Tailoring the micropore structure of 6FDA-based polyimide membrane for gas permselectivity studied by positron annihilation

Abstract Two series of 6FDA-based co-polyimide membranes were synthesized by adding different diamine monomer containing special functional groups: APAF (containing -OH) and DABA (containing -COOH). The ODA/APAF and ODA/DABA series were heat treated at 450 °C and 350 °C, respectively. Thermal rearrangement of polymer chain segments is confirmed in ODA/APAF membranes by infrared spectroscopy, while addition of DABA in ODA/DABA membranes causes decarboxylation crosslinking. Positron lifetime measurements reveal existence of ultramicropores in polyimides. The thermal rearrangement in ODA/APAF membranes induces remarkable increase in both size and number of ultramicropores and therefore increase in fractional free volume (FFV), but the crosslinking in ODA/DABA causes significant decrease in both size and number of ultramicropores. The increase in FFV is favorable for gas permeation, but too large size of the micropore drastically deteriorates the gas selectivity. Finally, the ODA/APAF(3:7) shows a high CO2 permeability of 127.4 Barrer with CO2/CH4 selectivity of 34.2, which surpasses the 1991 Robeson upper bound. Besides, the ODA/DABA(3:7) exhibits a H2 permeability of 22.6 Barrer with H2/CH4 selectivity of 256.8, which also exceeds the 1991 Robeson upper bound. Our results indicate that the gas permeability and selectivity of polymer membranes can be effectively adjusted by tailoring the ultramicropore structures, and positron can provide precise information about micropores.