Patent GB-1095932-A (GB)
Title: Dispersions of synthetic polymers
Inventor: DUELL ENID GILLIAN
IPC: C08G63/40
Filed: 1963-05-16
Abstract: A dispersion in an organic liquid of a polymer in which the links between the monomers or comers forming the polymeric chain involve an atom other than carbon is produced by precipitating the polymer in the form of particles dispersed in the organic liquid in which it is insoluble, there being present in the liquid a block or graft copolymer having one polymeric constituent which is solvated by the organic liquid and another polymeric constituent of a different degree of polarity which is non-solvated by the organic liquid and becomes associated with the precipitated polymer particles. The polymer dispersion may be made by polymerizing monomer or corners dissolved in the organic liquid, the polymer being precipitated in the form of dispersed particles as it is produced.  The polymer dispersion may be produced by polymerization of two comers, one together with the stabilizing block or graft copolymer, being dissolved in the organic liquid and the second comer dissolved in a liquid non-miscible with the first, the two being mixed to polymerize and the two liquids separated-such liquids are a non-polar liquid, e.g. an aliphatic or aromatic hydrocarbon and water.  The nature of the solvated polymeric constituent of the block or graft copolymer depends upon the nature of the organic liquid used, where it is an aliphatic hydrocarbon suitable solvatable polymeric constituents are polymers of long-chain esters of acrylic or methacrylic acid, polymeric vinyl esters of long-chain acids, polymeric vinyl alkyl ethers and polymers of ethylene, propylene, butadiene and isoprene, where it is an aromatic hydrocarbon suitable constituents are the above, shorter chain analogues, aromatic polyesters, alkyds, aromatic polyethers, aromatic polycarbonates and polymers of styrene and vinyl toluene, and where the liquid is polar, e.g. methyl or ethyl alcohol, the constituents include polymers of acrylic or methacrylic acid, carboxymethyl celluloses, polyethylene or polypropylene glycols, hydroxylated polymers, e.g. polyvinyl alcohol or polymers of glycol mono-methacrylates.  The non-solvated constituent of the stabilizing block or graft copolymer is one of three groups: (1) it is polar with respect to the organic liquid, (2) it is non-polar in this respect or (3) it is non-solvated due to its molecular structure.  Examples of (1) include esters of unsaturated acids with lower alcohols, esters of hydroxy-containing materials such as glycols, methanolamines, and glycidyl compounds with such unsaturated acids as maleic and itaconic esters or ethers of an unsaturated lower alcohols, e.g. vinyl alcohol, polymers of acrylic or methacrylic acids or their polar derivatives, e.g. acid chlorides; of (2) are polymers of styrene, vinyl toluene, divinyl benzene, di-isopropenyl benzene, isoprene, butadiene, isobutylene, and ethylene, of higher fatty esters of unsaturated acids, and higher fatty esters or ethers of unsaturated alcohols such as vinyl and allyl alcohol; and of (3) are polymers of vinyl chloride, vinylidine chloride and acrylonitrile. A suitable proportion of block or graft copolymer is from 1 to 25% of the disperse polymer.  In the Examples (1), (2) and (6) a block copolymer of lauryl methacrylate and methyl methacrylate/methacrylic acid in chloroform is refluxed with bis-(4-hydroxy-phenyl)-2,2-propane, terephthalydichloride, isophthaloyl dichloride and a mixture of ethyl acetate and methylene chloride, 2,6-butidine added and, after reflux a further amount of the polyester and organic liquid constituents. The polyester is precipitated with petroleum spirit as a stabilized fine particle size dispersion, (3) as above using isophthaloyl dichloride, n-hexane, bis - (4 - hydroxy - 3 - methylphenyl) - 2,2-propane and 2,6-butidine, (4) and (8) as above, using isophthaloyl dichloride, n-hexane, benzene, bis - (4 - hydroxy - 3 - methlphenyl)-2,2-propane and aqueous caustic soda, (5) as above, using isophthaloyl dichloride, benzene, hexamethylene diamine and 2,6-butidine, and (7) the block copolymer is of lauryl methacrylate and glycidyl methacrylate using isophthaloyl dichloride, n-hexane, bis-(4-hydroxy-3-methylphenyl) - 2,2 - propane and 2,6 - butidene. In Examples (9) and (10), the block copolymer is of lauryl methacrylate and methyl methacrylate/methacrylic acid and the monomer trioxane followed by trioxane/1:3-dioxolane, in (15) and (16) the block copolymer is of lauryl methacrylate and glycidyl methacrylate and the monomer formaldehyde while in (17) the block copolymer is of lauryl methacrylate and vinyl pyrrolidone and formaldehyde the monomer.  In Examples (11) glycidyl acetate is mixed with anisole and n-hexane and a 24% solution of a block copolymer of lauryl methacrylate and polyvinyl pyrrolidone, a solution of boron trifluoride etherate in anisole and n-hexane added and shaken when a fine particle size dispersion forms, (2) the glycidyl acetate of (11) is replaced by phenyl glycidyl ether, (13) a 25% solution of a block copolymer of lauryl methacrylate and methyl methacrylate in ethyl acetate are refluxed with phenyl glycidyl ether and n-hexane with aluminium triisobutyl and (14) the copolymer solution of (11) is refluxed with phenyl glycidyl ether, n-hexane and aluminium triisobutyl when a fine particle size dispersion begins to form and, on addition of further phenyl glycidyl ether a stable dispersion results.