Patent GB-973248-A (GB)
Title: Process for the preparation of copolymers of copolymers of alpha-beta-ethylenically unsaturated aldehydes
IPC: C08G2/00
Filed: 1961-12-19
Abstract: Alpha, beta-ethylenically unsaturated aldehydes are copolymerized with one or more other ethyleneically unsaturated compounds with the aid of a free radical yielding catalyst and in the presence of a sulphur dioxide or bisulphite derivative of a polymer of an alpha, beta-ethylenically unsaturated aldehyde. Many suitable catalysts are listed including hydrogen peroxide, alkali metal persalts, potassium permanganate and organic peroxides and hydroperoxides. The preferred derivatives are sulphur dioxide and bisulphite adducts with polyacroleins. Polymerization may be effected in aqueous media in the presence of cationic, anionic and non-ionic surface active agents, of which extensive lists are given.  The process may be effected batchwise or continuously, and the monomers may be added incrementally. Long lists of unsaturated aldehydes and comonomers are given and examples describe the preparation of copolymers of acrolein with (1 to 13) acrylonitrile, (14 to 17 and 20) 2-vinylpyridine, (18) N-vinyl-2-pyrrolidone, (19) methacrylamide, (21) 2-vinyl pyridine and the acetalization thereof with methanol, butanol, cyclohexanol and octanol, (22) 4-vinylpyridine, (23 to 30) ethyl acrylate and the acetalization thereof with methanol, ethanol, butanol and octanol, (31 and 32) maleic anhydride and the acetalization thereof with methanol, ethanol, butanol, and octanol, (33 and 34) maleic anhydride, (35) itaconic acid, (36 and 37) acrylic acid, (38 and 39) methacrylic acid and (40) the acetalization thereof with methanol, ethanol, butanol and octanol, (41 to 45) methyl vinyl ketone and the acetalization thereof with (49) methanol, ethanol, butanol, cyclohexanol and octanol, (46) methyl vinyl ketone, (47) butyl vinyl ketone or octyl vinyl-ketone, (48) methyl isopropenyl ketone, (50) isoprene and the acetalization thereof with methanol, (51, 53, 54 and 56) isoprene and the acetalization thereof with methanol, ethanol, butanol and octanol, (52, 55 and 57) isoprene and (58) butadiene, chloroprene, 2, 4-dimethyl pentadiene-1, 3 or cyclopentadiene.  The copolymers may be water solubilized by reaction with sulphur dioxide or bisulphites, cross-linked and vulcanized, acetalized and epoxidized.  They may be used for moulding, coating and laminating, making shaped articles such as films and fibres, treating textiles, paper and leather, or added to paper pulp.  Specification 901,897 is referred to.ALSO:Substrates may be coated with solutions and dispersions of copolymers of an alpha,beta-ethylenically unsaturated aldehyde with one or more other ethylenically unsaturated compound prepared in the presence of a free radical yielding catalyst and a sulphur dioxide or bisulphite derivative of a polymer of an alpha,beta-ethylenically unsaturated aldehyde.  In examples tin plates are coated by spreading or casting (7) with an aqueous solution of a sulphur dioxide solubilized copolymer of acrolein and acrylonitrile, and (53, 55 and 56) with aqueous latices of copolymers of acrolein and isoprene; and glass plates are coated by casting with (23) an aqueous solution of a sulphur dioxide solubilized copolymer of acrolein and ethyl acrylate. Specification 901,897 is referred to.ALSO:Textile materials and paper may be impregnated with copolymers of alpha, beta-ethylenically unsaturated aldehydes with one or more other ethylenically unsaturated compounds prepared in the presence of a free radical yielding catalyst and a sulphur dioxide or bisulphite derivative of a polymer of an alpha, beta-ethylenically unsaturated aldehyde.  Alternatively the copolymer may be added to paper pulp at the beater stage. Examples described the inpregnation of bleached Kraft paper with aqueous solutions of sulphur dioxide solubilized copolymers of acrolein with (1, 2, 3, 7 and 13 acrylonitrile; (23 to 28 and 30) ethyl acrylate; (31 and 33) maleic anhydride; (35) itaconic acid; (36) acrylic acid; (38) methacrylic acid; (41 and 43 to 46) methyl vinyl ketone; and (48) methyl isopropenyl ketone; and with aqueous latices of (50 to 57) acrolein-isoprene copolymers; the impregnation of bleached sulphite paper with aqueous solutions of sulphur dioxide solubilized copolymers of acrolein with (4 and 5) acrylonitrile; and (14, 15 and 22) 2-vinyl pyridine; the impregnation of cotton yarn with an aqueous solution of the sodium salt of a copolymer of (31) acrolein and maleic anhydride; and the addition to paper pulp of (10) an aqueous solution of a sulphur dioxide solubilized copolymer of acrolein and acrylonitrile.  The polymers are said to improve wet strength, water-resistance, abrasion resistance and fold endurance. Specification 901,897 is referred to.