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Postmodification of highly delocalized cations in an azide-based polymer via copper-catalyzed cycloaddition for anion exchange membranes

Polymer Journal volume 55, pages 171–180 (2023)Cite this article

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Abstract

We synthesized a styrene-based polymer containing fused expanded pyridinium (FEP) moieties as side chains for an anion exchange membrane. FEPs were incorporated into poly(4-azidomethylstyrene) via copper-catalyzed alkyne-azide cycloaddition (click chemistry) to yield an FEP content of 10.5 mol%, which depended on the FEP feed ratio. The FEP polymer membrane containing 10.5 mol% of FEP exhibited high hydroxide conductivity of 123.4 (±13.3) mS cm–1 with a relatively low ion-exchange capacity of 0.77 (±0.03) at 80 °C under 80% relative humidity. Density functional theory studies revealed that FEP is a considerably soft acid owing to substantial delocalization of the positive charge in the rigid π structure. The high ion conductivity and low ion-exchange capacity can be attributed to weak interactions between the hard base (hydroxide ions) and soft acid (FEP).

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Acknowledgements

This study was supported in part by the SPRING program (No. JPMJSP2136), ACT-X (No. AJ219069-a01) and CREST (No. AJ199002) from Japan Science and Technology Agency (JST), Japan; the Nanotechnology Platform Project from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT), Japan; and KAKENHI (No. JP18H01816) and the Bilateral Program (No. AJ190078) from the Japan Society for the Promotion of Science (JSPS), Japan.

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Authors and Affiliations

  1. Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan

    Yuki Motoishi, Naoki Tanaka & Tsuyohiko Fujigaya

  2. The World Premier International Research Center Initiative, International Institute of Carbon Neutral Energy Research, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan

    Yuki Motoishi, Naoki Tanaka & Tsuyohiko Fujigaya

  3. Center for Molecular Systems, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan

    Tsuyohiko Fujigaya

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Correspondence to Tsuyohiko Fujigaya.

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Motoishi, Y., Tanaka, N. & Fujigaya, T. Postmodification of highly delocalized cations in an azide-based polymer via copper-catalyzed cycloaddition for anion exchange membranes. Polym J 55, 171–180 (2023). https://doi.org/10.1038/s41428-022-00730-z

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