Patent GB-1011577-A (GB)
Title: Vinylidene fluoride copolymers
IPC: C08F214/22
Filed: 1964-06-02
Abstract: Copolymers comprising 50 to 97 weight per cent of units of vinylidene fluoride, 2.5 to 49.5 weight per cent of units of tetrafluoroethylene and 0.1 to 10 weight per cent of units of a compound of formula <FORM:1011577/C3/1> where A is hydrogen, C1- 10 alkyl or R1Z; B is hydrogen, chlorine, methyl, ethyl or R1Z; R1 is CnH2n or -CH2OCH2CH2 - where n is 0 to 10 and Z is -CO2R11, -SO3R11 or -P(O)(OR11)2 where R11 is hydrogen, C1- 6 alkyl or monochloro substituted alkyl, alkali metal or ammonium, provided that A and B are not simultaneously R1Z groups, the copolymers having an inherent viscosity of 0.35 to 2 as a 0.5% solution in dimethyl formamide at 25 DEG  C., may be prepared by heating the monomers at a pressure of 5 to 1000 atmospheres in the presence of an inert solvent and a free radical initiator.  Up to 50% by weight of the tetrafluoroethylene may be replaced by a vinyl ester of an alkanoic acid containing 2 to 18 carbon atoms.  Many suitable compounds of the given formula are listed including alkene carboxylic and dicarboxylic acids, alkene and aralkene sulphonic and disulphonic acids, and alkene phosphonic and diphosphonic acids, and the esters and salts thereof, particularly bis-(2-chlorethyl) vinyl phosphonate and itaconic acid.  Specified solvents are fatty acids, tertiary alcohols, nitriles, halogenated hydrocarbons and esters. Preferred initiators are dialkyl and diacyl peroxides and peroxy esters. The polymers may be coated, e.g. from solutions in methyl ethyl ketone, on metals, plastics, cement, concrete and brick.  In examples in which di-t.-butyl peroxide, dilauroyl peroxide and t.-butyl perbenzoate are used as initiators and acetic acid, t.-butanol, 1,1,2-trichloro-1,2,2-trifluoroethane and 2,2,3,3-tetrafluoropropyl acetate are used as liquid media the copolymerization of vinylidene fluoride and tetrafluoroethylene with (I to IV, XXVII and XXVIII) bis - (2 - chlorethyl) vinylphosphonate, (V) vinyl butyrate and bis-(2-chlorethyl) vinylphosphonate, (VI) acrylic acid, (VII) vinyl acetate and acrylic acid, (VIII and XXVII) t.-butyl acrylate, (IX) vinyl acetate and t.-butyl acrylate, (X) vinyl acetate and methacrylic acid, (XI) vinyl stearate and methacrylic acid, (XII) methacrylic acid, (XIII) methyl methacrylate, (XIV and XV) t.-butyl methacrylate, (XVI) vinyl acetate and t.-butyl methacrylate, (XVII) diethyl 2-methallyloxyethyl phosphonate, (XVIII) vinyl acetic acid, (XIX) dimethyl itaconate, (XX) sodium vinyl sulphonate, (XXI) dimethyl allylphosphonate, and (XXII and XXIII) vinyl butyrate and itaconic acid.ALSO:Substrates, e.g. of ferrous and non-ferrous metals, wood, plastics, cement, concrete and brick, may be coated with organic solvent solutions of copolymers of 50-97 weight per cent of vinylidene fluoride units, 2,5-49,5 weight per cent of units of tetrafluoroethylene or a mixture thereof with up to 50% by weight of a vinyl ester of a C2-18 alkanoic acid, and 0,1-10 weight per cent of units of an olefinically unsaturated compound of formula <FORM:1011577/B1-B2/1> in which A is hydrogen, C1-10 alkyl or R1Z, B is hydrogen, chlorine, methyl, ethyl or R1Z, R1 is CnH2n where n is 0 to 10 or -CH2OC2H4-and Z is -CO2R11, -SO3R11 or -PO(OR11)2 where R11 is hydrogen, C1-6 alkyl or monochloralkyl, alkali metal or ammonium, provided that A and B are not simultaneously R1Z, the copolymer having an inherent viscosity of 0,35 to 2 as a 0,5% solution in dimethyl formamide at 25  DEG C.  In examples vinylidene fluoride/tetrafluoroethylene/bis(chlorethyl)vinyl phosphonate copolymers are coated from (I) dimethyl formamide on aluminium and methyl ethyl ketone on steel, and (II) methyl ethyl ketone on tinplated steel and aluminium; (III) a composition of the above copolymer, methyl ethyl ketone and titanium dioxide is applied to aluminium; aluminium is coated with methyl ethyl ketone solutions of copolymers of vinylidene fluoride, tetrafluoroethylene and (IV) bis(chlorethyl)vinylphosphonate, (V) bis(chlorethyl) vinylphosphonate and vinyl butyrate, (VI) acrylic acid, (VII) acrylic acid and vinyl acetate, (VIII) t.butyl acrylate, (XI) methacrylic acid and vinyl stearate, (XII) methacrylic acid, (XIII) methyl methacrylate, (XVII) diethyl 2-methallyloxyethylphosphonate, (XVIII) vinylacetic acid, (XIX) dimethyl itaconate, (XX) sodium vinylsulphonate, (XXI) dimethyl allylphosphonate, (XXVI) t.butyl acrylate, and (XVII) bis(2-chlorethyl) phosphonate; (IX) redwood panels are coated with compositions of a vinylidene fluoride/tetrafluoroethylene/vinyl acetate/t.butyl acrylate copolymer, titanium dioxide and methyl ethyl ketone; (X) phosphated steel and aluminium are coated with compositions of a vinylidene fluoride/tetrafluoroethylene/vinyl acetate/methacrylic acid copolymer, zinc dust and methyl ethyl ketone; (XIV) magnesium and steel, and (XV) galvanized steel and aluminium are coated with methyl ethyl ketone solutions of vinylidene fluoride/tetrafluoroethylene/t.butyl methacrylate copolymers; (XXII) polyethylene terephthalate film, aluminium and polyvinyl dioxolane primed steel are coated with methyl ethyl ketone solutions of vinylidene fluoride/tetrafluoroethylene/vinyl butyrate/itaconic acid copolymers; and (XXIII) cement, polyvinyl dioxolane primed steel and rigid vinyl resin sheet are coated with methyl ethyl ketone solutions of vinylidene fluoride/tetrafluoroethylene/vinyl butyrate/itaconic acid copolymers pigmented with titanium dioxide.