Physical Aging Investigations of a Spirobisindane-Locked Polymer of Intrinsic Microporosity

Liu, M; Lu, X; Nothling, MD; Doherty, CM; Zu, L; Hart, JN; Webley, PA; Jin, J; Fu, Q; Qiao, GG

Physical Aging Investigations of a Spirobisindane-Locked Polymer of Intrinsic Microporosity

Liu, M Lu, X Nothling, MD Doherty, CM Zu, L Hart, JN Webley, PA Jin, J Fu, Q

Qiao, GG

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Publisher:: AMER CHEMICAL SOC
Publication Type:: Journal Article
Citation:: ACS Materials Letters, 2020, 2, (8), pp. 993-998
Issue Date:: 2020-08-03

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Field	Value	Language
dc.contributor.author	Liu, M
dc.contributor.author	Lu, X
dc.contributor.author	Nothling, MD
dc.contributor.author	Doherty, CM
dc.contributor.author	Zu, L
dc.contributor.author	Hart, JN
dc.contributor.author	Webley, PA
dc.contributor.author	Jin, J
dc.contributor.author	Fu, Q https://orcid.org/0000-0002-4012-330X
dc.contributor.author	Qiao, GG
dc.date.accessioned	2021-03-28T00:59:56Z
dc.date.available	2021-03-28T00:59:56Z
dc.date.issued	2020-08-03
dc.identifier.citation	ACS Materials Letters, 2020, 2, (8), pp. 993-998
dc.identifier.issn	2639-4979
dc.identifier.issn	2639-4979
dc.identifier.uri	http://hdl.handle.net/10453/147559
dc.description.abstract	Polymers of intrinsic microporosity (PIMs) have exceptional gas separation performance for a broad range of applications. However, PIMs are highly susceptible to physical aging, which drastically reduces their long-term performance over time. In this work, we leverage complementary experimental and density functional theory (DFT) studies to decipher the inter-/intrachain changes that occur during aging of the prototypical PIM-1 and its rigidified analogue PIM-C1. By elucidating this hereto unexplored aging behavior, we reveal that the dramatic decrease in gas permeability of PIM materials during aging stems from a loss of fractional free volume (FFV) due to PIM chain relaxations induced by π-πinteractions, hydrogen bonding, or van der Waals' forces. While the PIM-1 based membranes displayed enhanced gas pair selectivities after aging, the PIM-C1 based membranes showed an opposite trend with unexpected reductions for CO2/N2 and CO2/CH4. This is due to the reductions in CO2/N2 and CO2/CH4 solubility (S) selectivities and, unlike PIM-1, the spirobisindane locked PIM-C1 (i.e., maintenance of micropore sizes) has a stable diffusivity (D) selectivities that cannot offset such reductions. These fundamental insights into the intrinsic relaxation of different PIM polymer chains during physical aging can guide the future design of high-performance PIM materials with enhanced anti-aging properties.
dc.language	English
dc.publisher	AMER CHEMICAL SOC
dc.relation	http://purl.org/au-research/grants/arc/FT180100312
dc.relation.ispartof	ACS Materials Letters
dc.relation.isbasedon	10.1021/acsmaterialslett.0c00184
dc.rights	info:eu-repo/semantics/openAccess
dc.rights	This document is the Accepted Manuscript version of a Published Work that appeared in final form in [ACS Materials Letters, 2020, 2, (8), pp. 993-998], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see https://pubs.acs.org/doi/10.1021/acsmaterialslett.0c00184].”
dc.title	Physical Aging Investigations of a Spirobisindane-Locked Polymer of Intrinsic Microporosity
dc.type	Journal Article
utslib.citation.volume	2
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Engineering and Information Technology
pubs.organisational-group	/University of Technology Sydney/Faculty of Engineering and Information Technology/School of Civil and Environmental Engineering
pubs.organisational-group	/University of Technology Sydney/Strength - CTWW - Centre for Technology in Water and Wastewater Treatment
utslib.copyright.status	open_access	*
dc.date.updated	2021-03-28T00:59:53Z
pubs.issue	8
pubs.publication-status	Published
pubs.volume	2
utslib.citation.issue	8

Abstract:

Polymers of intrinsic microporosity (PIMs) have exceptional gas separation performance for a broad range of applications. However, PIMs are highly susceptible to physical aging, which drastically reduces their long-term performance over time. In this work, we leverage complementary experimental and density functional theory (DFT) studies to decipher the inter-/intrachain changes that occur during aging of the prototypical PIM-1 and its rigidified analogue PIM-C1. By elucidating this hereto unexplored aging behavior, we reveal that the dramatic decrease in gas permeability of PIM materials during aging stems from a loss of fractional free volume (FFV) due to PIM chain relaxations induced by π-πinteractions, hydrogen bonding, or van der Waals' forces. While the PIM-1 based membranes displayed enhanced gas pair selectivities after aging, the PIM-C1 based membranes showed an opposite trend with unexpected reductions for CO2/N2 and CO2/CH4. This is due to the reductions in CO2/N2 and CO2/CH4 solubility (S) selectivities and, unlike PIM-1, the spirobisindane locked PIM-C1 (i.e., maintenance of micropore sizes) has a stable diffusivity (D) selectivities that cannot offset such reductions. These fundamental insights into the intrinsic relaxation of different PIM polymer chains during physical aging can guide the future design of high-performance PIM materials with enhanced anti-aging properties.

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http://hdl.handle.net/10453/147559