Pure- and mixed-gas propylene/propane permeation properties of spiro- and triptycene-based microporous polyimides

Abstract

Solution-processable polyimides of intrinsic microporosity (PIM-PIs) comprising relatively inflexible and contorted backbones have demonstrated outstanding molecular-sieving behavior in membrane-based separation of gas/gas pairs. In this work, the effects of systematically increasing intra-chain rigidity on the propylene/propane separation properties were compared for PIM-PIs made from 2,3,5,6-tetramethyl-1,4-phenylene diamine (TMPD) and (i) spiro-centered dianhyride (SPDA-TMPD or PIM-PI-1) and (ii) 9,10-diisopropyltriptycene-based dianhydride (TPDA-TMPD or KAUST PI-1). Pure-gas experiments at 2bar and 35°C showed significant increases in C 3 H 6 permeability and C 3 H 6 /C 3 H 8 selectivity by transitioning from PIM-PI-1 (P(C 3 H 6)=393 Barrer, α(C 3 H 6 /C 3 H 8)=6) to KAUST-PI-1 (P(C 3 H 6)=817Barrer, α(C 3 H 6 /C 3 H 8)=16), positioning KAUST-PI-1 considerably above the experimentally observed pure-gas C 3 H 6 /C 3 H 8 polymer upper bound. However, 50:50 C 3 H 6 /C 3 H 8 mixed-gas feeds induced significant losses in C 3 H 6 permeability and C 3 H 6 /C 3 H 8 selectivity relative to the 2bar pure-gas data for PIM-PI-1 and KAUST-PI-1 as the C 3 H 6 /C 3 H 8 selectivity dropped from 6 to 3 and 16 to 5, respectively, at 2bar C 3 H 6 partial pressure due to plasticization and competitive sorption.