Verfahren zur Herstellung von Polymeren

摘要

The invention comprises polymers having a skeletal chain containing fluorocarbon acrylate or methacrylate ester units indicated by the formula: wherein Rf is a perfluoroalkyl group of 4 to 12 carbon atoms, R is an alkylene bridging group containing 1-12 carbon atoms, R1 is an alkyl group containing 1-6 carbon atoms and X is a hydrogen atom or a methyl group. The polymers may be prepared by polymerizing monomers of the formula Rf. SO2 N(R1) R CH2 OCO.CX = CH2 e.g. by bulk, solution or emulsion polymerization procedures using peroxide and persulphate catalysts. The monomers may also be copolymerized with other ethylenic monomers such as butadiene, maleic anhydride, acrylonitrile, vinyl acetate, vinyl chloride, vinyl silicones, styrene, methyl acrylate, methyl methacrylate, ethylene and isoprene. In examples monomers where Rf is C4F9, C6F13 and C8F17, R is (CH2)2, (CH2)4, (CH2)11 and R1 is CH3, C2H5, C3H7 and C4H9 are polymerized by emulsion polymerisation techniques in a water-acetone mixture using as emulsifying agent a salt of the formula C8F17. SO2 N (C2H5). CH2 COOK. The acrylate ester of N-ethyl-N-ethanol-perfluoro-octane sulphonamide and the methacrylate ester of N-ethyl-N-butanol-perfluorooctane sulphonamide are copolymerized with butadiene. The polymers and copolymers may be modified by treatment with plasticizers (e.g. fluorocarbon esters), by vulcanisation techniques or with carbon black or zinc oxide. The polymers may be used to provide surface coatings which are both water and oil repellent. Specifications 758,467, 857,335 and 857,906 are referred to.ALSO:The invention comprises acrylate and methacrylate esters of an N-alkyl-N-alkanol-perfluoroalkylsulphonamide of the general formula : RfSO2N(R1) R-CH2OH where Rf is a perfluoroalkyl group containing 4 to 12 carbon atoms, R is a divalent alkylene group containing 1 to 12 carbon atoms and R1 is an alkyl group containing 1 to 6 carbon atoms. The esters are prepared by conventional esterification of the corresponding alcohols with acrylic or methacrylic acids. The esters may be polymerised (see Group IV(a)) to yield polymers which, provide surface that is both oil and water repellent. In Examples (1) N-propyl-N-ethanolperfluorooctanesulphonamide is esterified with acrylic acid in the presence of sulphonic acid and copper flakes, (2) N-butyl-N-ethanol-perfluorooctanesulphonamide is esterified with acrylic acid in the presence of p-toluenesulphonic acid and hydroquinone, (3) N-ethyl-N-ethanolperfluorooctanesulphonamide is esterified with methacrylic acid in the presence of p-toluenesulphonic acid and hydroquinone, (4) N-butylN-butanol-perfluorooctanesulphonamide is esterified as in (3), (5) N-ethyl-N-undecanol-perfluorooctanesulphonamide is esterified with acrylic acid in the presence of p-toluensulphonic acid and hydroquinone, (6) N-ethyl-N-ethanol perfluorohexanesulphonamide, is esterified as in (5), N - methyl - N - butanol - perfluorobutanesulphonamide is esterified as in (5). Specifications 758,467, 857,335 and 857,906 are referred to.