Patent GB-592604-A (GB)
Title: Process for the production of co-polymers of unsaturated esters of ethereal oxygen-containing acids
IPC: C08F18/12
Filed: 1945-04-03
Abstract: The process comprises copolymerizing in the presence of a catalyst a polymerizable unsaturated ester of an ethereal oxygen-containing polycarboxylic acid with another polymerizable unsaturated organic compound containing two non-conjugated unsaturated carbon to carbon linkages.  Specified polycarboxylic acids are diglycollic, dilactic, dihydracrylic, oxy (acetic acid, a -propionic acid), oxy-di-b -acrylic acid, oxy (b -acrylic acid, a -propionic acid), methylene di-glycollic acid, oxy-di-hexahydro-p-benzoic acid, oxy-(acetic acid, b -propionic acid), oxy-di-p-benzoic acid and oxy-(p-toluic acid, 4-cyclohexene-1-carboxylic acid).  Unsaturated alcohols with which the polycarboxylic acids may be esterified are vinyl-type, e.g. vinyl alcohol, isopropenol, butene-1-ol-2, propene-1-ol-1, butene-1-ol-1, cyclohexene-1-ol-1 and cyclopentene-1-ol-1; b -unsaturated alcohols, e.g. propargyl alcohol, 2 - methyl - butyn - 3 - ol - 2, 2 - methyl - hexyn - 3 - ol - 2, octyn - 2 - ol - 1, nonyn - 2 - ol - 1, decyn - 3 - ol - 2 and 2 - methyl - nonyn - 3 - ol - 2; allyl-type alcohols, e.g. allyl, methallyl, ethallyl and chlorallyl alcohols, butene-1-ol-3, pentene-1-ol-3, hexene-1-ol-3, heptene-1-ol-3, octene-1-ol-3, the methyl and dimethyl butenes-1-ol-3, the methyl and dimethyl pentenes-1-ol-3, methyl hexene-1-ol-3, dimethyl hexene-1-ol-3, the methyl heptenes-1-ol-3, the phenyl, tolyl, xylyl and naphthyl butenes-1-ol-3 and propenes-1-ol-3, 4-chloro-butene-1-ol-3, pentadiene-1.4-ol-3, hexene-1-yn-5-ol-3, 2-methyl pentene-1-yn-4-ol-3, 2.5-dimethyl-hexadiene-1.5-ol-4; crotyl, tiglyl and cinnamyl alcohols, 3-chloro-butene-2-ol-1, hexadiene-2.4-ol-1, 2.5-ol-1, and 3.5-ol-2, butadiene-2.3-ol-1, 2-methyl-hexene-2-ol-1, 2-methyl-pentene-2-ol-1, 3.7-dimethyl-octadiene-2.7-ol-1, cyclopentene-2-ol-1 and cyclohexene-2-ol-1.  The carboxyl groups of the acid may be esterified by the same or different unsaturated acids, or by one or more unsaturated and one or more saturated alcohols or one or more groups may be unesterified.  A list of unsaturated esters of ethereal oxygen containing polycarboxylic acids is given, the preferred esters being diallyl diglycollate, allyl methallyl diglycollate and allyl vinyl diglycollate.  Specified other polymerizable compounds with which the unsaturated esters are polymerized are unsaturated polyesters of ethereal oxygen-containing polycarboxylic acids, unsaturated aliphatic polyesters of saturated poly-basic acids, unsaturated aliphatic polyethers of saturated polyhydric alcohols, unsaturated aliphatic polyesters of polyhydric alcohols, unsaturated aliphatic esters of unsaturated aliphatic acids and esters containing one or more polymerizable organic radicals and one or more inorganic radicals or elements, e.g. vinyl, allyl and methallyl esters of phosphoric acid and the ortho acids of silicon and boron.  The preferred compounds are diallyl and dimethallyl phthalate and allyl vinyl phthalate.  In carrying out the copolymerization, the polymerizable substances may be mixed prior to polymerization or partially polymerized before admixture or one or more monomers may be mixed with one or more partial polymers or copolymers before copolymerization.  The process may be carried out continuously or batchwise, under superatmospheric or reduced pressure in solution, dispersion or in bulk, and preferably under the influence of heat. Catalysts specified are peroxides, alkaline earth metal salts, salts of cadmium, mercury and lead, manganous salts, and normal salts of divalent and tetravalent nickel; lists are given.  Mixtures of two or more catalysts can be used.  As the copolymerization progresses, the fusibility and solubility of the product decreases, the fully-polymerized product being substantially infusible and insoluble.  Cast shapes are prepared by copolymerization in moulds or a partially polymerized syrup may be transferred to a mould and the process completed.  Laminates may be obtained (see Group VIII) by coating or impregnating with a syrup sheets of glass cloth, woven netted textile fabrics, felt or paper and subsequently rendering the resin infusible.  The copolymers may be modified by addition of plasticisers, stabilizers, lubricants, dyes, pigments, fillers, drying and semi-drying oils, natural resins, other synthetic resins or cellulose derivatives.  Non-reactive modifying agents may be added during the copolymerization.  Specification 572,858 is referred to.