Bifunctionalized Intrinsically Microporous Polyimides with Simultaneously Enhanced Gas Permeability and Selectivity

Two novel intrinsically microporous copolyimides synthesized by condensation reaction of 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,3,3′,3′-tetramethyl-1,1′-spirobisindane-5,5′-diamino-6,6′-diol, and 3,5-diaminobenzoic acid with diamine ratios of 80/20 (Co-80/20) and 50/50 (Co-50/50) are reported. Unexpectedly, the Co-80/20 not only demonstrates higher microporosity (300 m2 g−1) than the PIM-6FDA-OH homopolymer (190 m2 g−1) but also exhibits simultaneously enhanced CO2 permeability (from 119 to 171 Barrer) and CO2/CH4 selectivity (from 35 to 41) after thermal annealing at 250 °C. This higher permeability originates from enhanced diffusivity (D CO2) and the higher selectivity results from its increased diffusion selectivity (D CO2/D CH4). After crosslinking at 300 °C, the Co-80/20 exhibits an even higher CO2 permeability (261 Barrer) and almost unchanged CO2/CH4 selectivity.