Patent GB-1018448-A (GB)
Title: Heat curable acrylate rubbers
IPC: C08F2/22
Filed: 1964-08-26
Abstract: Heat-curable acrylate rubbers are prepared by polymerizing in aqueous emulsion (a) 50 to 99.8% by weight of b -methoxy- or b -ethoxyethyl acrylate; (b) 0 to 40% by weight of one or more rubber-producing alkyl or cyanoalkyl esters of acrylic or methacrylic acid, whose homopolymers have second order transition temperatures below 10 DEG C.; (c) 0 to 20% by weight of acrylonitrile; (d) 0.2 to 2.5% by weight of an N-alkoxy methyl-acrylamide or -methacrylamide wherein the alkoxy radical contains 1 to 8 carbon atoms; and (e) 0 to 3.8% by weight of a monoolefinically and terminally unsaturated amide containing at least one hydrogen on the amide nitrogen and wherein the olefinic unsaturation is alpha-beta to the carbonyl group of the amide and the remainder of the molecule consists only of hydrogen atoms or carbon and hydrogen atoms, the total of constituents (d) and (e) not exceeding 4% by weight.  Preferred monomers (b) have the formulae CH2 = CH-COOR, and CH2 = C(CH3)COOR2 wherein R1 is an alkyl group having 1 to 12 carbon atoms or a cyanoalkyl group having from 3 to 12 carbon atoms and R2 is an alkyl group having from 5 to 14 carbon atoms.  Preferred monomers (e) have the formula CH2 = CR3-CONH-R4, wherein R3 is hydrogen or an alkyl group having from 1 to 4 carbon atoms and R4 is hydrogen, an alkyl group having from 1 to 6 carbon atoms up to 6 carbon atoms.  The polymerization is generally effected in the presence of a free radical catalyst which may be water-soluble or monomer soluble.  Catalysts specified are potassium persulphate, hydrogen peroxide, benzoyl peroxide, tert-butyl peroxide, caprylyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, potassium perphosphate, diisopropyl percarbonate, azobisisobutyronitrile and the alkylborane-peroxide systems disclosed in Specification 865,651.  Redox catalyst systems are preferred, and actinic radiation, e.g. U.V. light and X-rays, may also be used. The emulsifier used may be anionic, cationic or nonionic (many examples are given).  The pH is generally between 4 and 7.5 and at low temperatures an antifreeze such as ethylene glycol or ethanol may be included in the polymerization mixture. The polymerized product is separated out by freeze coagulation or by agglomeration with a conventional coagulant, followed by filtration.  The rubber polymers are cured by heating, optionally in the presence of an acid catalyst such as butadiene sulfone, toluenesulphonic acid, morpholinium toluene sulphonate, salicylic acid, benzoic acid, stearic acid, acidic carbon black and acidic clay filler. The rubber is generally compounded with fillers, pigments, e.g. carbon black, lubricants and preferably, also, a rubber anti-oxidant (several specified), particularly an aromatic amine.ALSO:N-Alkoxymethyl-acrylamide or N-alkoxymethyl-methacrylamide, wherein the alkoxy group has from 1 to 8 carbon atoms, is prepared by reacting N-methylol-acrylamide or N-methylolmethacrylamide with an excess of an appropriate alkanol in the presence of an acid catalyst, e.g. p-toluenesulphonic acid, and a polymerization inhibitor, e.g. pyrogallol or hydroquinone. The etherification is desirably effected at reflux temperature with azeotropic removal of the water of reaction.