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

Journal Article · · Polymers

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 (PCO2 = 38.4 Barrer), while maintaining modest selectivities (αCO2/CH4 = 20.2, αCO2/N2 = 23.6). Additionally, these metrics were similarly improved with the integration of more ionic content bonded to the polymeric matrix; increased PCO2 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.

Research Organization:
Univ. of Alabama, Tuscaloosa, AL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of Education
Grant/Contract Number:
SC0018181; P200A180056
OSTI ID:
1780517
Alternate ID(s):
OSTI ID: 1852530
Journal Information:
Polymers, Journal Name: Polymers Vol. 13 Journal Issue: 9; ISSN 2073-4360
Publisher:
MDPI AGCopyright Statement
Country of Publication:
Switzerland
Language:
English

References (45)

MATERIALS SCIENCE: A Unique Platform for Materials Design journal July 2008
The solution-diffusion model: a review journal November 1995
Tailored CO 2 -Philic Anionic Poly(ionic liquid) Composite Membranes: Synthesis, Characterization, and Gas Transport Properties journal March 2020
CO2/H2 separation through poly(ionic liquid)–ionic liquid membranes: The effect of multicomponent gas mixtures, temperature and gas feed pressure journal March 2021
One-Step Synthesis of Thermosensitive Nanogels Based on Highly Cross-Linked Poly(ionic liquid)s journal August 2012
CO2/light gas separation performance of cross-linked poly(vinylimidazolium) gel membranes as a function of ionic liquid loading and cross-linker content journal April 2012
Synthesis and gas separation properties of poly(ionic liquid)-ionic liquid composite membranes containing a copper salt journal October 2016
Imidazole- and imidazolium-containing polymers for biology and material science applications journal May 2010
Synthesis and Performance of 6FDA-Based Polyimide-Ionenes and Composites with Ionic Liquids as Gas Separation Membranes journal July 2019
Tailoring macromolecular architecture with imidazole functionality: A perspective for controlled polymerization processes journal April 2011
Supramolecular Structures from Polycarbene Ligands and Transition Metal Ions journal January 2011
In Situ Preparation of Crosslinked Polymer Electrolytes for Lithium Ion Batteries: A Comparison of Monomer Systems journal July 2020
Recent Advances in the Design of Ionenes: Toward Convergence with High‐Performance Polymers journal May 2019
Gas permeation studies in supported ionic liquid membranes journal July 2010
Toward controlled functional sequencing and hierarchical structuring in imidazolium ionenes journal September 2020
Olefin metathesis-crosslinked, bulky imidazolium-based anion exchange membranes with excellent base stability and mechanical properties journal March 2020
Combination of ionic liquids with membrane technology: A new approach for CO2 separation journal January 2016
Membrane-based gas separation journal August 1993
Ionic Polyimides: Hybrid Polymer Architectures and Composites with Ionic Liquids for Advanced Gas Separation Membranes journal April 2017
Energy-efficient polymeric gas separation membranes for a sustainable future: A review journal August 2013
Synthesis of imidazolium-mediated Poly(benzoxazole) Ionene and composites with ionic liquids as advanced gas separation membranes journal February 2021
Guide to CO 2 Separations in Imidazolium-Based Room-Temperature Ionic Liquids journal March 2009
Preparation of Thermo-Responsive Poly(ionic liquid)s-Based Nanogels via One-Step Cross-Linking Copolymerization journal September 2015
Imidazolium-Based Poly(ionic liquid)/Ionic Liquid Ion-Gels with High Ionic Conductivity Prepared from a Curable Poly(ionic liquid) journal May 2016
Polymeric ionic liquids: Broadening the properties and applications of polyelectrolytes journal December 2011
Ionic Liquid Cross-Linked Multifunctional Cationic Polymer Nanobeads via Dispersion Polymerization: Applications in Anion Exchange, Templates for Palladium, and Fluorescent Carbon Nanoparticles journal February 2015
Vibrational Spectroscopy of Ionic Liquids journal January 2017
Synthesis and Performance of Polymerizable Room-Temperature Ionic Liquids as Gas Separation Membranes journal August 2007
Designing Imidazolium Poly(amide-amide) and Poly(amide-imide) Ionenes and Their Interactions with Mono- and Tris(imidazolium) Ionic Liquids journal May 2020
High performance membranes based on ionic liquid polymers for CO2 separation from the flue gas journal January 2012
Recent Advances in Innovative Polymer Electrolytes based on Poly(ionic liquid)s journal September 2015
Syntheses, structures, and properties of Co(II)/Zn(II) mixed-ligand coordination polymers based on 4-[(3,5-dinitrobenzoyl)amino]benzoic acid and 1,4-bis(1-imidazolyl) benzene journal May 2015
Self‐healing imidazolium‐based ionene‐polyamide membranes: an experimental study on physical and gas transport properties journal March 2019
Preparation and characterization of directional conducting and lower methanol permeable ultrathin membrane based on poly (vinyl alcohol) and imidazolium compounds journal October 2014
Systematic Investigation of the Photopolymerization of Imidazolium-Based Ionic Liquid Styrene and Vinyl Monomers: Systematic Investigation of the Photopolymerization of Imidazolium-Based Ionic Liquid Styrene and Vinyl Monomers
  • Whitley, John W.; Jeffrey Horne, William; Shannon, Matthew S.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 56, Issue 20 https://doi.org/10.1002/pola.29211
journal September 2018
Ionic liquid-based materials: a platform to design engineered CO 2 separation membranes journal January 2016
Synthesis and Performance of Aromatic Polyamide Ionenes as Gas Separation Membranes journal March 2020
Recent progress in ionic liquid membranes for gas separation journal September 2018
Design and Synthesis of Imidazolium-Mediated Tröger’s Base-Containing Ionene Polymers for Advanced CO 2 Separation Membranes journal February 2019
Vinyl-Functionalized Poly(imidazolium)s: A Curable Polymer Platform for Cross-Linked Ionic Liquid Gel Synthesis journal January 2014
Thermomechanical and Conductive Properties of Thiol–Ene Poly(ionic liquid) Networks Containing Backbone and Pendant Imidazolium Groups journal November 2018
Reaction of Diazole Anions with Hexafluorobanzene: An Unexpectedly Facile Entry into Hexa(diazol-1-yl)benzenes journal January 1993
Poly(ionic liquid)s: An update journal July 2013
Main-chain imidazolium polymer membranes for CO2 separations: An initial study of a new ionic liquid-inspired platform journal September 2010
Membrane Gas Separation: A Review/State of the Art journal May 2009