Perfluorodioxolane polymers for gas separation membrane applications

Since the discovery of polytetrafluoroethylene (PTFE) in 1938, fluorinated polymers have drawn attention in the chemical and pharmaceutical field, as well as in optical and microelectronics applications. The reasons for this attention are their high thermal and oxidative stability, excellent chemical resistance, superior electrical insulating ability, and optical transmission properties. Despite their unprecedented combination of desirable attributes, PTFE and copolymers of tetrafluoroethylene (TFE) with hexafluoropropylene and perfluoropropylvinylether are crystalline and exhibit poor solubility in solvents, which makes their processability very challenging. Since the 1980s, several classes of solvent-soluble amorphous perfluorinated polymers showing even better optical and gas transport properties were developed and commercialized. Amorphous perfluoropolymers exhibit, however, moderate selectivity in gas and liquid separations. Recently, we have synthesized various new perfluorodioxolane polymers which are amorphous, soluble, chemically and thermally stable, while exhibiting much enhanced selectivity. In this article, we review state-of-the-art and recent progress in these perfluorodioxolane polymers for gas separation membrane applications.