Fluorothiocarbonyl compounds. VI. Free‐radical polymerization of thiocarbonyl fluoride

AbstractThiocarbonyl fluoride, CF2S, and thiocarbonyl chlorofluoride, CFClS, undergo addition polymerization in free radical‐initiated systems. In addition, both compounds copolymerize with various unsaturated compounds, including typical vinyl and vinylidene monomers. The chlorofluoride, because of its rapid polymerization rate, copolymerizes best with very active monomers, of which 2,3‐dichloro‐1,3‐butadiene is an example. Thiocarbonyl fluoride polymerizes best at low temperatures. The trialkylborane—oxygen redox couple has been adapted to free‐radical polymerizations and copolymerizations from −60 to −120°C. With such initiation CF2S has been copolymerized with terminal and internal olefins, vinyl compounds, allyl compounds, and acrylic esters. Copolymerization with propylene is unusual, in that it proceeds in a manner that strongly favors a product composed of two molecules of CF2S for each propylene. In other cases, product compositions are more responsive to the ratio of monomers charged.