Patent GB-964284-A (GB)
Title: A process for the preparation of copolymers of alpha, beta-ethylenically unsaturated aldehydes with a free radical yielding catalyst
IPC: C08F246/00
Filed: 1961-12-21
Abstract: Terpolymers may be prepared by reacting an a ,b -ethylenically unsaturated aldehyde, butadiene and/or isoprene and as third component an a ,b -ethylenically unsaturated compound essentially free from aldehydic groups, in the presence of a free radical-yielding catalyst and a sulphur dioxide or bisulphite adduct of a polymer of an a ,b -ethylenically unsaturated aldehyde as reducing agent.  Specified aldehydes are acrolein, methacrolein, a -ethylacrolein, a -butylacrolein, a -chloroacrolein, b -phenylacrolein, a -decylacrolein and a -cyclohexylacrolein. Specified third components are styrene, a -methylstyrene, chlorostyrene, allyl benzene, propylene, butylene, ethylene, octylene, cyclohexene, methylcyclohexene, methyl acrylate, methyl methacrylate, ethyl acrylate, vinyl acetate, vinyl butyrate, vinyl benzoate, allyl benzoate, allyl alcohol, methallyl alcohol, butenol, methacrylic acid, acrylic acid, crotonic acid, pentenoic acid, acrylonitrile, methacrylonitrile, vinyl and allyl ethers, vinyl ketones, vinyl and vinylidene halides, vinyl pyridine and vinyl pyrrolidone. Specified catalysts include hydrogen peroxide, organic peroxides and hydroperoxides, peresters, persalts and potassium permanganate, many suitable examples being listed.  The preferred reducing agents are adducts of polyacroleins, though others such as sulphinic acids and their salts, oxysulphones, sulphoxylates, amino-sulphones and thioethers may be used. Polymerisation may be effected in an aqueous medium in the presence of anionic, cationic or non-ionic surface active agents of which many examples are listed. The resulting latices may be used for coating wood, metal, cement and plaster or for impregnating leather, textiles and paper. The polymers may be reacted with sulphur dioxide or bisulphites to form adducts, and with alcohols to form organic solvent soluble derivatives which may be cured with phenolics to form infusible plastics. The terpolymers may be vulcanised with sulphur to give elastomers. Examples describe the preparation in the presence of water, dioctyl sulphosuccinate, polyacrolein sulphur dioxide adduct and tertiary butyl hydroperoxide of terpolymers of (I to VIII and XVII) acrolein, styrene and isoprene; and (XI) acrolein, styrene and butadiene; and in the presence of water, polyacrolein sulphur dioxide adduct and tertiary butyl hydroperoxide of terpolymers of (IX, X and XIII-XV) acrolein, allyl alcohol and isoprene; (XII) acrolein, acrylonitrile and isoprene; and (XVI) acrolein, allyl alcohol and butadiene. In Example XVIII the products of Examples I to IV are vulcanised by heating with sulphur.ALSO:Substrates, e.g. of wood, metal, cement and plaster, may be coated with aqueous dispersions of terpolymers of an a ,b -ethylenically unsaturated aldehyde, butadiene and/or isoprene and as third component an a ,b -ethylenically unsaturated compound essentially free from aldehydic groups, prepared in the presence of a free radical catalyst and a sulphur dioxide or bisulphite adduct of a polymer of an a ,b -ethylenically unsaturated aldehyde.  The preferred aldehyde is acrolein.  The preferred third components are styrene, allyl alcohol and acrylonitrile, but many others are listed including styrene derivatives, olefins and cycloolefins, acrylic and methacrylic acids and esters, unsaturated alcohols and esters thereof, unsaturated ethers and ketones, vinyl and vinylidene halides and vinyl heterocyclic compounds.  Examples describe the coating of tinplate panels with aqueous latices of terpolymers of (I-IV and VII) acrolein, styrene and isoprene; and (IX, X and XIII) acrolein, allyl alcohol and isoprene, to give, on drying, tough flexible films.ALSO:The strength and water resistance of paper may be increased by the use of latices of terpolymers of an a ,b -ethylenically unsaturated aldehyde, butadiene and/or isoprene and as third component an a ,b -ethylenically unsaturated compound essentially free from aldehydic groups, prepared in the presence of a free radical catalyst and a sulphur dioxide or bisulphite adduct of a polymer of an a ,b -ethylenically unsaturated aldehyde.  The latices may be added to the paper pulp, e.g. during the beater stage, or used to impregnate finished papers by spraying, roller application, dipping or padding.  The paper may be prepared from wood, cotton, linen, hemp, jute, mulberry, straw, bamboo, cane or agone fibres by sulphate, soda or sulphite processes, and may be coloured or white. The preferred aldehyde is acrolein.  The preferred third components are styrene, allyl alcohol and acrylonitrile, but many others are listed including styrene derivatives, olefins and cycloolefins, acrylic and methacrylic esters and acids, unsaturated alcohols and esters thereof, unsaturated ethers and ketones, vinyl and vinylidene halides and vinyl heterocyclic compounds.  In Examples I and III bleached Kraft paper is impregnated by padding with latices of terpolymers of acrolein, styrene and isoprene to give papers with improved strength and water repellency.  The papers are suitable for towels, maps, filing cards, construction paper, and wrapping papers and containers, e.g. for food.