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Highly sulfonated poly(phenylene sulfones): optimization of the polymerization conditions

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Abstract

The preparation of highly sulfonated poly(phenylene sulfone) (ion exchange capacity = 4.45 meq g−1) by polycondensation of sulfonated difluorodiphenyl sulfone with metal sulfide and subsequent oxidation with hydrogen peroxide is optimized. The monomer/metal sulfide ratio, polymerization time and temperature, and type of metal sulfide have been varied. For the best conditions high molecular weights of up to 300 kg mol−1 are obtained reproducibly. This high molecular weight polyelectrolyte is meant to be used as main constituent of heterogeneous membrane structures such as interpenetrating networks, polymer blends, or simple physical mixtures with other polymers, e.g., for application in PEM fuel cells.

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References

  1. Park HB, Freeman BD, Zhang ZB, Sankir M, McGrath JE (2008) Highly chlorine-tolerant polymers for desalination. Angew Chem 120:6108–6113

    Article  Google Scholar 

  2. Kreuer KD (2001) On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells. J Membr Sci 185:29–39

    Article  CAS  Google Scholar 

  3. Goto K, Rozhanskii I, Yamakawa Y, Otsuki T, Naito Y (2009) Development of aromatic polymer electrolyte membrane with high conductivity and durability for fuel cell. Polym J 41(2):95–104

    Article  CAS  Google Scholar 

  4. Schuster M, Kreuer KD, Andersen HT, Maier J (2007) Sulfonated poly(phenylene sulfone) polymers as hydrolytically and thermooxidatively stable proton conducting ionomers. Macromolecules 40:598–607

    Article  CAS  Google Scholar 

  5. Saarinen V, Kreuer KD, Schuster M, Merkle R, Maier J (2007) On the swelling properties of proton conducting membranes for direct methanol fuel cells. Solid State Ion 178:533–537

    Article  CAS  Google Scholar 

  6. Schuster M, Araujo CC, Atanasov V, Andersen HT, Kreuer KD, Maier J (2009) Highly sulfonated poly(phenylene sulfone): preparation and stability issues. Macromolecules 42(8):3129–3137

    Article  CAS  Google Scholar 

  7. Araujo CC, Kreuer KD, Schuster M, Portale G, Mendil-Jakani H, Gebel G, Maier J (2009) Poly(p-phenylene sulfone)s with high ion exchange capacity: ionomers with unique microstructural and transport features. Phys Chem Chem Phys 11:3305–3312

    Article  Google Scholar 

  8. Ueda M, Toyota H, Ouchi T, Sugiyama J-I, Yonetake K, Masuko T, Teramoto T (1993) Synthesis and characterization of aromatic poly(ether sulfone)s containing pendant sodium sulfonate groups. J Polym Sci Part A Polym Chem 31:853–858

    Article  CAS  Google Scholar 

  9. Harrison WL, Wang F, Mecham JB, Bhanu VA, Hill M, Kim YS, McGrath JE (2003) Influence of the bisphenol structure on the direct synthesis of sulfonated poly(arylene ether) copolymers. I. J Polym Sci Part A Polym Chem 41:2264–2276

    Article  CAS  Google Scholar 

  10. Fahey DR, Ash CE (1991) Mechanism of poly(p-phenylene sulfide) growth from p-dichlorobenzene and sodium sulfide. Macromolecules 24(15):4242–4249

    Article  CAS  Google Scholar 

  11. Koch W, Risse W, Heitz W (1985) Radical ions as chain carriers in polymerization reactions. Makromol Chem Suppl 12:105–123

    Article  CAS  Google Scholar 

  12. Lubowitz HR, Sheppard CH (filed Jan 9, 1991, issued Jul 14, 1998) Reactive polyarylene sulfide oligomers. US Patent 5780583

  13. Matsuzaki M, Kagoshima M (filed Jul 18, 2002) Process for producing polyarylene sulfide. PCT Patent application 2004009674 A1

  14. Iizuka Y (filed May 25, 1989) Process for the preparation of cross-linked polyarylene sulfide. European Patent application 0344977 A2

  15. Kawashiwa K, Adachi T (filed Jul 29, 1999) Polyarylenesulfide resin composition. Patent application 0982369 A1

  16. Nishihata N, Tada M (filed Oct 27, 2003) Resin composition. European Patent application 1416015 A1

  17. Hedhli L, Lesclingant C, Fradet A, Maréchal E (1997) Kinetics of the reaction between alkaline sulfides and aryl dichlorides—model study on 4-chloro- and 4,4′-dichlorobenzophenones. Macromol Chem Phys 198:1–18

    Article  CAS  Google Scholar 

  18. Kricheldorf HR, Meier J, Schwarz G (1987) New polymer syntheses, 15†Syntheses of aromatic polyethers from difluorobenzonitriles and silylated diphenols. Makromol Chem Rapid Commun 8:529–534

    Article  CAS  Google Scholar 

  19. Robello DR, Ulman A, Urankar EJ (1993) Poly(p-phenylene sulfone). Macromolecules 26:6718–6721

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors acknowledge Annette Fuchs for IEC measurements, Udo Klock for TGA, and DSC analysis and Wolfgang Koenig for FT-IR spectra. R. Merkle is gratefully acknowledged for reading the proofs. BMBF (project HiPEM 03SF0323C) and the Stiftung Energieforschung Baden-Württemberg (FKZ A 23305) are acknowledged for financial support.

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  1. Vladimir Atanasov

    Present address: Institute of Chemical Process Engineering, University of Stuttgart, Böblingerstr. 78, 70569, Stuttgart, Germany

Authors and Affiliations

  1. Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569, Stuttgart, Germany

    Vladimir Atanasov, Matthias Buerger, Andreas Wohlfarth, Klaus-Dieter Kreuer & Joachim Maier

  2. FuMA-Tech GmbH, Am Grubenstollen 11, 66386, St. Ingbert, Germany

    Michael Schuster

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  1. Vladimir Atanasov
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  2. Matthias Buerger
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  3. Andreas Wohlfarth
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  4. Michael Schuster
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  5. Klaus-Dieter Kreuer
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  6. Joachim Maier
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Corresponding authors

Correspondence to Vladimir Atanasov or Klaus-Dieter Kreuer.

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Atanasov, V., Buerger, M., Wohlfarth, A. et al. Highly sulfonated poly(phenylene sulfones): optimization of the polymerization conditions. Polym. Bull. 68, 317–326 (2012). https://doi.org/10.1007/s00289-011-0539-3

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  • DOI: https://doi.org/10.1007/s00289-011-0539-3

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