Polyperfluorobutadiene. V. Photopolymerization of Perfluorobutadiene

Abstract

Despite the ease of polymerization of tetrafluoroethylene, the homopolymerization of other perfluoroolefins and perfluorodienes is difficult to accomplish (1). The homopolymerization of hexafluoropropene to high polymer was brought about under extreme conditions, at a temperature of 210^°C and using pressures in the range of 3000–5000 atm. (2). A heavy oil was reported by Roberts, when a mixture of bis(trifluoromethyl)peroxide and hexafluoropropene was irradiated by Hg 2537 A^° radiation (3). Wall and his coworkers attacked the polymerization resistance problem using Y-ray initiation and high pressure (up to 20,000 atm.). High polymers were obtained from terminally unsaturated perfluoropentadiene (4), perfluorohexadiene, perfluoroheptadiene and perfluorooctadiene (5). The polymerization of perfluorobutadiene was reported by Miller to give high polymer under very high pressure with oxygen and peroxide promotion (6). Recently Toy and her coworkers reported bulk polymerization of perfluorobutadiene under low pressure and temperature in the presence of free radical catalysts to give polyperfluoro-1,2- and 1,4-butadiene (7,8,9). In this paper, the photopolymerizations of perfluorobutadiene by γ-ray initiation, ultraviolet light and in the presence of CF₃OOCF₃ are described.