Patent GB-958849-A (GB)
Title: Process for polymerisation of halogenated nitrosoalkanes
IPC: C08G73/24
Filed: 1962-03-27
Abstract: Halogen containing nitrosoalkanes are prepared. The mono-nitroso-alkanes are prepared by reacting a halogen-containing alkyl halide of less than 13 carbon atoms with nitric oxide in equal molar ratios in the presence of mercury and ultraviolet light for about 24 hours at ambient temperatures, e.g. trifluoro-methyl bromide or iodide with nitric acid gives trifluoronitrosomethane, pentafluoroethyl bromide or iodide gives pentafluoronitrosoethane and heptafluoropropyl bromide or iodide gives heptafluoronitrosopropane. Also the chlorofluoronitrosoalkanes are prepared from chlorotrifluoroethylene tolomers of trichlorobromomethane and nitric oxide.  The dinitroso- and nitronitrosoalkanes are prepared by reacting nitric oxide with a fluorine-containing olefin.  The olefin is preferably an acyclic monoolefin-1 of not more than 12 carbon atoms preferably with at least one halogen atom attached to at least one of the combinations of the double bond.  Specified olefins are tetrafluoroethylene, trifluorochloroethylene, perfluoropropene, perfluorobutene-1, unsymmetrical difluorodichloroethylene, 2-chloropentafluoropropene-1, -1-dichlorotetrafluoropropene-1, and partially halogenated olefins, e.g. vinylidene fluoride, difluoromonochloroethylene, 1-1-chlorofluoroethylene, trifluoroethylene, 1-1-dihydroperfluoropropene-1 and 1-1-dihydroperfluoro-butene-1. The resulting adducts are the 1-2-nitronitrosoalkanes and 1-2-dinitrosoalkanes such as 1-2-nitronitroso-tetrafluoroethane and 1-2-dinitrosotrifluorochloroethane. In an example (1) A 50/50 mol. ratio change of CF3Br and nitric oxide are agitated in the presence of mercury and ultraviolet light for 25 hours, the pressure being kept at one atmosphere by intermittently charing NO as the pressure decreased.  Distillation gave a 60% yield of trifluoronitrosomethane.ALSO:A halogen-containing nitrosoalkane is co-polymerised dispersed in an aqueous medium with an insoluble inorganic dispersing agent at 0 DEG C. or below. Specified nitrosoalkanes are trifluoronitrosomethane 2-hydroperfluoro or pentafluoro-, tetrafluorodi-, tetrafluoronitro-, trifluorochlorodi-, trifluorodichloro-, nitroso ethanes, heptafluoro or hexafluorodi-, or hexafluoronitro-, nitroso propanes, mononitrosoperfluorobutane, octafluorodinitrosobutane, mononitrosoperfluorooctane, 1 - nitroso-1.3.5.7.7.7-hexachlorononafluoroheptane and 1-nitroso-1.3.5.7-9.9.9-heptachlorododecafluorononane. Specified comonomers include butadiene, vinylidene fluoride, trifluoroethylene, difluoromonochloroethylene, tetrafluoroethylene, trifluorochloroethylene, unsymmetrical difluorodichloroethylene, perfluoropropene, 1-1-di-fluorobutadiene, 1-1-2-trifluorobutadiene, The acrylate ester of 1-1-dihydroheptafluorobutanol, the methacrylate ester of n-ethyl perfluorooctane sulphonamido-ethanol, the acrylate ester of n-propyl perfluorooctane sulphonamido ethanols 2.2.2-trifluoroethylvinylether, methyltrifluorovinyl ether, gamma-trifluoromethoxytetrafluoropropyl vinyl ether propyl vinyl ether acrylonitrile and styrene.  Specified dispersing agents are zinc oxide, magnesium carbonate, titanium dioxide, barium sulphate, and calcium phosphate. An inorganic freezing point depressant may also be present e.g. lithium bromide, lithium chloride and zinc nitrate.