Patent GB-1104482-A (GB)
Title: Perfluoro-olefin derivatives
IPC: C11D1/00
Filed: 1965-04-08
Abstract: Polymers containing -C3F6O- and -C3F4O-O-units, with or without-C2F4O-and-C2F4O-O-units, distributed at random in a polymer chain are prepared by subjecting C3F6, with or without C2F4, in the liquid phase to a photochemical reaction with molecular oxygen at between - 100 DEG  C. and + 25 DEG  C. at a pressure between 0.1 and 10 atmospheres absolute in the presence of U.V. radiation.  Liquid or gaseous diluents for the reactants may be present.  The products have terminal -COF groups and may be represented by the average formula (MOx)n, where M is the perfluoroolefin unit and x is 1-2, the value of x depending on reaction conditions and treatment of the products. If the U.V. radiation is mainly in the region 1000-3000 <\>rA, x is 2 or nearly 2; if substantial amounts of longer wavelength radiation, e.g. 2600-4000 <\>rA, are present, x is less than 2, and the more intense is the longer wavelength radiation, the closer x approaches 1. Peroxides (x = 2) show a loss in 0 content (x approaches 1) on further treatment with U.V. radiation or on heating; this applies also to derivatives of the initial products, e.g. those obtained by hydrolysis or salt, ester or amide formation, or de-carboxylation of terminal -COOH groups derived from the -COF groups.  Decarboxylated products with x = 1 are thermally stable and are useful as lubricants, heat exchange fluids, plasticizers and solvents for polymers, and for dielectric insulation.  Acid derivatives are useful as surface active agents and impregnating agents for fibres, paper and fabrics to render them oil- and water-repellant.ALSO:Compounds suitable as lubricants are obtained by reacting C3F6, with or without C2F4, in the liquid phase with oxygen at - 100 DEG  C. to + 25 DEG C. and 0.1-10 atmospheres pressure in the presence of U.V. radiation to obtain a polymer with -COF terminal groups and containing -C3F6OO- and -C3F6O- units, with or without -C2F4OO- and -C2F4O-units, heating or treating with U.V. radiation to reduce the peroxide content, and decarboxylating; e.g. a product of empirical composition C3F6O1.1 is decarboxylated by heating at 300-350 DEG  C. with molten KOH. ALSO:Compounds containing -C3F6O- and -C3 F6O-O-, with or without -C2F4O- and -C2F4O-O-, units distributed at random in a polymer chain are prepared by subjecting C3F6, with or without C2F4, in the liquid phase to a photochemical reaction with molecular oxygen at between - 100 DEG  C. and +25 DEG  C. at a pressure between 0.1 and 10 atmospheres absolute in the presence of U.V. radiation. Liquid or gaseous diluents for the reactants may be present.  The products have terminal -COF groups and may be represented by the average formula (MOx)n where M is the perfluoroolefin unit and x is 1-2, the value of x depending on reaction conditions and treatment of the products. If the U.V. radiation is mainly in the region 1000-3000 <\>rA, x is 2 or nearly 2; if substantial amounts of longer wavelength radiation, e.g. 2600-4000 <\>rA, are present, x is less than 2, and the more intense is the longer wavelength radiation, the closer x approaches 1. Peroxides (x2) show a loss in 0 content (x approaches 1) on further treatment with U.V. radiation or on heating; this applies also to derivatives of the initial products, e.g. those obtained by hydrolysis or salt, ester or amide formation, or de-carboxylation of terminal -COOH groups derived from the -COF groups.  Decarboxylated products with x1 are thermally stable and are useful as lubricants, heat-exchange fluids, plasticizers and solvents for polymers, and for dielectric insulation. Acid derivatives are useful as surface-active agents and impregnating agents for fibres, paper and fabrics to render them oil- and water-repellent.