Regioisomeric Spirobifluorene CANAL Ladder Polymers and Their Gas Separation Performance

Robinson, Ashley M.; Xia, Yan

doi:10.1021/acsmacrolett.3c00725

Regioisomeric Spirobifluorene CANAL Ladder Polymers and Their Gas Separation Performance

Journal Article · Tue Jan 09 00:00:00 EST 2024 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.3c00725· OSTI ID:2337849

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Stanford Univ., CA (United States); Stanford University
Stanford Univ., CA (United States)

For this work, we synthesized and characterized two isomeric microporous hydrocarbon ladder polymers from catalytic arene norbornene annulation (CANAL) of regioisomeric bis-norbornene fused spirobifluorenes, where the ladder chains are connected either through the same fluorene unit or across two different fluorene units in spirobifluorene. This pair of isomeric polymers was used to investigate the effect of ladder macromolecular structures on the microporosity and transport properties. Both polymers form mechanically intact films with thermal stability up to 480 °C and relatively high BET surface areas. The polymer formed from 2,7-dibromospirobifluorene showed higher BET surface area and higher gas permeability than the polymer from 2,2'-dibromospirobifluorene despite similar intersegmental spacing as indicated by X-ray scattering. The aging behavior for both polymers followed the same trend as the previously reported CANAL-fluorene polymers, with dramatically increased permselectivities over time, resulting in gas separation performance above the 2008 upper bounds for H₂/CH₄ and O₂/N₂.

View Accepted Manuscript (DOE)

Research Organization:: Stanford Univ., CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0023252

OSTI ID:: 2337849

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Vol. 13; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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