Patent GB-983486-A (GB)
Title: Fluoro-nitroso-compounds and their polymers
IPC: C08L75/00
Filed: 1960-06-15
Abstract: The invention comprises fluorine-containing aliphatic compounds having a nitroso-group attached to one of a pair of adjacent carbon atoms, and a nitroso-group or a nitro-group attached to the other of said pair; and their production by reacting nitric oxide with a fluorine-containing aliphatic olefin, e.g. at 10-100 DEG  C. The reaction may be liquid or vapour phase; irradiation, e.g. with i.r. light, may be used.  Specified products are 1,2-dinitroso perfluoroethane, 1,2 - dinitroso - trifluorochloroethane, 1,2 - dinitrosoperfluoropropane, 1 - nitro - 2 - nitroso perfluoroethane, and nitro-nitroso - perfluoropropane. Starting olefines for these and other products are listed.  The compounds of the invention form telomers and polymers with ethylenic compounds (see Division C3). Reference has been directed by the Comptroller to Specification 847,212.ALSO:The invention comprises copolymers and cross-linked copolymers derived from an ethylenically unsaturated compound and a fluorinecontaining aliphatic compound having a nitrosogroup attached to one of a pair of adjacent carbon atoms, and a nitroso-group or a nitro-group attached to the other of said pair (see Division C2). Specified nitroso compounds are 1,2-dinitroso perfluoroethane, 1,2 - dinitroso - trifluorochloroethane, 1,2 - dinitroso - perfluoropropane, 1 - nitro - 2 - nitroso - perfluoroethane and nitro-nitroso-perfluoropropane.  Olefines from which these and other compounds as defined may be obtained are specified; these include hydrogen- and/or chlorine-containing olefines.  Comonomers with which the nitroso compounds may be polymerized include trifluoroethylene, difluoromonochloroethylene, tetrafluoroethylene, trifluorochloroethylene, asym. difluorodichloroethylene, perfluoropropene, 1,1 - difluoro, 1,1,2 - trifluoro-, 1,1,3-trifluoro-, 1,1-difluoro-2-methyl-, 1,1-difluoro-3-methyl-, 1,1 - difluoro - 2 - trifluoromethyl- and 1,1,2,4,4-pentafluoro-butadiene, 2,2,2-trifluoroethyl vinyl ether, methyl trifluorovinyl ether, CF3OC2F4CH2OCH=CH2, 1,1 - dihydroheptafluorobutyl, acrylate, N-ethylperfluoro-octane-sulphonamidoethyl methacrylate, N - propylperfluoro-octanesulphonamidoethyl acrylate, propyl vinyl ether, acrylonitrile, styrene, and butadiene.  Polymerization may be effected in bulk or aqueous emulsion, e.g. with perfluoroalkanoic acids or perfluorochloroalkanoic acids or their salts as emulsifiers. Tetrafluoroethylene can be reacted with nitric oxide to give the copolymer directly.  The monomeric fluoro-nitroso-compounds are said to be solvents for the above polymers.  The polymers may be cross-linked with, e.g., dimercaptans or amines, such as hexamethylene dithiol, hexamethylene diamine and its carbamate, and triethylene tetramine.  The copolymers are useful as coating compounds (see Division B2), lubricants, sealants, adhesives, chemical intermediates, plasticizers and in insulating and dielectric compositions. Solid polymers may be preformed or fabricated into articles such as gaskets and O-rings.  Reference has been directed by the Comptroller to Specification 847,212.ALSO:Surfaces such as fabrics, metal and glass are coated with copolymers derived from an ethylenically unsaturated compound and a fluorine-containing aliphatic compound having a nitroso-group attached to one of a pair of adjacent carbon atoms, and a nitroso-group or nitro-group attached to the other of a said pair (see Division C3).  The polymers can be coated on to the surface directly from the aqueous latex produced by aqueous emulsion polymerization, or the separated and dried polymers can be dissolved in a fluorocarbon or chlorofluorocarbon solvent and then coated on the surface.  Reference has been directed by the Comptroller to Specification 847,212.