New industrial fluoropolymer science and technology

Abstract Teflon® AF, a family of copolymers of perfluoro‐2,2‐dimethyldioxole with tetrafluoroethylene, and Cytop®, a ring‐cyclized homopolymer of CF 2 =CFO(CF 2 ) 2 CF=CF 2 are the first commercial amorphous perfluoroplastics which combine high optical clarity and solubility with outstanding chemical, thermal and electrical properties. The processes for making these materials are described and recent structure‐property studies that reveal dramatic substituent effects on polymer T g and related properties are reviewed. The results of some initial fundamental kinetic studies on fluorinated free‐radical cyclizations that relate to efficient cyclopolymerization of fluorinated dienes and the design of new ring‐containing fluoroplastics are discussed.