Effects on Carbon Molecular Sieve Membrane Properties for a Precursor Polyimide with Simultaneous Flatness and Contortion in the Repeat Unit

Abstract Carbon molecular sieve (CMS)‐based membrane separation is a promising solution for hydrogen separation due to its great advantages on perm‐selectivity, thermal stability, and chemical stability. To prepare high‐performance CMS membranes, the molecular structure of polymer precursors and their arrangements should be primarily considered. In this work, a benzimidazole‐based 6FDA (2,2′‐bis(3,4′‐dicarboxyphenyl) hexafluoropropane dianhydride)‐type polyimide (PABZ‐6FDA‐PI) is chosen as precursor to prepare the CMS membrane. Effects of chain flatness and contortion in the polyimide precursor on gas‐separation performance of CMS membranes were studied in detail by gas adsorption and permeation experiment. The H 2 permeability of CMS is up to 9500 Barrer and ideal selectivity of gas pairs of H 2 /CH 4 and H 2 /CO 2 is up to 3800 and 13, respectively. The comprehensive performance of hydrogen separation including H 2 /CO 2 , H 2 /N 2 , and H 2 /CH 4 gas pairs is located well above previously reported upper bounds for polymers.