Patent GB-1092724-A (GB)
Title: Polymers and their production
IPC: C08F20/54
Filed: 1965-03-04
Abstract: Copolymers comprise a major proportion of at least one ester of a terminally unsaturated monohydric alcohol and a saturated aliphatic monocarboxylic acid having up to 8 carbon atoms and minor proportions of an ethylenically unsaturated carboxylic acid, anhydride or amide and at least one alkyl ester of an a ,b -ethylenically unsaturated monocarboxylic acid, said alkyl ester having up to 8 carbon atoms in the alkyl group and forming 25-75% of its combined weight with said acid, anhydride or amide. Specified monomers are vinyl and allyl acetates, propionates, butyrates, isobutyrates, valerates and caproates; acrylic, methacrylic, crotonic, angelic, tiglic, atropic, cinnamic, 2 - hexenoic, 2,4 - pentadienoic, itaconic, fumaric, maleic, citraconic, mesaconic and aconitic acids, halogen-substitution derivatives thereof, maleic and citraconic anhydrides, and amides and N-alkylol amides of the above acids; and C1- 8 alkyl esters of acrylic, methacrylic, pentylacrylic and phenylacrylic acids.  Polymerization may be effected in the presence of conventional free radical catalysts, e.g. peroxy compounds and redox systems, in aqueous emulsion or suspension in the presence of conventional emulsifiers and suspending agents, and buffers. Polymerization ingredients may be added portionwise during the reaction.  The products may be used in coating compositions and as binders for non-woven fabrics.  They may be mixed with plasticizers, e.g. ester, alkyd resin, chlorinated diphenyl and substituted biphenyl plasticizers; pigments and fillers. Examples describe the copolymerization in aqueous emulsion of (1 and 4) vinyl acetate, ethyl acrylate and N-methylol acrylamide, (2) vinyl acetate, methyl methacrylate and N-methylolacrylamide and (4) vinyl acetate and ethyl acrylate with acrylic acid and N-methylolacrylamide or with maleic acid.  The emulsion of Example (1) is mixed with an aqueous paste of calcium carbonate, iron oxides and potassium tripolyphosphate.ALSO:Non-woven fabrics of natural and synthetic fibres may be prepared using as adhesive binder a copolymer of a major proportion of at least one ester of a terminally unsaturated monohydric alcohol and a saturated aliphatic monocarboxylic acid having up to 8 carbon atoms and minor proportions of an ethylenically unsaturated carboxylic acid, anhydride or amide and at least one alkyl ester of an a ,b -ethylenically unsaturated monocarboxylic acid, said alkyl ester having up to 8 carbon atoms in the alkyl group and forming 25 to 75 per cent of the combined weight with said acid, anhydride or amide.  Specified fibres are of cotton, wool, flax, silk, nylon, polyester, polyacrylonitrile, cellulose acetate and rayon.  The copolymer is preferably applied as an aqueous dispersion thickened, e.g. to a viscosity of 300 to 3000 cps, with an agent such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, gum arabic, starch, sodium alginate, glue and gelatin. The polymers may be derived from vinyl and allyl acetates, propionates, butyrates, isobutyrates, valerates and caproates; acrylic, methacrylic, crotonic, angelic, tiglic, atropic, dinnamic, 2-hexenoic, 2,4-pentadionoic, itaconic, fumaric, maleic, citraconic, mesaconic and aconitic acids, halogen-substituted derivatives thereof, maleic and citraconic anhydrides, and amides and N-methylolamides of the above acids, and alkyl esters of acrylic, methacrylic, pentylacrylic and phenylacrylic acids.  In Example (1) an non-woven fabric of rayon fibres containing about 10 per cent of cured binder is prepared using as binder an aqueous dispersion of a copolymer of vinyl acetate, N-methylolacrylamide and ethyl acrylate.ALSO:Substrates may be coated with compositions particularly aqueous dispersions, comprising copolymers of a major proportion of at least one ester of a terminally unsaturated monohydric alcohol and a saturated aliphatic monocarboxylic acid having up to 8 carbon atoms and minor proportions of an ethylenically unsaturated carboxylic acid, anhydride or amide and at least one alkyl ester of an a ,b -ethylenically unsaturated monocarboxylic acid, said alkyl ester having up to 8 carbon atoms in the alkyl group and forming 25 to 75 per cent of its combined weight with said acid, anhydride or amide. The coatings are generally thermosetting.  The compositions may comprise plasticisers, fillers, pigments and stabilisers.  The polymers may be derived from vinyl and allyl acetates, propionates, butyrates, isobutyrates, valerates and cuproates; acrylic, methacrylic, crotonic, angelic, tiglic, atropic, cinnamic, 2-hexenoic, 2,4-pentadienoic, itaconic, fumaric, maleic, citraconic, mesaconic and aconitic acids, halogen-substituted derivatives thereof, maleic and citraconic anhydrides, and amides and N-methylolamides of the above acids; and alkyl esters of acrylic, methacrylic, pentylacrylic and phenyl acrylic acids.  Examples describe (4c) the coating of paper stock with an aqueous emulsion of a copolymer of vinyl acetate, maleic acid and ethyl acrylate, and (6) the coating of asbestos cement tiles with aqueous emulsions comprising a copolymer of vinyl acetate, N-methylolacrylamide and ethyl acrylate, octylphenol/ethylene oxide condensate, calcium carbonate, iron oxides, potassium tripolyphosphate, wetting and stabilising agents, and oxalic acid as curing catalyst.