| 摘要 |
Polymerization reactions (see Group IV(a)) are catalyzed with nitrogen fluorides which may be used in admixture with perfluorocarbons and perfluorocarbon nitrides. The nitrogen fluorides used are dinitrogen di- and tetrafluorides and compounds F-N=(X1)(X2), where X1 and X2 are each fluorine or a perfluoroalkyl or perfluoroalicyclic radical (examples of which range from C1 to C12). Examples using mixed catalysts are Nos. XXII (NF3, cis.-N2F2 and trans.-N2F2 with traces of air and nitrous oxide); XXXV (NF3 and N2F2 with traces of nitrous oxide and nitrogen); and XXXVII (NF3, cis.-N2F2, and trans.-N2F2). Specifications 572,810, 583,118, 583,181 and 888,765 are referred to.ALSO:Unsaturated monomers capable of catalytic polymerization under at least atmospheric pressure are polymerized or copolymerized in the presence of a catalytic amount of dinitrogen difluoride or tetrafluoride or a nitrogen fluoride of the formula F-N = (X1)(X2) where X1 and X2 are each fluorine or a perfluoroalkyl or perfluoroalicyclic radical. Monomers specified are butadiene; 2-fluorobutadiene; 2-phenoxybutadiene; 1,1,4,4-tetrafluorobutadiene; 2-chlorobutadiene-1,2; 2-methylbutadiene-1,2; 2-cyanobutadiene-1,3; 2,3-dimethylbutadiene-1,3; vinyl -acetate, -trimethyl acetate, -chloroacetate and stearate; vinyl, allyl and crotyl methacrylates; ethylene glycol monomethacrylate; methallyl and di-allyl acrylates; divinyl adipate; vinyl succinate; acrolein; methyl vinyl ketone; methyl vinyl ether; vinyl dioxolane; ethylene; propylene; butenes; styrene; vinyl naphthalene; methyl styrene; vinylcyclohexene; o-divinyl benzene; 1,2,4-trivinyl benzene; acryloand methacrylonitriles; acrylic and methacrylic acids and their anhydrides, esters and amides, e.g. methyl acrylate, methyl-, glycidyl-, propyl-, octyl-, n-butoxyethoxyethyl-, chloroethyl-, and -diethylaminoethylmethacrylates, acrylamide, methacrylamide and N-butyl acrylamide; maleic anhydride; maleimide; diethyl-, dipropyl- and dicyclohexyl fumarates; perchloropropylene; vinyl chloride and fluoride; vinylidene chloride; chlorotrifluoroethylene; 1-chloro-2-fluoroethylene; 1-chloro-1-fluoroethylene; 1-chloro-1,2-difluoroethylene; 1,1-dichloro-2,2-difluoroethylene; tetrafluoroethylene; N-vinyl imides, e.g. phthalimide and succinimide; N-vinyl lactams, e.g. caprolactam; vinylene carbonate; perfluoro2-butyne, -pentyne, and -hexyne; and perfluoro3-hexyne; they may be homopolymerized or copolymerized with each other or modified by forming telomers by effecting the polymerization in the presence of hydrogen or such compounds as carbon tetrachloride, chloroform, isobutyric acid, acetic anhydride, methyl acetate or propionate, dioxolane, or a mercaptan, bisulphite, alcohol, ether, silicon halide or hydrogen halide. Nitrogen fluorides F-N = (X1)(X2) specified are trifluoromethyldifluoronitride; bis (trifluoromethyl) fluoronitride; pentafluoroethyldifluoronitride; bis (pentafluoroethyl)-fluoronitride; nonafluorobutyldifluoronitride; heptadecafluorooctyldifluoronitride; bis (uncosafluorodecyl)fluoronitride; pentacosafluorodecyldifluoronitride; bis (undecafluorocyclohexyl) fluoronitride; undecafluorocyclohexyldifluoronitride and decafluoropyridylfluoronitride. They may be used in admixture with perfluorocarbons and perfluorocarbon nitrides. The amount of catalyst is normally at least 0,0001% by weight of the monomer, preferably 0,1 to 30%. Polymerization may be effected at -80 DEG to 300 DEG C. and 1 to 500 atmospheres for 0,5 to 15 hours and may be promoted by light of 3,100 to 4,500 DEG A. The reaction can take place without a reaction medium or in the presence of media unreactive towards the catalyst under the reaction conditions, e.g. benzene, water, methanol, ethanol, acetone, diethyl ketone, chlorobenzene, tetrachloroethylene and dichlorodifluoromethane. Examples are given of the polymerization of the following monomers:-butadiene (to give a rubbery polymer by polymerization in water containing sodium dodecyl sulphate and sodium hydroxide); vinyl acetate; vinyl chloroformate; ethylene; styrene; ethylene/carbon monoxide; methyl methacrylate; acrylonitrile; tetrafluoroethylene; hexafluoropropylene; vinyl fluoride; tetrafluoroethylene/hexafluoropropylene and/or hexafluoropropylene dimer; hexafluoropropylene/vinylidene fluoride (in a further example the product is cured with magnesium oxide, furnace black and hexamethylene diamine carbamate); 1-chloro1,2 difluoroethylene; vinylidene fluoride; omega-hydro perfluorooctene/tetrafluoroethylene; and perfluorobutyne-2. Besides the reaction media mentioned above perfluorodimethylcyclobutane is employed in some examples. Specifications 572,810, 583,118, 583,181 and 888,765 are referred to. |
