Patent GB-908222-A (GB)
Title: New copolymers and their manufacture and use
IPC: D06M15/267
Filed: 1959-06-05
Abstract: Copolymers are prepared from 28 to 50% vinylidene chloride; 4 to 10% of an acid <FORM:0908222/IV(a)/1> where R1 is H or a C1 to C4 alkyl group; a least 35% of an ester <FORM:0908222/IV(a)/2> where R1 is C1-4 alkyl and R2 is derived from an aliphatic, heterocyclic or alicyclic alcohol; and, optionally, up to 20% of a further monomer containing a single ethylenic double bond.  Mixtures of monomers of the specified formulae may be used. Numerous alcohols R2OH from which the acrylate or alkacrylate ester may be derived are specified including alkyl, alkenyl, alicyclic, heterocyclic, hydro-aromatic, terepene and alkoxy alcohols.  Optional further monomers specified are acrylonitrile, methacrylonitrile, styrene, vinyl chloride, chlorotrifluoroethylene, 1:1-difluoroethylene, acrylamide or methacrylamide which may have a C1-8 radical substituted on the N atom, vinyl C2-10 alkyl ethers, e.g. the butyl, 2-ethyl-butyl, and 2-ethyl-hexyl ethers, and vinyl esters of C2-4 carboxylic acids, e.g. vinyl acetate.  Polymerization may be in bulk, solution or, preferably, emulsion.  Emulsifying agents mentioned include fatty alcohol acid sulphates; sulphonated castor oil; alkyl, alkaryl or oxyalkyl sulphonates; sulpho-dicarboxylic acid esters, e.g. the sodium salt of sulphosuccinic acid dioctyl ester; polyglycol ethers of higher alcohols such as cetyl, oleyl, octadecyl and dodecyl alcohols, and of octyl phenol; and the sulphuric acid esters of octyl-phenol polyglycol ether.  Protective colloids which may be used with the emulsifiers are alginic acid esters, polyvinyl alcohols, partially hydrolysed polyvinyl esters, proteins, starches, and starch derivatives.  Catalysts mentioned are organic and inorganic peroxides or per-salts, e.g. peracetic acid, acetyl-, benzoyl-, benzoyl acetyl-, lauryl- or hydrogen peroxide, percarbonates, persulphates and perborates.  Two or more catalysts may be used and heat and/or actinic rays may be used instead of, or to augment, the catalyst. Regulators and activators may also be used, e.g. mercaptans; inorganic oxidizable oxygen-containing sulphur compounds such as sulphur dioxide, sodium bisulphate, sulphite, hydrosulphite or thiosulphate, and ammonium bisulphite (which may form redox systems with oxidizing catalysts); water-soluble aliphatic tertiary amines such as triethanolamine or diethyl-ethanolamine; multivalent heavy metal compounds in a lower valence state; and complex cyanides of one or more of iron, cobalt, molybdenum, mercury, copper, zinc and silver.  The polymerization may be effected in the absence of air or oxygen and the presence of inert gas, e.g. nitrogen or carbon dioxide. The polymerization may take place in two stages and one of the components may be partially prepolymerized.  The product dispersions are generally acidic thin liquids which may be neutralized and thickened with concentrated ammonia; pigments, fillers and plasticizer, e.g. dibutyl or dioctyl phthalate or sebacate esters may be incorporated therein.  Applications of copolymer compositions.  The compositions are used to produce elastic coatings on fabrics which may be made from cotton, linen, jute, hemp straw, polyesters, artificial or natural silk, regenerated cellulose or cellulose esters, wool, polyamides, polyacrylonitrile, glass, or mixtures thereof.  They are of particular application as binding agents in pigment dyeing and printing, but may also be spread on fabrics to produce water-resistant raincoat materials, imitation wax or oil cloth, oiled silk material, and rear dressings on corduroy or carpets.  They may also be used as a filling dressing for fabrics by the immersion method to produce bed ticking material, feel-modified wash-resistant cloths, water-resistant tent materials, and dry-cleaning-resistant lining materials. Other uses are as backing layers under polyvinyl chloride coatings, e.g. for artificial leather; as binding agents for colouring compositions applied to leather; and as a laminating adhesive for polyvinyl chloride foils or for paper/paper, paper/metal, or metal/metal laminates.  In an example bleached cotton is dyed with a composition of a vinylidene chloride/isobutylacrylate/acrylic acid copolymer emulsion, sodium alginate, diammonium phosphate and a copper phthalocyanine or an azo pigment.  Specification 908,223 is referred to.ALSO:Copolymers are prepared from 28 to 50% vinylidene chloride; 0.2 to 10% of an acid <FORM:0908222/IV (b)/1> , where R1 is H or a C1-4 alkyl group; at least 35% of an ester <FORM:0908222/IV (b)/2> , where R1 is C1-4 alkyl and R2 is derived from an aliphatic, alicyclic or heterocyclic alcohol; and, optionally, up to 20% of a further monomer containing a single ethylenic double bond.  Mixtures of monomers of the specified formulae may be used.  Numerous alcohols R2OH from which the acrylate or alkacrylate ester may be derived are specified including alkyl, alkenyl, alicyclic, heterocyclic, hydro-aromatic, terepene and alkoxy alcohols.  Optional further monomers specified are acrylonitrile, methacrylonitrile, styrene, vinyl chloride, chlorotrifluoroethylene, 1 : 1-difluoroethylene, acrylamide or methacrylamide which may have a C1-8 radical substituted on the N atom, vinyl C2-10 alkyl ethers, e.g. the butyl, 2-ethyl-butyl, and 2-ethyl-hexyl ethers, and vinyl esters of C2-4 carboxylic acids, e.g. vinyl acetate (see also Group IV(a)).  The product dispersions are generally acidic thin liquids which may be neutralised and thickened with concentrated ammonia; pigments, fillers and plasticizer, e.g. dibutyl or dioctyl phthalate or sebacate esters, may be incorporated therein.  The compositions are of particular application as binding agents in pigment dyeing and printing or as binding agents for colouring compositions applied to leather.  In an example bleached cotton is dyed with a composition of a vinylidene chloride/isobutylacrylate/acrylic acid copolymer emulsion, sodium alginate, diammonium phosphate and a copper phthalocyanine or an azo pigment.  Numerous examples are given which describe the treatment of cotton, polyglycol terephthalate fibre fabric and regenerated cellulose fibre fabrics with compositions containing various of the following ingredients:-Turkey red oil; triethanolamine; sodium alginate; ammonium sulphate; copper phthalocyanine or azo pigments; concentrated ammonia solution; ammonium nitrate; gas soot paste; a silicone anti-foam agent: ammonium chloride; and petroleum.  Specification 908,223 is referred to.