Abstract

Glassy perfluoropolymers have become an exciting materials platform for membrane gas separation as they define the upper bounds for some gas separations, such as He/H2, He/CH4, and N2/CH4. However, due to the difficulty in synthesis, only a few glassy perfluoropolymers are commercially available, including Teflon AF and Hyflon AD derived from dioxoles and Cytop derived from dihydrofuran. In this study, two perfluoropolymers based on dioxolanes, poly(perfluoro-2-methylene-1,3-dioxolane) (poly(PFMD)) and poly(perfluoro-2-methylene-4-methyl-1,3-dioxolane) (poly(PFMMD)), were synthesized by radical polymerization and characterized thoroughly for physical properties such as glass transition temperature (Tg), d-spacing between polymer chains, and fractional free volume (FFV). The gas permeability and solubility were determined at 35 °C for a series of pure gases in these perfluorodioxolanes and compared with the commercial perfluoropolymers. Poly(PFMD) and poly(PFMMD) exhibit separation properties of He/H2, He/...

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