Tailoring the Micropore Structure of 6FDA-Based Network Polyimide Membranes for Advanced Gas Separation by Decarboxylation.

The 6FDA-based network PI has attracted significant attention for gas separation. A facile strategy to tailor the micropore structure within the network PI membrane prepared by the in situ crosslinking method is extremely significant for achieving an advanced gas separation performance. In this work, the 4,4'-diamino-2,2'-biphenyldicarboxylic acid (DCB) or 3,5-diaminobenzoic acid (DABA) comonomer was incorporated into the 6FDA-TAPA network polyimide (PI) precursor via copolymerization. The molar content and the type of carboxylic-functionalized diamine were varied in order to easily tune the resulting network PI precursor structure. Then, these network PIs containing carboxyl groups underwent further decarboxylation crosslinking during the following heat treatment. Properties involving thermal stabilities, solubility, d-spacing, microporosity, and mechanical properties were investigated. Due to the decarboxylation crosslinking, the d-spacing and the BET surface areas of the thermally treated membranes were increased. Moreover, the content of DCB (or DABA) played a key role in determining the overall gas separation performance of the thermally treated membranes. For instance, after the heating treatment at 450 °C, 6FDA-DCB:TAPA (3:2) showed a large increment of about ~532% for CO2 gas permeability (~266.6 Barrer) coupled with a decent CO2/N2 selectivity~23.6. This study demonstrates that incorporating the carboxyl-containing functional unit into the PI backbone to induce decarboxylation offers a practical approach with which to tailor the micropore structure and corresponding gas transport properties of 6FDA-based network PIs prepared by the in situ crosslinking method.