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Covalently and ionically crosslinked sulfonated poly(arylene ether ketone)s as proton exchange membranes

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Abstract

A series of covalently and ionically crosslinked sulfonated poly(arylene ether ketone)s (SPAEKs) were prepared via the cyclocondensation reaction of crosslinkable SPAEKs with 3,3′-diaminobenzidine to form quinoxaline groups, where crosslinkable SPAEKs were synthesized by copolymerization of 4,4′-biphenol with 2,6-difluorobenzil, 4,4′-difluorobenzophenone, and 5,5′-carbonyl-bis(2-fluorobenzene sulfonate). The SPAEK membranes had high mechanical properties and the isotropic membrane swelling. The covalent and ionical crosslinking significantly improved the membrane performance, i.e., the crosslinked membranes showed the lower membrane dimensional change, lower methanol permeability, and higher oxidative stability than the corresponding uncrosslinked membranes, with keeping the reasonably high proton conductivity. The crosslinked membrane (CK3) with measured ion exchange capacity of 1.62 mequiv g−1 displayed a reasonably high proton conductivity of 110 mS/cm with water uptake of 33 wt% at 80 °C, and exhibited a low methanol permeability of 1.7 × 10−7 cm2 s−1 for 32 wt% methanol solution at 25 °C. The covalently and ionically crosslinked SPAEK membranes have potential for polymer electrolyte membrane fuel cells and direct methanol fuel cells.

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Acknowledgments

The authors would like to thank the Key Technologies R&D Program of Shaanxi Province (No. 2009K06-08), Program for Changjiang Scholars and Innovative Research Team in University (IRT1070), the Fundamental Research Funds for the Central Universities (No. GK200902002, GK201002002), and the Scientific Research Foundation for Returned Scholars, Ministry of Education for financial support of this work.

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Authors and Affiliations

  1. Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an, 710062, People’s Republic of China

    Pei Chen, Xinbing Chen & Zhongwei An

  2. Xian Modern Chemistry Research Institute, Xi’an, 710065, People’s Republic of China

    Zhongwei An

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  1. Pei Chen
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  2. Xinbing Chen
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Correspondence to Xinbing Chen.

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Chen, P., Chen, X. & An, Z. Covalently and ionically crosslinked sulfonated poly(arylene ether ketone)s as proton exchange membranes. Polym. Bull. 68, 1369–1386 (2012). https://doi.org/10.1007/s00289-011-0638-1

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