Free Volume Manipulation and In Situ Oxidative Crosslinking of Amine-Functionalized Microporous Polymer Membranes
Name
2024_TJ_ChemMater_PIM_TOX_main_article.pdf
Description
Accepted version
Size
7.02 MB
Format
Adobe PDF
Checksum (MD5)
43623298f3076815bfaf9f15d1f6eec2
Name
2024_TJ_ChemMater_PIM_TOX_SI.pdf
Description
Supporting information
Size
4.34 MB
Format
Adobe PDF
Checksum (MD5)
69b4431a16b0ba25cab70425a5420865
Author(s)
Joo, Taigyu
Lee, Tae Hoon
Kaser, Samuel J
Wu, Wan-Ni
Wi, Sungsool
Yeo, Jing Ying
Smith, Zachary P
Date Issued
April 25, 2024
Journal
Chemistry of Materials
Publisher
American Chemical Society
Citation
Free Volume Manipulation and In Situ Oxidative Crosslinking of Amine-Functionalized Microporous Polymer Membranes. Taigyu Joo, Tae Hoon Lee, Samuel J. Kaser, Wan-Ni Wu, Sungsool Wi, Jing Ying Yeo, and Zachary P. Smith. Chemistry of Materials 2024 36 (9), 4275-4290.
Version
Author's final manuscript
Abstract
Membranes for gas separations are limited by the trade-off relationship between permeability and selectivity. In this study, we demonstrate an in situ thermal oxidative crosslinking strategy for amine-functionalized polymers using tert-butoxycarbonyl (tBOC) groups to improve separation performance. The use of labile tBOC groups offers two major benefits for inducing thermal oxidative crosslinks: (1) they trigger free radical chain reactions at more moderate temperatures, preventing polymer backbone degradation pathways that otherwise occur at elevated temperatures, and (2) they enable free volume manipulation (FVM) conditions that yield increased free volume and narrower free volume element size distribution. This thermal oxidative crosslinking strategy is demonstrated using an amine-functionalized polymer of intrinsic microporosity (PIM-NH2). The resulting crosslinked polymer yielded up to a 22-fold increase in H2/CH4 selectivity while retaining 96% of H2 permeability from pristine PIM-NH2 films. By combining thermal oxidative crosslinks and FVM, we demonstrate an effective approach to overcome the traditional permeability–selectivity trade-off and offer a greater resistance to major performance stability issues like plasticization and physical aging, making membranes better suited for industrial applications.
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/acs.chemmater.3c03190
