Tuning gas separation performance of polyimide membranes with macrocyclic crown ether units

Su, Yiwei; Seeger, Andrew; Guo, Ruilan

doi:10.1016/j.polymer.2025.128677

Tuning gas separation performance of polyimide membranes with macrocyclic crown ether units

Journal Article · Wed Jun 11 00:00:00 EDT 2025 · Polymer

DOI:https://doi.org/10.1016/j.polymer.2025.128677· OSTI ID:3008389

Su, Yiwei ^[1]; ^[1]; ^[1]

University of Notre Dame, IN (United States)

Membrane-based gas separation is an energy-efficient alternative to conventional thermally-driven separation processes. However, polymer membranes face the permeability-selectivity trade-off challenge, which stems from the broad size distribution of free volume voids. Here, this study reports a molecular design strategy to address this challenge through incorporating macrocyclic crown ether (CE) moieties into the backbone of Matrimid® polyimide, a commercial gas separation membrane. A series of CE-containing Matrimid®-like copolyimides were synthesized with systematically varied CE molar contents ranging from 3 to 20%. These copolyimides formed ductile, defect-free thin films suitable for membrane fabrication. Gas permeation tests revealed a non-monotonic relationship between permeability/selectivity and CE content. Notably, the copolyimide with only 5% CE demonstrated a 61% increase in CO₂/CH₄ selectivity and a 13% increase in CO₂ permeability relative to pristine Matrimid®. Higher CE contents did not yield further performance improvements, which is likely due to the competing effects of chain packing disruption and π–π interactions among CE moieties at high content. This hypothesis was supported by wide-angle X-ray scattering (WAXS) analysis, density measurements, and fractional free volume calculations. These findings highlight the potential of macrocyclic crown ether incorporation strategies in fine tuning the microstructure of commercial polyimide gas separation membranes to surpass the traditional permeability-selectivity trade-off.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0024384

OSTI ID:: 3008389

Journal Information:: Polymer, Journal Name: Polymer Vol. 333; ISSN 0032-3861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (31)

