The synthesis, chain-packing simulation and long-term gas permeability of highly selective spirobifluorene-based polymers of intrinsic microporosity

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Abstract

Membranes composed of Polymers of Intrinsic Microporosity (SBF-PIMs) have potential for commercial gas separation. Here we report a combined simulation and experimental study to investigate the effect on polymer microporosity and gas permeability by placing simple substituents such as methyl, t-butyl and fused benzo groups onto PIMs derived from spirobifluorene (PIM-SBFs). It is shown that methyl or t-butyl substituents both cause a large increase in gas permeabilities with four methyl groups enhancing the concentration of ultramicropores (<0.7 nm), which contribute to selective gas transport. The t-butyl substituents lower selectivity by generating a greater concentration of larger, less selective, micropores (>1.0 nm). Long-term ageing studies (>3.5 years) demonstrate the potential of PIM-SBFs as high-performance membrane materials for gas separations. In particular, the data for the PIM derived from tetramethyl substituted SBF reaches the proposed 2015 Robeson upper bound for O2/N2 and, hence, hold promise for the oxygen or nitrogen enrichment of air. Mixed gas permeation measurements for CO2/CH4 of the aged PIM-SBFs also demonstrate their potential for natural gas or biogas upgrading.

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Bezzu, C. G., Carta, M., Ferrari, M. C., Jansen, J. C., Monteleone, M., Esposito, E., … McKeown, N. B. (2018). The synthesis, chain-packing simulation and long-term gas permeability of highly selective spirobifluorene-based polymers of intrinsic microporosity. Journal of Materials Chemistry A, 6(22), 10507–10514. https://doi.org/10.1039/c8ta02601g

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