Polymer Bulletin

, Volume 75, Issue 11, pp 5321–5331 | Cite as

Synthesis and properties of ABPPQ for high-temperature proton exchange membrane fuel cells

  • Steve Lien-Chung Hsu
  • Chia-Wei Liu
  • Chia-Hui Tu
  • Hung-Yi Chuang
  • Elena Bulycheva
  • Natalya Belomoina
Original Paper


In this study, the one-pot synthesis of self-polymerizable quinoxaline monomer was developed. 3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline and 2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxaline mixture (M1a,b) was synthesized from benzyl 4-hydroxyphenyl ketone and 1,2-diamino-4-fluorobenzene, catalyzed by 1,4-diazabicyclo[2.2.2]octane. Then, an ether-containing AB type polyphenylquinoxaline (ABPPQ) was synthesized successfully from the monomer M1a,b. The ether-containing ABPPQ is organosoluble, and has good proton conductivity at high temperatures after doping with phosphoric acid. It is suitable for use in high-temperature proton exchange membrane fuel cells. Compared to polybenzimidazole (PBI), ABPPQ has higher acid doping level at the same doping time, because it has more sites that can be doped with phosphoric acid in the PPQ’s molecular structure than PBI.


Fuel cell Polyphenlyquinoxaline Phosphoric acid doping 



The authors are grateful for the financial support from the Ministry of Science and Technology (Taiwan, ROC) through project MOST 105-2923-E-006-003-MY3. Also, this research was, in part, supported by the Russian Foundation for Basic Research through project 16-53-52032 MNT.


  1. 1.
    Wycisk R, Pintauro PN, Park JW (2014) New developments in proton conducting membranes for fuel cells. Curr Opin Chem Eng 4:71–78CrossRefGoogle Scholar
  2. 2.
    Smitha B, Sridhar S, Khan AA (2005) Solid polymer electrolyte membranes for fuel cell applications—a review. J Membr Sci 259:10–26CrossRefGoogle Scholar
  3. 3.
    Shao Y, Yin G, Wang Z, Gao Y (2007) Proton exchange membrane fuel cell from low temperature to high temperature: material challenges. J Power Sources 167:235–242CrossRefGoogle Scholar
  4. 4.
    Rikukawa M, Sanui K (2000) Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers. Prog Polym Sci 25:1463–1502CrossRefGoogle Scholar
  5. 5.
    Li Q, He R, Jensen JO, Bjerrum NJ (2003) Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100 °C. Chem Mater 15:4896–4915CrossRefGoogle Scholar
  6. 6.
    Mader J, Xiao L, Schmidt TJ, Benicewicz BC (2008) Polybenzimidazole/acid complexes as high-temperature membranes. Adv Polym Sci 216:63–124Google Scholar
  7. 7.
    Bose S, Kuila T, Nguyen TXH, Kim NH, K-T Lau, Lee JH (2011) Polymer membranes for high temperature proton exchange membrane fuel cell: recent advances and challenges. Prog Polym Sci 36:813–843CrossRefGoogle Scholar
  8. 8.
    Asensio JA, Sánchez EM, Gómez-Romero P (2010) Proton-conducting membranes based on benzimidazole polymers for high-temperature PEM fuel cells. Chem Soc Rev 39:3210–3239CrossRefGoogle Scholar
  9. 9.
    Chandan A, Hattenberger M, El-kharouf A, Du S, Dhir A, Self V, Pollet BG, Ingram A, Bujalski W (2013) High temperature (HT) polymer electrolyte membrane fuel cells (PEMFC)—a review. J Power Sources 231:264–278CrossRefGoogle Scholar
  10. 10.
    Hergenorther PM, Levine HH (1970) Polyquinoxalines. 1. Synthesis and preliminary mechanical properties as laminating and adhesive resins. J Appl Polym Sci 14:1037–1048CrossRefGoogle Scholar
  11. 11.
    Hergenrother PM (1974) Polyphenylquinoxalines: synthesis, characterization, and mechanical properties. J Appl Polym Sci 18:1779–1791CrossRefGoogle Scholar
  12. 12.
    Hergenrother PM (1983) Polyphenylquinoxalines containing pendant phenylethynyl groups: preliminary mechanical properties. J Appl Polym Sci 28:355–366CrossRefGoogle Scholar
  13. 13.
    Gong F, Li N, Zhang S (2009) Synthesis and properties of novel sulfonated poly(phenylquinoxaline)s as proton exchange membranes. Polymer 50:6001–6008CrossRefGoogle Scholar
  14. 14.
    Rusanov AL, Belomoina NM, Bulycheva EG, Yanul NA, Likhatchev DY, Dobrovolskii YA, Iojoiu C, Sanchez J-Y, Voytekunas VY, Abadie MJM (2008) Preparation and characterization of sulfonated polyphenylquinoxalines. High Perform Polym 20:627–641CrossRefGoogle Scholar
  15. 15.
    Vasil’ev V, Buzin M, Nikiforova G, Belomoina N, Bulycheva E, Papkov V (2014) Ionomers of a new type based on sulfonated polyphenylquinoxalines. Dokl Phys Chem 458:149–152CrossRefGoogle Scholar
  16. 16.
    Seel DC, Benicewicz BC (2012) Polyphenylquinoxaline-based proton exchange membranes synthesized via the PPA process for high temperature fuel cell systems. J Membr Sci 405–406:57–67CrossRefGoogle Scholar
  17. 17.
    Klein DJ, Modarelli DA, Harris FW (2001) Synthesis of poly(phenylquinoxaline)s via self-polymerizable quinoxaline monomers. Macromolecules 34:2427–2437CrossRefGoogle Scholar
  18. 18.
    Qi C, Jiang H, Huang L, Chen Z, Chen H (2011) DABCO-catalyzed oxidation of deoxybenzoins to benzils with air and one-pot synthesis of quinoxalines. Synthesis 3:387–396Google Scholar
  19. 19.
    Chuang S-W, Hsu SL-C (2006) Synthesis and properties of a new fluorine-containing polybenzimidazole for high temperature fuel cell applications. J Polym Sci Part A Polym Chem 44:4508–4513CrossRefGoogle Scholar
  20. 20.
    Shen C-H, Hsu SL-C, Bulycheva E, Belomoina N (2012) Polybenzimidazole/1H-imidazole-4-sulfonic acid hybrid membranes for high-temperature proton exchange membranes fuel cells. J Membr Sci 399–400:11–15CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Materials Science and Engineering, Research Center for Energy Technology and Strategy, Center for Micro/Nano Science and TechnologyNational Cheng-Kung UniversityTainanTaiwan, ROC
  2. 2.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussia

Personalised recommendations