New classes of amorphous perfluorinated polymers with extraordinary properties were developed and commercialized by DuPont (as Teflon® AF), Asahi Glass (as Cytop®), and Solvay (as Hyflon® AD). Teflon® AF and Hyflon® AD are a family of copolymers of 2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole (I) and 2,2-bis(trifluoromethyl)-4-fluoro-5-trifluoromethoxy-1,3-dioxole (II) with TFE, respectively. This chapter discusses the synthesis of Teflon®, Hyflon®, and Cytop® monomers. Typical preparation method for perfluoro-2-methylene-1,3-dioxolanes monomers and polymers is shown in the chapter. The physical properties of perfluorodioxolane polymers are modified by copolymerizing the dioxolane monomers. The amorphous polymers have high potential in many applications. The chapter describes two examples of the use of the amorphous perfluorinated polymers: optical fibers and gas separation membranes.
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