Patent GB-762010-A (GB)
Title: Improvements in or relating to polymeric compositions and methods for their preparation
IPC: D06M15/39
Filed: 1954-02-17
Abstract: A synthetic resin composition comprises at least two oppositely charged ionic polyelectrolyte polymers united through a plurality of cross-linkages and at least 10 per cent, preferably from 50 to 90 per cent, of the blend, of a water-insoluble, water-dispersible, non-electrolyte film-forming polymer.  The polyanionic polymer may be polyacrylic, polymethacrylic, polyethacrylic or poly-alpha-chloroacrylic acid, a copolymer of methacrylic acid with methyl methacrylate, vinyl acetate, styrene or 1,3-butadiene, an acrylic acid-acrylonitrile copolymer, a hydrolysed copolymer of maleic anhydride with ethylene, propylene, isobutylene, styrene, methyl vinyl ether, vinyl acetate, vinyl chloride or methyl acrylate, polyvinyl sulphonic acid, polyvinylbenzenesulphonic acid, the polymeric acids of Specification 759,863 obtained by reacting phosphoric acid with polymers containing epoxy groups, lignic acid, alginic acid or carboxymethylcellulose.  The polyanionic polymers are usually neutralized with a base such as ammonia, sodium hydroxide or potassium hydroxide prior to reacting wit the polycationic polyelectrolyte in order to increase their solubility in water. The polycationic polyelectrolyte may be polyvinylamine, a hydrogenated 1,3-butadieneacrylonitrile or 1,3-butadiene-methacrylonitrile copolymer, a polyamine obtained by reductive amination of an ethylene-carbon monoxide copolymer, polyethyleneimine, poly-N-methylethyleneimine, a polyvinyl pyridine or polyvinyl quinoline, polymerized beta-dimethylaminoethyl acrylate, beta-di-n-butylaminoethyl methacrylate, triethanolamine monomethacrylate, beta - dicyclohexylaminoethyl methacrylate, 1 - (beta - methacrylyloxyethyl)piperidine, 4 - (beta - methacrylyloxyethyl)morpholine, or a quaternary ammonium salt thereof, a linear polyamide containing intralinear tertiary amino groups, an animated product obtained by catalytically hydrogenating a resin having ketone groups in the presence of ammonia or amines, the reaction product of a vinyl ketone polymer with ammonia or a primary amine, a linear polyamine resulting from the condensation of a diamine with evolution of ammonia, a polymeric amine resulting from the reaction of ammonia or an amine with a polymer containing epoxy groups, as described in Specification 722,258, or a polymeric quaternary ammonium salt obtained by reacting a polymer containing epoxy groups with tertiary amines and water or acids.  The polycationic polymers are preferably used in more water-soluble form such as their salts with acetic, hydrochloric or sulphuric acid or, in the case of polymers containing tertiary amino groups, as quaternary ammonium salts.  The non-electrolyte film-forming polymer may be polyhexamethyleneadipamide, polyhexamethylenesebacamide, polydecamethyleneadipamide, polyethylene terephthalate, a polyesteramide disclosed in Specification 561,108, [Group IV], a polymer or copolymer of vinyl fluoride, chloride, bromide or iodide, vinylidene fluoride or chloride, 1,1 - dichloro - 2,2 - difluoroethylene, tetrafluoroethylene, trifluorochloroethylene, ethylene, propylene, isobutylene, 1,3 - butadiene, isoprene, vinylcyclohexane, styrene, vinyl naphthalene, 2-phenyl-1,3-butadiene, 2-fluoro-, 2-chloro-, or 2-iodo-1,3-butadiene, 2,3 - dichloro - 1,3 - butadiene, ethyl acrylate, methyl, butyl, methoxymethyl or chloroethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl formate, acetate, chloroacetate, butyrate or laurate, acrolein, methacrolein, methyl vinyl ketone, N-vinyl phthalimide or succinimide, vinyl ethyl ether, vinyl isobutyl ether, 2-phenoxy - 1,3 - butadiene, N - vinyl caprolactam or butyrolactam, or a copolymer of dimethyl or diethyl fumarate or maleate.  The composition may be prepared by mixing an aqueous dispersion of the non-electrolyte filmforming polymer with an aqueous solution of at least one polyelectrolyte polymer having a plurality of ionic charges of the same sign as that of the surface charge of the particles of the dispersed non-electrolyte polymer, and adding to the mixture an aqueous solution of at least one polyelectrolyte polymer having a plurality of ionic charges of the opposite sign, thereby ionically cross-linking the polyelectrolate polymers and coprecipitating therewith the non-electrolyte polymer as a water-insoluble, homogeneous polymer blend.  The ionically cross-linked electrolytes may also be crosslinked by methods such as (a) by using a polyelectrolyte containing an epoxy group which will open and cross-link on heating; (b) by reacting the ionically cross-linked polymer with a polyfunctional reagent such as an alkylene dihalide, an aralkylene dihalide, ethylene oxide, propylene oxide, formaldehyde, dimethylolurea, dimethylolmelamine, a dimethyloluron, a dimercaptan or a glycol; or (c) by reacting an ionically cross-linked polymer containing hydroxy groups with a diisocyanate, diisothiocyantae or dicarboxylic acid chloride. The properties of the compositions may be varied by an after treatment with salts of polyvalent cations or of polyvalent anions, such as barium calcium, magnesium or aluminium chloride, tin tetrachloride, cadmium acetate, lead nitrate, mercuric or zinc chloride, nickel diacetate, aluminium potassium sulphate, basic chromium sulphate, sodium silicate, sodium cobaltinitrite or sodium chloroplatinate. Synthetic rubber compositions may be milled with curing agents, and the compositions may contain other materials such as carbon black, dibutyl phthalate, stearic acid and dioctyl phthalate.  The compositions may be used for the production of films or for the impregnation of fabrics.