Patent GB-815745-A (GB)
Title: Improvements in quaternary ammonium compounds and preparation thereof
IPC: C08F16/28
Filed: 1955-09-16
Abstract: Relates to quaternary ammonium homopolymers and copolymers of monoethylenically unsaturated monomers comprising at least 20 mol. per cent of monomeric units having the general formula <FORM:0815745/IV (a)/1> in which A is ethylene, trimethylene or -CHR-CH2-, where R may be any alkyl or alkenyl group having from 1 to 16 carbon atoms, R1 and R2 may be (1) separate groups selected individually from the group consisting of alkyl or alkenyl groups having 1 to 12 carbon atoms, hydroxyalkyl, alkoxyalkyl or (polyalkoxy)-alkyl groups having 2 to 12 carbon atoms or (2) R1 and R2 may together represent the morpholino residue: (C2H4)2: O, the pyrrolidino residue, -C4H8-, the piperidino residue, -C5H10-, and an N-alkylpiperazino residue: (C2H4)2: NR0, where R0 is an alkyl group of 1 to 18 carbon atoms, such as methyl, ethyl, isopropyl, R3 is selected from saturated and ethylenically unsaturated aliphatic hydrocarbon groups having 1 to 18 carbon atoms (polyalkoxy) alkyl, alkoxyalkyl, or hydroxyalkyl groups having 2 to 18 carbon atoms, an aralkyl or substituted aralkyl group having 7 to 24 carbon atoms, or a phenoxyalkyl group having 7 to 24 carbon atoms, at least one of R1, R2 and R3 has at least 12 carbon atoms, and X is OH or a negative, salt-forming atom or radical, preferably of monovalent character, such as halide, sulphate and sulphonate.  The polymers may be prepared by polymerizing one or more amines of formula CH2 = CHOANR1R2 and quaternizing the product or by quaternizing first and then polymerizing.  The amine may be dimethylaminoethyl, dibutylaminoethyl, didodecylaminoethyl, 2-dicyclohexylamino-1-benzyl - ethyl, 2 - morpholinoethyl or 2 - (di(butoxyethyl) amino)-ethyl vinyl ether, and the quaternizing agent may be methyl, ethyl, benzyl, allyl, dodecylallyl, dodecenyl, octylbenzyl, or chlorobenzyl chloride, chloromethylated naphthalene, thiophene or furane, phenoxyethyl bromide, methyl iodide, dimethyl sulphate, sulphite or phosphite, and ethylene, propylene, butylene or styrene oxide. Monomers which may be copolymerized with one or more of the above amines include styrene, isopropenyl toluene, dialkyl styrenes, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, acrylamide, methacrylamide, ethacrylamide, N - methylol acrylamide, N - monomethyl, - ethyl, - propyl, - butyl, N - dimethyl, -ethyl, -propyl, -butyl and N-monophenyl and -diphenyl acrylamides and methacrylamides, vinyl acetate, propionate, butyrate, isobutyrate and valerate, acrylic, methacrylic, ethacrylic and phenylacrylic acid, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert-butyl, amyl, hexyl, heptyl, octyl, decyl and dodecyl acrylate, methacrylate, ethacrylate and phenylacrylate, N-vinyl pyrrolidone, ethylene, vinylidene fluoride, methyl, butyl, aminoethyl, aminoisobutyl, amidoethyl, N - dimethyl - or N - methylamidoethyl, and ureidoethyl vinyl ether.  Polymerization may be effected in the presence or absence of a solvent such as water, methanol, ethanol, isobutanol, butanol, benzene, toluene and dimethylformamide, and in the presence of a catalyst such as azodiisobutyronitrile, azodiisobutyramide, dimethyl, diethyl or dibutyl azodiisobutyrate, azobis (a ,g -dimethyl-valeronitrile), azobis (a -methylbutyronitrile), azobis (a -methylvaleronitrile) dimethyl azobismethylvalerate, butyl perbenzoate, benzoyl peroxide and ammonium persulphate.  The polymers may be used as bactericides, fungicides, antistatic agents, for the absorption of acid ions from liquids, as softening agents for rayon, cellulose acetate and cotton, to improve the dyeing of cellulose acetate and acrylonitrile polymers containing at least 75 per cent acrylonitrile in the polymer molecule, especially when a common solvent such as acetone, dimethylformamide or dimethylacetamide, is used to prepare a spinning or extrusion dope containing the film-forming polymer and dye-modifying polymer.  Permselective ion-exchange membranes may be produced by introducing a quaternary ammonium polymer of the invention into a cellulose acetate-acetone dope or into an aqueous solution of a water-soluble film former, such as polyvinyl alcohol, the solutions obtained being coagulated in the form of films or membranes of the desired thickness and then insolubilized where necessary, as by the use of formaldehyde in the case of polyvinyl alcohol.  Specification 747,184 is referred to.ALSO:Quaternary ammonium homopolymers and copolymers of monoethylenically unsaturated monomers comprising at least 20 mol. per cent of monomeric units having the general formula <FORM:0815745/IV (c)/1> in which A is ethylene, trimethylene or -CHR-CH2-, where R is alkyl or alkenyl, R1, R2 and R3 are selected from a large variety of radicals, at least one of R1, R2 and R3 havin at least 12 carbon atoms, and X is OH or a negative, salt-forming atom or radical (see Group IV (a)), may be used as antistatic agents for treatment of cellulose acetate, vinyl resins, nylon and polyethylene terephthalate, in the form of fibres, filaments, films, yarns and fabrics, as softening agents for cellulosic textiles or films, especially rayon, cellulose acetate and cotton, and for shrink-proofing wool fabrics or felts.  The treatment of wool may be effected by preparation by emulsion polymerization of a polymer of 50 to 80 per cent by weight of butyl acrylate with 50 to 20 per cent by weight of a quaternary of an amine of formula CH2= CHOANR1R2 and the application of the resultant copolymer in an amount of 5 to 10 per cent on the weight of the fabric and subsequent drying thereon, or, alternatively, a polymer or copolymer of an amine of the above formula may be partially quaternized and applied to the felt or fabric and then insolubilized in situ by completing the quaternization with ethylene dibromide or xylene dichloride, and heating the dried treated fabric at 80 DEG  to 100 DEG  C. for five to ten minutes. Specification 747,184 is referred to.