Maleimide-induced crosslinking of polyimide membranes for high gas separation performance and plasticization resistance

Abstract

Trade-off effect and plasticization are the key issues confronted in the area of membrane separation when dealing with applications involving high-pressure, soluble gases like CO2. In this study, a novel diamine (TAPA-MAA) was synthesized derived from tris(4-aminophenyl)amine (TAPA) and maleic anhydride (MA). This diamine was copolymerized with DAM (2,4,6-trimethylbenzene-1,3-diamine) and 6FDA (4,4′-(hexafluoroisopropylidene)diphthalic anhydride) to form the polyimide (PI) membrane containing maleimide (MI) cross-linking sites via chemical imidization way. Then, under the action of heat treatment, the crosslinked PI (cPI) membrane was constructed since the MI crosslinking initiates a radical cycloaddition reaction to form a succinimide-linked structure, and named as cPSI membrane for short. Further, an increase in the ratio of TAPA-MAA gives rise to the resultant cPSI membrane with elevated cross-linking density. The obtained cPSI membranes showed significantly enhanced gas selectivities and superior anti-plasticization property compared to the un-crosslinked PI membranes due to the MI-induced crosslinking reaction in the PI main chain, resulting in a marked increment (24 %) in ultra-microporosity (<7 Å) and a reduction in the d-spacing value (6.10 Å vs 5.80 Å), generating a strong molecular sieving effect. Meanwhile, the highly interconnected covalent structure formed by the MI-induced crosslinking will suppress the plasticizing phenomenon induced by high-pressure soluble gases. The typical membrane (cPSI-3:7-350) possessed great CO2/CH4 separation performance, CO2 permeability of 334.4barrer and a CO2/CH4 selectivity of 61.9 that is exceeded the 2008Roberson upper bound, along withCO2 plasticization pressures above 44 bar. Besides, its mixed CO2/CH4 separation performance exceeded the 2018 upper gas mixture limit when the upstream pressure changed from 2-20 bar. This study provides valuable insights for the design of PIs containing MI cross-linking sites, which can enhance the performance of membrane-based gas separation.