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

Bezzu, Caterina Grazia, Carta, Mariolino ORCID: https://orcid.org/0000-0003-0718-6971, Ferrari, Maria-Chiara, Jansen, Johannes C., Monteleone, Marcello, Esposito, Elisa, Fuoco, Alessio, Hart, Kyle, Liyana-Arachchi, T. P., Colina, Coray M. and McKeown, Neil 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) , pp. 10507-10514. 10.1039/C8TA02601G

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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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	2050-7488
Date of First Compliant Deposit:	11 October 2018
Date of Acceptance:	10 May 2018
Last Modified:	06 May 2023 03:17
URI:	https://orca.cardiff.ac.uk/id/eprint/115750

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