Patent GB-741654-A (GB)
Title: Improvements in or relating to the preparation of elastic polymeric compositions
IPC: C08F220/12
Filed: 1951-11-13
Abstract: Elastic polymeric compositions are made by heating together at 125 DEG  to 400 DEG  F. an oxide or hydroxide of a polyvalent metal with either (1) an interpolymer comprising an alkyl ester of acrylic acid and an olefinically unsaturated carboxylic acid, or (2) a polymer of an alkyl ester of acrylic acid having free and combined hydroxyl groups, obtained by partially hydrolysing a polymeric alkyl acrylate ester, or (3) mixtures of (1) and (2), there being between 0.01 and 0.30 chemical equivalents of carboxyl groups per 100 parts of polymeric material, the amount of metal oxide or hydroxide used being equivalent to at least one half of the combined carboxyl groups. Alkyl acrylates and olefinically unsaturated acids specified are methyl, chlormethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 3-hydroxybutyl, n-amyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isononyl, n-decyl, and lauryl acrylates, and linoleic, linolenic, oleic, undecylenic, acrylic-alpha - chloroacrylic, methacrylic, ethacrylic, alpha - isopropylidene acrylic, alpha - styryl acrylic, beta-vinyl acrylic, alpha-vinyl acrylic, beta-acryloxy acetic, beta-acryloxy propionic, polyhydracryloxy propionic, crotonic, alphabutyl crotonic, angelic, hydrosorbic, cinnamic, m- and p-chlorocinnamic, umbellic, beta-benzal acrylic, isocrotonic, sorbic alpha-methyl, ethyl, chloro, and bromo sorbic, beta-chloro sorbic, alpha-, beta-, or gamma-epsilon dimethyl sorbic, alpha-methyl-gamma benzal crotonic, beta - (2 - butenyl) - acrylic, 2,4 - pentadienoic, 2,4,6 - octatrienoic, 2,4,6,8 - decatrienoic, 1-carboxy - 1 - ethyl - 4 - phenyl butadiene-1,3,2,6 - dimethyl decatriene - (2,6,8) - oic - 10, alpha - beta - isopropylidene propionic, alpha-vinyl cinnamic, alpha - isopropenyl furfural acetic, alpha - isopropenyl - cinnamenyl acrylic, hydromuconic, glutaconic, maleic, fumaric, muconic, and 3-carboxy-pentadiene-(2,4)-oic-1 acids.  The polymers may also contain copolymerized therewith acrylonitrile, alpha - chloroacrylonitrile, N,N - dimethylacrylamide, acrylyl chloride, styrene, isobutylene, divinyl benzene, vinyl chloride, vinylidene chloride, vinyl acetate, propionate, and benzoate, diallyl maleate, chloroethyl vinyl ether, and vinyl pyridine.  Metal oxides and hydroxides specified are those of calcium, strontium, magnesium, barium, aluminium, cadmium, lead, copper, tin (including dibutyl tin oxide), titanium, cobalt, and iron.  The interpolymers of type (1) may be prepared by polymerization under acid conditions in solution, or, preferably, in an aqueous medium which may contain an emulsifier such as sodium lauryl sulphate, the sodium salts of sulphonated petroleum or paraffin oils, sodium dodecane - 1 - sulphonate and octadecane - 1-sulphonate, sodium isopropyl benzene sulphonand isobutyl naphthalene sulphonate, sodium dioctyl sulphosuccinate, sodium-N-octadecyl sulphosuccinate, dodecylamine hydrochloride, laurylamine hydrochloride, diethyl aminoethyloleylamide hydrochloride, trimethyl cetyl ammonium bromide, dodecyl trimethyl ammonium bromide, the diethylcyclohexylamine salt of cetyl sulphuric ester, polyether alcohols, fatty alkylol-amine condensates, the diglycol esters of lauric, oleic, and stearic acids, and gelatin. Polymerization may be assisted by actinic light and catalysts such as hydrogen peroxide, benzoyl peroxide, caprylyl peroxide, pelargonyl peroxide, cumene hydroperoxide, tert.-butyl hydroperoxide, 1-hydroxycyclohexyl hydroperoxide, tert.-butyl diperphthalate, tert.-butyl perbenzoate, and sodium, ammonium, and potassium persulphates; also present may be buffers, mercaptan modifiers, and fillers such as carbon black.  The content of carboxyl groups in the interpolymer may be controlled by the gradual addition of the polymerizable acid to the reaction mixture.  The polymers of type (2) may be prepared in bulk, solution, or, preferably in aqueous emulsion employing a catalyst such as potassium persulphate and an emulsifier such as the sodium salt of n-octadecyl-N-1,2-dicarboxyethyl sulphosuccinamate and a mixture of fatty acid soap flakes and the sodium salt of polymerized alkyl naphthalene sulphonic acids. Hydrolysis of these polymers may be carried out in solution in a solvent such as benzene, methyl ethyl ketone, acetone, and mixtures of benzene and ethyl alcohol, in aqueous suspension, or by mastication of the solid polymer. Hydrolysis may also be carried out during polymerization by including a hydrolysing agent in the reaction mixture. Hydrolysing agents specified are hydrochloric, hydrobromic, hydriodic, sulphuric, nitric, phosphoric, dichloracetic, maleic, and oxalic acids, sodium potassium, and ammonium hydroxides, cetyl dimethylammonium hydroxide, cetyl dimethylbenzylammonium bromide, ethylamine, diethylamine, diethylbenzylamine, methyldiethylamine, piperdine, and sodium carbonate, bicarbonate, silicate, metasilicate, oxalate, and lactate.  The use is also exemplified of sulphur, carbon black, stearic acid, and triethyltrimethylene triamine in conjunction with zinc oxide in a curing recipe.  The polymeric metallo-carboxylates may be used in the manufacture of films, in coating applications, and for electrical insulation.