Gas separation using polymer membranes: an overview Ghosal, Kanchan; Freeman, Benny D. Polymers for Advanced Technologies, Vol. 5, Issue 11 https://doi.org/10.1002/pat.1994.220051102	journal	November 1994
Correlation of separation factor versus permeability for polymeric membranes Robeson, Lloyd M. Journal of Membrane Science, Vol. 62, Issue 2 https://doi.org/10.1016/0376-7388(91)80060-J	journal	October 1991
Correlation and prediction of gas permeability in glassy polymer membrane materials via a modified free volume based group contribution method Park, J. Y.; Paul, D. R. Journal of Membrane Science, Vol. 125, Issue 1 https://doi.org/10.1016/S0376-7388(96)00061-0	journal	March 1997
High performance polymer membranes for CO2 separation Kim, Seungju; Lee, Young Moo Current Opinion in Chemical Engineering, Vol. 2, Issue 2 https://doi.org/10.1016/j.coche.2013.03.006	journal	May 2013
Current and future trends in polymer membrane-based gas separation technology: A comprehensive review Sidhikku Kandath Valappil, Riya; Ghasem, Nayef; Al-Marzouqi, Mohamed Journal of Industrial and Engineering Chemistry, Vol. 98 https://doi.org/10.1016/j.jiec.2021.03.030	journal	June 2021
Gas permeability properties of Matrimid® membranes containing the metal-organic framework Cu–BPY–HFS Zhang, Yanfeng; Musselman, Inga H.; Ferraris, John P. Journal of Membrane Science, Vol. 313, Issue 1-2 https://doi.org/10.1016/j.memsci.2008.01.005	journal	April 2008
The upper bound revisited Robeson, Lloyd M. Journal of Membrane Science, Vol. 320, Issue 1-2, p. 390-400 https://doi.org/10.1016/j.memsci.2008.04.030	journal	July 2008
Preparation and gas permeation of crown ether-containing co-polyimide with enhanced CO2 selectivity Wu, Dongyun; Yi, Chunhai; Wang, Yixuan Journal of Membrane Science, Vol. 551 https://doi.org/10.1016/j.memsci.2018.01.028	journal	April 2018
Polymeric membranes for CO2 separation and capture Han, Yang; Ho, W. S. Winston Journal of Membrane Science, Vol. 628 https://doi.org/10.1016/j.memsci.2021.119244	journal	June 2021
Materials selection guidelines for membranes that remove CO₂ from gas mixtures Lin, Haiqing; Freeman, Benny D. Journal of Molecular Structure, Vol. 739, Issue 1-3, p. 57-74 https://doi.org/10.1016/j.molstruc.2004.07.045	journal	April 2005
Polymers of intrinsic microporosity for energy-intensive membrane-based gas separations Wang, Y.; Ma, X.; Ghanem, B. S. Materials Today Nano, Vol. 3 https://doi.org/10.1016/j.mtnano.2018.11.003	journal	August 2018
Advanced functional polymer membranes Ulbricht, Mathias Polymer, Vol. 47, Issue 7 https://doi.org/10.1016/j.polymer.2006.01.084	journal	March 2006
Energy-efficient polymeric gas separation membranes for a sustainable future: A review Sanders, David F.; Smith, Zachary P.; Guo, Ruilan Polymer, Vol. 54, Issue 18 https://doi.org/10.1016/j.polymer.2013.05.075	journal	August 2013
State of the art and prospects of chemically and thermally aggressive membrane gas separations: Insights from polymer science Deng, Jing; Huang, Zihan; Sundell, Benjamin J. Polymer, Vol. 229 https://doi.org/10.1016/j.polymer.2021.123988	journal	August 2021
Crosslinked Matrimid®-like polyimide membranes with unimodal network structure for enhanced stability and gas separation performance Li, Si; McGinness, Hannah; Wang, Tao Polymer, Vol. 237 https://doi.org/10.1016/j.polymer.2021.124323	journal	December 2021
The strategies of molecular architecture and modification of polyimide-based membranes for CO2 removal from natural gas—A review Xiao, Youchang; Low, Bee Ting; Hosseini, Seyed Saeid Progress in Polymer Science, Vol. 34, Issue 6 https://doi.org/10.1016/j.progpolymsci.2008.12.004	journal	June 2009
A highly-efficient lithium adsorptive separation membrane derived from a polyimide-containing dibenzo-14-crown-4 moiety Zhu, Quanji; Ma, Xiaohua; Pei, Hongchang Separation and Purification Technology, Vol. 247 https://doi.org/10.1016/j.seppur.2020.116940	journal	September 2020
Enhanced gas separation by free volume tuning in a crown ether-containing polyimide membrane Zhang, Beibei; Qiao, Jie; Wu, Dongyun Separation and Purification Technology, Vol. 293 https://doi.org/10.1016/j.seppur.2022.121116	journal	July 2022
Gas Permeation Properties, Physical Aging, and Its Mitigation in High Free Volume Glassy Polymers Low, Ze-Xian; Budd, Peter M.; McKeown, Neil B. Chemical Reviews, Vol. 118, Issue 12 https://doi.org/10.1021/acs.chemrev.7b00629	journal	May 2018
High-Performance Carbon Molecular Sieve Membrane Derived from a Crown Ether-Containing Co-Polyimide Precursor for Gas Separation Wu, Dongyun; Qu, Xiwei; He, Xinping Industrial & Engineering Chemistry Research, Vol. 62, Issue 25 https://doi.org/10.1021/acs.iecr.3c01004	journal	June 2023
A Crown Ether-Containing Copolyimide Membrane with Improved Free Volume for CO₂ Separation Wu, Dongyun; Yi, Chunhai; Doherty, Cara M. Industrial & Engineering Chemistry Research, Vol. 58, Issue 31 https://doi.org/10.1021/acs.iecr.9b02502	journal	July 2019
Fine-Tuned Intrinsically Ultramicroporous Polymers Redefine the Permeability/Selectivity Upper Bounds of Membrane-Based Air and Hydrogen Separations Swaidan, Raja; Ghanem, Bader; Pinnau, Ingo ACS Macro Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsmacrolett.5b00512	journal	August 2015
van der Waals Volumes and Radii Bondi, A. The Journal of Physical Chemistry, Vol. 68, Issue 3, p. 441-451 https://doi.org/10.1021/j100785a001	journal	March 1964
Cyclic polyethers and their complexes with metal salts Pedersen, Charles J. Journal of the American Chemical Society, Vol. 89, Issue 26 https://doi.org/10.1021/ja01002a035	journal	December 1967
Stacking of Main Chain-Crown Ether Polymers in Thin Films Rueda, Daniel R.; Nogales, Aurora; Hernández, Jaime J. Langmuir, Vol. 23, Issue 25 https://doi.org/10.1021/la701734y	journal	December 2007
Seven chemical separations to change the world Sholl, David S.; Lively, Ryan P. Nature, Vol. 532, Issue 7600 https://doi.org/10.1038/532435a	journal	April 2016
Redefining the Robeson upper bounds for CO ₂ /CH ₄ and CO ₂ /N ₂ separations using a series of ultrapermeable benzotriptycene-based polymers of intrinsic microporosity Comesaña-Gándara, Bibiana; Chen, Jie; Bezzu, C. Grazia Energy & Environmental Science, Vol. 12, Issue 9 https://doi.org/10.1039/C9EE01384A	journal	January 2019
Macromolecular design strategies toward tailoring free volume in glassy polymers for high performance gas separation membranes Corrado, Tanner; Guo, Ruilan Molecular Systems Design & Engineering, Vol. 5, Issue 1 https://doi.org/10.1039/C9ME00099B	journal	January 2020
Hierarchically microporous membranes for highly energy-efficient gas separations Luo, Shuangjiang; Han, Tianliang; Wang, Can Industrial Chemistry & Materials, Vol. 1, Issue 3 https://doi.org/10.1039/D2IM00049K	journal	January 2023
Matrimid® 5218 in preparation of membranes for gas separation: Current state-of-the-art Castro-Muñoz, Roberto; Martin-Gil, Violeta; Ahmad, Mohd Zamidi Chemical Engineering Communications, Vol. 205, Issue 2 https://doi.org/10.1080/00986445.2017.1378647	journal	December 2017
Development of CO2-Selective Polyimide-Based Gas Separation Membranes Using Crown Ether and Polydimethylsiloxane Kim, Dongyoung; Hossain, Iqubal; Husna, Asmaul Polymers, Vol. 13, Issue 12 https://doi.org/10.3390/polym13121927	journal	June 2021

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CO2 separation
Crown ether
Free volume
Polyimide

Tuning gas separation performance of polyimide membranes with macrocyclic crown ether units

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