Patent GB-1123425-A (GB)
Title: Copolymer solutions and method for production thereof
IPC: C08F8/00
Filed: 1965-08-10
Abstract: Curable copolymer solutions are prepared by copolymerizing 1 to 30% by weight of an amide group - containing ethylenically unsaturated monomer or an ethylenically unsaturated melamine derivative containing free amino groups, 0 to 30% by weight of an a ,b -ethylenically unsaturated carboxylic acid or anhydride or salt thereof, and 40 to 99% by weight of at least one other ethylenically unsaturated compound (the percentages of the monomers totalling 100%); and reacting the copolymer obtained with 0.5 to 3.0 moles of formaldehyde per molar equivalent of amide or amino groups in the copolymer in the presence of a base and in solvent free from alcohols or containing less than 6 moles of alcohol per molar equivalent of amide or amino groups in the copolymer, under such conditions that at least about 50% of the amide or amino groups of the copolymer have a hydrogen atom replaced by the group -CH2OH; and incorporating an acidic curing catalyst in the composition by using an a ,b -ethylenically unsaturated carboxylic acid or anhydride or salt thereof in the copolymerization and/or adding an acidic substance to the solution during or after the methylolation reaction, the equivalent ratio of the base to the acidic curing catalyst being maintained at a value greater than 1. The copolymerization can be effected in bulk or emulsion but is preferably carried out in solution. Suitable amide monomers include acrylamide, methacrylamide, itaconic acid diamide, fumaric acid diamide and maleic acid monoamide; other suitable methylolatable monomers are those in which a hydrogen atom of melamine or urea is substituted by an ethylenically unsaturated group.  The unsaturated acidic monomer may be acrylic, methacrylic, crotonic, angelic, tiglic, maleic or fumaric acid or maleic anhydride; water-soluble polymers can be obtained by converting the acidic units into salt from, e.g. with ammonia or an amine. The other essential monomer component of the copolymer may be selected from C1-C12-alkyl acrylates or methacrylates, nitriles of acrylic, methacrylic or a -chloroacrylic acid, styrene and derivatives, vinyl carboxylate esters, dienes, allyl chloride, allyl acetate or propionate, allyl or methallyl alcohol, hydroxyalkyl esters of acrylic, methacrylic or fumaric acid, and alkyl vinyl or alkyl isopropenyl ketones. Suitable polymerization catalysts include inorganic peroxides, e.g. hydrogen peroxide, organic peroxides, e.g. benzoyl peroxide, methyl ethyl ketone peroxide, methyl hydroperoxide, di-t-butyl peroxide and peracetic acid, and azobis-isobutyronitrile. A regulator such as an alkyl mercaptan may additionally be used. The base used in the methylolation reaction may be an aliphatic amine, ammonia or ammonium hydroxide.  Where a separate acidic substance is added, this may be phthalic anhydride, an acid such as oxalic, malonic, succinic, adipic or phthalic acid, or an acidic polymer or resin. The copolymer solutions may be admixed with pigments, e.g. titanium dioxide, inert fillers, natural or synthetic resins, e.g. a melamine resin, cellulose derivatives, or plasticizers, e.g. dioctyl phthalate.  The solutions are suitable for forming coatings which can be cured on baking. In examples, the copolymers are derived from (1) and (6) acrylamide, maleic anhydride, styrene and n-butyl acrylate; (2) acrylamide, maleic anhydride, methyl methacrylate and ethyl acrylate; (3) acrylamide, acrylic acid, methyl methacrylate and n-butyl acrylate; (4) acrylamide, acrylic acid, styrene and n-butyl acrylate; (5) acrylamide, styrene and n-butyl acrylate; (7) acrylamide, b -hydroxy ethyl methacrylate, maleic anhydride, styrene and ethyl acrylate; (8) acrylamide, b -hydroxy ethyl methacrylate, styrene, methyl methacrylate, ethyl acrylate and acrylic acid.  A solution of the copolymer of (8) is mixed with a melamine resin solution to give a stoving lacquer.ALSO:In Examples iron plate, which may be phosphate-treated, or tin plate is spray-coated with solutions of methylolated amide copolymers in organic solvents, and the coatings obtained cured by baking.  In some cases, the copolymer solutions include dioctyl phthalate, titanium dioxide or a melamine resin.  The parent copolymers are derived from (1) and (6) acrylamide, maleic anhydride, styrene and n-butyl acrylate, (2) acrylamide, maleic anhydride, methyl methacrylate and ethyl acrylate, (3) acrylamide, acrylic acid, methyl methacrylate and n-butyl acrylate, (4) acrylamide, acrylic acid, styrene and n-butyl acrylate, (5) acrylamide, styrene and n-butyl acrylate, (7) acrylamide, b -hydroxy ethyl methacrylate, maleic anhydride, styrene and ethyl acrylate, (8) acrylamide, b -hydroxy ethyl methacrylate, styrene, methyl methacrylate, ethyl acrylate and acrylic acid.  The solutions also include a base and an acidic component (the latter being an acidic monomer component of the copolymer or phthalic anhydride), with the base being present in an excess, in relation to the amount of acidic component.