Preparation of Ester-Crosslinked PI Membranes with Enhanced Gas Selectivity and Plasticization Resistance

Fabricating polyimide (PI) membranes with outstanding anti-plasticization ability and gas separation performance remains a challenge. In this study, two novel diamine monomers, DAMBO (methyl 3,5-diamino-4-methylbenzoate) and DAPGBO (3-hydroxypropyl 3,5-diamino-4-methylbenzoate), were synthesized through esterification reactions. Then, we copolymerized each of these two new monomers with 4,4'-diaminodiphenylmethane (DAM) and 4,4'-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) separately to yield two monoesterified PIs. Following this, we further prepared the ester-crosslinked PIs by inducing a transesterification crosslinking reaction within the PI-PGBO membrane via thermal treatment. As expected, we found that the formation of cross-linked structures can effectively regulate the microporous structure, enhance its sieving performance, and thus improve the membrane's gas selectivity. Furthermore, the resulting network structure endowed the thermally treated PI membrane with excellent anti-plasticization ability. Physical characterization results show that after heat treatment, both the d-spacing and BET surface area of the PI membrane decreased, but the solvent resistance of the thermally treated PIs was significantly improved. Gas separation experiments revealed that the representative membrane (PI-PGBO-300) exhibited the optimal CO₂/CH₄ separation performance, with a CO₂ permeability of 371.05 Barrer, a CO₂/CH₄ selectivity of 28.11, and a CO₂ plasticization pressure exceeding 30 bar. This study provides valuable insights into the design of cross-linked polyimides (PIs) via transesterification reactions, which are capable of enhancing the performance of membrane-based gas separation processes.