Title: Design and Gas Separation Performance of Imidazolium Poly(ILs) Containing Multivalent Imidazolium Fillers and Crosslinking Agents

Abstract

This work introduces a series of vinyl-imidazolium-based polyelectrolyte composites, which were structurally modified via impregnation with multivalent imidazolium-benzene ionic liquids (ILs) or crosslinked with novel cationic crosslinkers which possess internal imidazolium cations and vinylimidazolium cations at the periphery. A set of eight [C₄vim][Tf₂N]-based membranes were prepared via UV-initiated free radical polymerization, including four composites containing di-, tri-, tetra-, and hexa-imidazolium benzene ILs and four crosslinked derivatives which utilized tri- and tetra- vinylimidazolium benzene crosslinking agents. Structural and functional characterizations were performed, and pure gas permeation data were collected to better understand the effects of “free” ILs dispersed in the polymeric matrix versus integrated ionic crosslinks on the transport behaviors of these thin films. These imidazolium PIL:IL composites exhibited moderately high CO₂ permeabilities (~20–40 Barrer), a 4–7x increase relative to corresponding neat PIL, with excellent selectivities against N₂ or CH₄. The addition of imidazolium-benzene fillers with increased imidazolium content were shown to correspondingly enhance CO₂ solubility (di- < tri- < tetra- < hexa-), with the [C₄vim][Tf₂N]: [Hexa(Im⁺)Benz ][Tf₂N] composite showing the highest CO₂ permeability (P_CO2 = 38.4 Barrer), while maintaining modest selectivities (α_CO2/CH4 = 20.2, α_CO2/N2 = 23.6). Additionally, these metrics were similarly improved with the integration of more ionic contentmore » bonded to the polymeric matrix; increased P_CO2 with increased wt% of the tri- and tetra-vinylimidazolium benzene crosslinking agent was observed. This study demonstrates the intriguing interactions and effects of ionic additives or crosslinkers within a PIL matrix, revealing the potential for the tuning of the properties and transport behaviors of ionic polymers using ionic liquid-inspired small molecules.« less

Authors:

O’Harra, Kathryn E. ;

• Search DOE PAGES for author "O’Harra, Kathryn E."
• Search DOE PAGES for ORCID "0000-0001-5328-0024"

DeVriese, Emily M.; Turflinger, Erika M.; Noll, Danielle M.; Bara, Jason E.

• Search DOE PAGES for author "Bara, Jason E."
• Search DOE PAGES for ORCID "0000-0002-8351-2145"

Publication Date:

Sat Apr 24 00:00:00 EDT 2021

Research Org.:

Univ. of Alabama, Tuscaloosa, AL (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of Education

OSTI Identifier:

1780517

Alternate Identifier(s):

OSTI ID: 1852530

Grant/Contract Number:  

SC0018181; P200A180056

Resource Type:

Published Article

Journal Name:

Polymers

Additional Journal Information:

Journal Name: Polymers Journal Volume: 13 Journal Issue: 9; Journal ID: ISSN 2073-4360

Publisher:

MDPI AG

Country of Publication:

Switzerland

Language:

English

Subject:

36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; gas separation; ionic liquids; imidazolium; polyelectrolytes; crosslinkers; membranes