Patent GB-1032244-A (GB)
Title: Copolymers of fluorine containing unsaturated monomers
IPC: C08F214/18
Filed: 1964-03-23
Abstract: 1,2-Dihydrohexafluoropropane may be prepared by catalytic hydrogenation of hexafluoropropylene in the gas phase in the presence of palladiated alumina at 30 DEG  to 300 DEG  C. 1,2,3,3,3-Pentafluoropropylene may be prepared by dehydrofluorinating the above product in an alkaline liquid medium, e.g. melted potassium hydroxide or aqueous potassium hydroxide solution at temperatures above 100 DEG  C.  Mixtures of 1,2,3,3,3- and 1,1,3,3,3-pentafluoropropylene may be prepared by dehydrofluorinating the hexafluoropropane in the gas phase at 300 DEG  to 900 DEG  C., optionally in the presence of an alkali metal halide.ALSO:Copolymers of 30 to 99 weight per cent of vinylidene fluoride with 1,2,3,3,3-pentafluoropropylene or mixtures thereof with 1,1,3,3,3-pentafluoropropylene containing at least 1% of 1,2,3,3,3-pentafluoropropylene, may be prepared by copolymerizing the monomers in the presence of a free-radical polymerization initiator at -30 DEG  to 200 DEG  C. under a pressure of atmospheric pressure to 300 atmospheres. Copolymerization may be effected batchwise or continuously in bulk, emulsion, suspension or solution.  Specified solvents are fluorotrichloromethane, dichlorotetrafluoroethane, perfluorocyclobutane, perfluorodimethylcyclobutane, perfluorocyclohexane, perfluoropropylpyrane and excess liquid monomer, and suitable initiators are benzoyl, p-chlorobenzoyl, 2,4-dichlorobenzoyl, acetyl, lauroyl, cyclohexanone, trichloroacetyl, trifluoroacetyl, perfluoropropionyl and heptafluorobutyric peroxides, t-butylperbenzoate, azo-diisobutyronitrile and azo-diisopropionitrile.  Suitable initiators for aqueous media are persulphates, perphosphates, perborates and percarbonates of sodium, potassium, ammonium, calcium and barium, hydrogen peroxide and barium peroxide, optionally together with activators, e.g. sodium bisulphite, metabisulphite and thiosulphate and salts of variable valency metals such as iron, copper, silver and titanium.  Buffers, e.g. sodium metaborate and phosphates, and chain transfer agents, e.g. lauryl mercaptan, chloroform and carbon tetrachloride, may also be present.  The copolymers may be thermoplastic or elastomeric, and may be formed into films, plates, tapes, fibres, coatings, gaskets, tubings, liners and containers.  The elastomeric copolymers may be compounded with vulcanizing agents and accelerators, acid-acceptors, fillers, plasticizers, lubricants and reinforcing agents and vulcanized. Vulcanization may be effected by polyamines, peroxides or radiation.  Compounding ingredients specified are magnesium oxide, carbon black and powdered coal.  Examples describe the copolymerization of vinylidene fluoride and 1,2,3,3,3-pentafluoropropylene (1 to 6) in aqueous media in the presence of ammonium persulphate, sodium metabisulphite, disodium phosphate, monopotassium phosphate and ammonium perfluorocaprylate or ammonium salts of o -hydroperfluorocarboxylic acids; and in perfluorocyclobutane in the presence of (7) perfluorobutyric anhydride, (8) azodiisobutyronitrile and (9) lauroyl peroxide; and the copolymerization of vinylidene fluoride, 1,2,3,3,3-pentafluoropropylene and 1,1,3,3,3-pentafluoropropylene in aqueous medium in the presence of ammonium persulphate, sodium metabisulphite, disodium phosphate, monopotassium phosphate and ammonium salts of o -hydroperfluoro-carboxylic acids.  The vulcanization of the products of Examples 2 to 6 and 10 by mixing with magnesium oxide, carbon black and dicinnamylidene hexamethylene diamine and heating is described.