Patent GB-983205-A (GB)
Title: Process for the preparation of stable polymer emulsions from n-methylol substituted amides of ª-ª-ethylenically unsaturated monocarboxylic or dicarboxylic acids or theethers of such n-methylolamides
IPC: C08F20/62
Filed: 1963-07-04
Abstract: Stable copolymers of N-methylol-substituted amides of a ,b -ethylenically unsaturated monoor di-carboxylic acids, or of ethers of these methylolamides are prepared by polymerizing the monomers together with comonomers containing -CH=CH-; CH2=CH- or CH2= C= groups, but which are free from N-methylol groups and alkaline earth metal atoms, in an aqueous medium containing emulsifiers in the presence of 0.25 to 10% by weight of a water-soluble alkaline earth metal salt of an a -b -ethylenically unsaturated monocarboxylic acid, based on the total weight of monomers including the alkaline earth metal salt. In the copolymers, the amount of N-methylol-substituted amide or ether thereof is 0.25 to 3.0% by weight and the amount of comonomer or comonomers as above 99.5 to 60% by weight.  Long lists of monomers are given.  The polymers of the invention may be used to coat and impregnate various substrates and they may be mixed with silicon dioxide.  In the examples copolymers are prepared from the following monomers:-(1) calcium acrylate, N-methylolacrylamide, n-butyl acrylate and vinylidene chloride; (2) calcium acrylate, N-methylolacrylamide, methyl acrylate and vinylidene chloride; (3) calcium acrylate, N-methylolmethacrylamide, n-butyl-acrylate and vinylidene chloride; (4) calcium acrylate, N-methylolacrylamide methyl ether, n-butyl acrylate and vinylidene chloride; (5) calcium acrylate, N-methylolacrylamide allyl ether, n-butyl acrylate and vinylidene chloride; (6) calcium acrylate, N - methylolacrylamide and vinyl acetate; (7) calcium acrylate, N-methylolacrylamide and styrene; (8) calcium crotonate, N-methylolacrylamide, vinylidene chloride and vinyl acetate; (9) magnesium acrylate, N - methylolacrylamide, vinylidene chloride and lauryl acrylate; (10) barium acrylate, N-methylolacrylamide, vinyl acetate and N-tertiary butyl acrylamide; (11) calcium acrylate, N-methylolacrylamide, 2-ethylhexyl-acrylate, N:N-di-ethylaminopropyl acrylamide and vinylidene chloride; (12) calcium acrylate, N:N-diethylaminopropyl acrylamide quaternated with chloracetamide, vinylidene chloride and N-methylolacrylamide; (13) calcium acrylate, N-methylolacrylamide, acrylonitrile and 2-ethylhexylacrylate; (14) strontium acrylate, N-methylolacrylamide, vinyl acetate and vinylidene chloride and (15) calcium acrylate, N-methylolacrylamide methyl ether and vinyl acetate.ALSO:Leather may be dressed with a copolymer emulsion formed by polymerizing an N-methylol-substituted amide of an a ,b -ethylenically unsaturated mono- or di-carboxylic acid or an ether of such a methylol amide with a comonomer or comonomers containing -CH = CH - ; CH2 = CH - or CH2 = C = groups, but free from N-methylol groups and alkaline earth metal atoms, in an aqueous medium containing emulsifiers in the presence of 0.25-10% by weight of a water-soluble alkaline earth metal salt of an a ,b -ethylenically unsaturated monocarboxylic acid, based on the total weight of monomers, to produce an unbreakable dressing on the leather which is fast to acetone and hot ironing.ALSO:Fabrics, paper, cardboard, foils or webs of plastic materials, e.g. of polyethylene, polyesters or polyamides and fabric-like materials woven from polyamide, polyacrylonitrile or polyester fibres are coated with a copolymer emulsion formed by polymerizing an N-methylol substituted amide of an a ,b -ethylenically unsaturated mono- or di-carboxylic acid or an ether of such a methylolamide with a comonomer or comonomers containing -CH=CH-; CH2=CH- or CH2=C= groups, but free from N-methylol groups and alkaline earth metal atoms, in an aqueous medium containing emulsifiers, in the presence of 0,25-10% by weight, based on the total weight of monomers, of a water-soluble alkaline earth metal salt of an a ,b -ethylenically unsaturated monocarboxylic acid.  In the examples: (1) A nylon fabric is coated with an emulsion formed from a copolymer of calcium acrylate, N-methylolacrylamide and n-butyl acrylate to which is added before polymerization is complete a previously prepared emulsion of a copolymer of vinylidene chloride and N-methylol acrylamide, and the mixture is further polymerized. Silicon dioxide may be present.  The nylon fabric is coated with this emulsion twice, with intermediate drying, and then hardened for 5 minutes at 140  DEG C.; (2) A fabric is coated with an emulsion formed from a copolymer of calcium acrylate, N-methylol-acrylamide, acrylonitrile and 2-ethylhexyl acrylate, and the coated fabric is then coated with foamed polyurethane and the composite fabric is then cured; (3) Paper consisting of 80% of bleached sulphite cellulose, 20% of birch cellulose; 15% of kaolin, 0,5% resin size and 2% of aluminium sulphate is coated three times on one side with an emulsion formed from a copolymer of calcium acrylate, N-methylolacrylamide, methyl acrylate and vinylidene chloride; and (4) A cotton fabric is coated with an emulsion of a copolymer of vinyl acetate, N-methylolacrylamide methyl ether and calcium acrylate.ALSO:Cotton and nylon tricot fabrics may be stiffened by immersion in a copolymer emulsion formed by polymerizing an N-methylol-substituted amide of an a , b -ethylenically unsaturated mono-or di-carboxylic acid or an ether of such a methylolamide with a comonomer or comonomers containing -CH = CH-; CH2 = CH- or CH2 = C = groups, but free from N-methylol groups and alkaline earth metal atoms, in an aqueous medium containing emulsifiers, in the presence of 0.25 to 10% by weight of a water-soluble alkaline earth metal salt of an a , b -ethylenically unsaturated monocarboxylic acid, based on the total weight of monomers.  Fabrics woven from polyamide, polyacrylonitrile or polyester fibres may be similarly treated with the copolymer emulsion.  In the case of textiles such as cotton, the copolymer emulsions are preferably used in admixture with urea resins or other aminoplasts.  Textiles so treated are fast to washing, are abrasion resistant, have a soft handle, are fast to dry-cleaning agents and have a high tear strength and crease angle.  In an example a cotton fabric and a nylon tricot fabric are immersed in an emulsion of a copolymer of N-methylolacrylamide, vinyl acetate, vinylidene chloride and calcium acrylate, padded and dried on a stenter at 80 DEG C. and then cured for 4 1/2 minutes at 160 DEG C.  In another example a cotton fabric is immersed in an aqueous emulsion of a copolymer of vinyl acetate, N-methylolacrylamide methyl ether and calcium acrylate.