GB1298099A - Unsaturated quaternary ammonium compounds and copolymers containing them - Google Patents

Abstract

1298099 Emulsion polymerization KENDALL CO 2 Oct 1970 [20 Oct 1969 (2) 26 May 1970] 46997/70 Heading C3P [Also in Division C2C] This invention provides a polymerization process which comprises copolymerizing with an ethylenically unsaturated monomer 0À1-10% by weight based on the weight of said monomer of a quarternary ammonium compound which acts as an emulsion stabilizer in the process and has the formula wherein: V is an ethylenically -unsaturated radical selected from: (a) acid ester groups or acid amido groups derived from maleic, fumaric, citraconic or itaconic acid and reoresented bv the formulµ (b) acrylic ester or acrylamido groups represented by the formulµ CH 2 =CR 4 -COO- and CH 2 =CR 4 -CONH-, where R 4 is H or CH 3 ; (c) allyl, CH 2 =CH-CH 2 -; methallyl, CH 2 =C(CH 3 )-CH 2 -; vinyloxy, allyloxy, CH 2 =CH-CH 2 -O-; methallyloxy, CH 2 =C(CH 3 )-CH 2 -O-; vinyloxycarbonylmethyl, CH 2 = CH-O-CO-CH 2 -; allyloxycarbonylmethyl, or methallyloxy carbonylmethyl groups, CH 2 =C(CH 3 )-CH 2 -O-CO-CH 2 -; A is absent when V is an allyl, methallyl, vinyloxycarbonylmethyl, allyloxycarbonylmethyl, or methallyloxycarbonylmethyl group. Otherwise, A is a divalent radical selected from ethylene, -CH 2 CH 2 -; propylene, 2 - hydroxypropylene, -CH 2 -CHOH-CH 2 -; 2-acetoxypropylene, and isopropylene, -CH 2 -CH(CH 3 ) - groups, ethylene, propylene, isopropylene, and 2- hydroxypropylene groups being preferred. R 3 is a lipophilic radical which contains an aliphatic hydrocarbon chain of 7 to 28 carbon atoms, a chain of 9 to 18 carbon atoms being preferred. This hydrocarbon chain may be covalently linked to the nitrogen either directly or through one of the following intermediate linkages, wherein L represents the hydrocarbon chain: the benzyl group; an ester group such as -CH 2 -CH 2 -O-CO-L; a methylcarbonyloxy or methylcarbonylamino group an alkylene ether group such as -CH 2 -O-L; an alkyl amide group such as a 4-hydroxysuccinyloxy group a 4 - hydroxysuccinylamino group wherein R 8 is a diradical, preferably ethylene, propylene, isopropylene, 2 - hydroxy - propylene, 2-acetoxypropylene or an isomer of the aforesaid 4 - hydroxysuccinyloxy or 4- hydroxysuccinylamino groups wherein the hydrocarbon group L is attached to the carbon atom adjacent to the carboxyl group. The aliphatic hydrocarbon chain L may be linear or branched, saturated or unsaturated. R 1 is an alkyl group containing 1 to 7 carbon atoms or the benzyl group, and R 2 is an alkyl group containing 1 to 7 carbon atoms, the benzyl group or a group selected from - R 5 being H or an alkyl group containing 1 to 4 carbon atoms. Preferably R 1 and R 2 are alkyl groups containing 1 to 4 carbon atoms, especially methyl groups. N, R 1 and R 2 may also together form part of a heterocyclic amine of formula X- is a simple acid radical selected from F-, Cl-, Br-, I-, CH 3 SO 4 -, C 2 H 5 SO 4 - and Cl-, Br-, and CH 3 SO 4 - being preferred; or X- is an alkyl sulphate wherein the alkyl moiety contains 7 to 28 carbon atoms; an alkyl benaene sulphonate wherein the alkyl moiety contains 7 to 12 carbon atoms; a phenoxy (or alkyl phenoxy) alkylene (or polyalkylenoxy alkylene) sulphate having the formula R<SP>11</SP> being hydrogen or an alkyl group containing 1 to 12 carbon atoms, R<SP>111</SP> being hydrogen or methyl, and n being zero or an integer; a dialkyl sulphosuccinate wherein the alkyl groups contain 1 to 24 carbon atoms; or an alkyl phosphate wherein the alkyl group contains 1 to 18 carbon atoms, with the proviso that R 3 is then a lipophilic radical containing a hydrocarbon chain of 8 to 28 carbon atoms. Suitable ethylenically unsaturated monomers for copolymerizing with the above-defined compounds are vinyl acetate, vinyl chloride, acrylonitrile and compounds CH 2 =CR 6 .COOR 7 where R 6 is H or CH 3 and R 7 is C 1-14 alkyl. More than one quarternary ammonium compound may be used in the process, and a minor proportion of the main monomer may be replaced by another ethylenic monomer, e.g. a vinyl ester, a vinyl ether or a diunsaturated monomer, such as vinyl laurate, vinyl stearate, vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether, diethyleneglycol diacrylate, ethyleneglycol diitaconate, diallyl phthalate or divinyl benzene; or acrylic or methacrylic acid, acrylamide, methacrylamide, hydroxyethyl or hydroxypropyl acrylate or methacrylate, or styrene. The polymerization can be batch or continuous. Reference has been directed by the Comptroller to Specification 1,140,520.