigments, dyes, and waxes if desired, may be used in lacquers and paints, coating and impregnating fibrous material, and for cast and moulded articles. In examples: (1) glyoxal sulphate is added in portions to methacrylic anhydride, containing diphenylamine as a polymerization inhibitor, at 100-110 DEG  C., the product cooled, and diluted with water in stages to separate solid acetylene tetramethacrylate which is dried, and which polymerizes above its melting point; (2) in place of methacrylic anhydride, methacrylic acid, acetic anhydride and benzene sulphonic acid are used; (3) the glyoxal sulphate of (1) is replaced by glyoxal and benzene sulphonic acid; (4) styrene and acetylene tetramethacrylate in a ratio of 95 : 5 are heated to 80 DEG  C. in nitrogen until a thin syrup is formed which is cooled, mixed with benzoyl peroxide in styrene, poured into a casting cell, polymerized at 75 DEG  C. and 150 p.s.i. for 16 hrs., and seasoned in an air oven to produce a polymer sheet; (5) methyl methacrylate, acetylene tetramethacrylate, and benzoyl peroxide in the ratio 95 : 5 : .03 are polymerized by heating for 2 hrs. at 70 DEG  C.; (6) a rubbery polymer is prepared by heating butadiene, acrylonitrile and acetylene tetramethacrylate in ratio 67 : 30 : 3 for 70 hrs. at 60 DEG  C. while emulsified in water containing ammonium persulphate and sodium bisulphite; (7) styrene, acetylene tetramethacrylate and benzoyl peroxide in the ratio 95 : 5 : .5 are heated for 160 mins. at 94-97 DEG  C. while suspended in water containing neutralized polymethacrylic acid to yield a granular polymer; (8) styrene, methyl methacrylate, acetylene tetramethacrylate and benzoyl peroxide in the ratio 442 : 245 : 35 : .7 are heated at 80 DEG  C. to give a syrup which is further polymerized in a casting cell to yield a polymer sheet.