Chapter 9:Research and Non-major Commercial Co- and Terpolymers of Tetrafluoroethylene

Co- and terpolymers of tetrafluoroethylene (TFE) are ubiquitous in terms of commercial fluoropolymers, and the preparations, properties and applications of these outstanding materials have been well documented in monographs, book chapters, review articles, and the patent and scientific journal literature. The purpose of this chapter is not to cover these major commercial materials again, but rather to overview what is known in the patent and scientific journal literature about research-level TFE-based fluoropolymers and some of those TFE-based fluoropolymers that are available only at a minor commercial level. Since our research group represents one of the few academic laboratories that can safely work with TFE on a kilogram scale, it behooves us to be aware of the scientific literature in this field, and it was an instructive exercise for the coauthors to undertake this literature review. As certainly perfluoroalkyl trifluorovinyl ethers, especially CF2CFOCF3 and CF2CFOCF2CF2CF3, have a prominent place in commercial co- and terpolymers of TFE (e.g. PFA resins, fluoroelastomers), it was decided to begin this chapter with an overview of co- and terpolymers of TFE with all alkyl vinyl ethers, non-fluorinated, partially fluorinated and perfluorinated alkyl vinyl ethers, including those with a reactive functionality(ies) on the end of the alkyl group. We then move to a coverage of co- and terpolymers of TFE with ethylenic monomers, again non-fluorinated, partially fluorinated and perfluorinated ethylenic monomers, with the obvious exclusion of major commercial TFE-based fluoropolymers such as ETFE, FEP and others. The final section is devoted to overviewing co- and terpolymers of TFE with cyclic monomers, an area that became especially important in the 2000s as fluoropolymer chemistry attempted to aid the continuance of Moore's law with improved materials for photoresists, etc. Overall, the accompanying literature survey is not meant to be exhaustive, but rather to provide as comprehensive a review as possible within the space available.