Precisely segmented PEEK–ionene + ionic liquid composite membranes for CO2 separation

Ravula, Sudhir; Chen, Ying; Wise, Kevin W.; Shinde, Pravin S.; Walter, Eric D.; Karkamkar, Abhi; Heldebrant, David J.; Bara, Jason E.

doi:10.1039/d3ta05223k

Precisely segmented PEEK–ionene + ionic liquid composite membranes for CO₂ separation

Journal Article · Tue Dec 19 23:00:00 EST 2023 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d3ta05223k· OSTI ID:2310368

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Univ. of Alabama, Tuscaloosa, AL (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Ionenes, polymers with ionic groups incorporated directly within the backbone are a highly versatile class of materials, although they have received much less attention than polyelectrolytes which have ionic groups pendant from the polymer backbone. By designing ionenes that incorporate robust properties of poly(ether ether ketone) (PEEK), we have achieved new imidazolium-containing PEEK–ionene architectures that create opportunities for enhanced CO₂ separation membranes. To achieve these materials, an new imidazole-functionalized PEEK oligomer (ImK(EEK)₂KIm) was synthesized through facile and straightforward routes. This molecule was then polymerized via condensation reactions with two different aromatic (α,α'-dibromo-p-xylene) and aliphatic (dibromohexyl containing-bis(imidazolium)hexane dibromide salt) comonomers and exchanged with bistriflimide ([Tf₂N]) anion to obtain two unique PEEK–ionenes containing distinct PEEK and ionic segments: p([ImK(EEK)₂Im-p-xyl][Tf₂N]₂) and p([ImK(EEK)₂(ImC₆)₃][Tf₂N]₄). While the neat PEEK–ionenes exhibited high molecular weight but were not able to form high-quality films, adding stoichiometric amounts of “free” IL (1-methyl-3-butylimidazolium bistriflimide, [C₄mIm][Tf₂N]), greatly improved the flexibility and processability of the resultant membranes. Further, the structure–property relationships of bulk PEEK–ionenes and corresponding composites were extensively characterized by different analytical techniques (thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, and solid-state NMR). In conclusion, the gas separation properties were investigated, with the PEEK–ionenes + IL composites exhibiting CO₂ permeabilities of 14–94 barrer and good CO₂/N₂ permselectivities of 26–35, indicating that new designs of segmented ionenes and composites with ILs a promising material design strategy for developing gas separation membranes.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

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

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2310368

Alternate ID(s):: OSTI ID: 2274850

Report Number(s):: PNNL-SA-194694

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 4 Vol. 12; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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