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Synthesis and hydrolytic stability of soluble sulfonated polybenzoxazoles derived from bis(3-sulfonate-4-carboxyphenyl) sulfone

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Abstract

As a kind of high performance polymer, polybenzoxazoles are of interest as the matrix of proton exchange membrane (PEM). Soluble sulfonated polybenzoxazoles (sPBO) were synthesized by incorporation of the hexafluoroisopropylidene moieties into the polymer backbone, which show high molecular weight and excellent thermal stability. The hydrolytic stability of sPBO was investigated in detail in order to determine whether it is suitable for PEM applications or not. Contrary to expectation, sPBO membranes underwent hydrolysis under mild conditions. The hydrolysis of sPBO was confirmed by NMR, IR spectroscopy, and gel permeation chromatography. This work showed that sPBO membranes could not be used as PEM due to the poor hydrolytic stability.

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References

  1. Jones DJ, Rozière J (2003) Non-fluorinated polymer materials for proton exchange membrane fuel cells. Annu Rev Mater Res 33:503

    Article  CAS  Google Scholar 

  2. Savadogo O (2004) Emerging membranes for electrochemical systems Part II. High temperature composite membranes for polymer electrolyte fuel cell (PEFC) applications. J Power Sources 127:135

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  4. Rikukawa M, Sanui K (2000) Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers. Prog Polym Sci 25:1463

    Article  CAS  Google Scholar 

  5. Kerres J (2006) Covalent-ionically cross-linked poly(etheretherketone)-basic polysulfone blend ionomer membranes. Fuel Cells 6:251

    Article  CAS  Google Scholar 

  6. Li QF, He RH, Jensen JO, Bjerrum NJ (2003) Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100°C. Chem Mater 15:4896

    Article  CAS  Google Scholar 

  7. Lee HS, Roy A, Lane O, Dunn S, McGrath JE (2008) Hydrophilic–hydrophobic multiblock copolymers based on poly(arylene ether sulfone) via low-temperature coupling reactions for proton exchange membrane fuel cells. Polymer 49:715

    Article  CAS  Google Scholar 

  8. Wang Z, Ni HZ, Zhao CJ, Li XF, Zhang G, Shao K, Na H (2006) Influence of the hydroquinone with different pendant groups on physical and electrochemical behaviors of directly polymerized sulfonated poly(ether ether sulfone) copolymers for proton exchange membranes. J Membrane Sci 285:239

    Article  CAS  Google Scholar 

  9. Nakabayashi K, Matsumoto K, Ueda M (2008) Synthesis and properties of sulfonated multiblock copoly(ether sulfone)s by a chain extender. J Polym Sci Part A: Polym Chem 46:3947

    Article  CAS  Google Scholar 

  10. Matsumura S, Hlil AR, Lepiller C, Gaudet J, Guay D, Shi ZQ, Holdcroft S, Hay AS (2008) Ionomers for proton exchange membrane fuel cells with sulfonic acid groups on the end groups: novel branched poly(ether-ketone)s. Macromolecules 41:281

    Article  CAS  Google Scholar 

  11. Liu BJ, Robertson GP, Kim DS, Guiver MD, Hu W, Jiang ZH (2007) Aromatic poly(ether ketone)s with pendant sulfonic acid phenyl groups prepared by a mild sulfonation method for proton exchange membranes. Macromolecules 40:1934

    Article  CAS  Google Scholar 

  12. Bai ZW, Dang TD (2006) Direct synthesis of fully sulfonated polyarylenethioether sulfones as proton-conducting polymers for fuel cells. Macromol Rapid Commun 27:1271

    Article  CAS  Google Scholar 

  13. Genies C, Mercier R, Sillion B, Cornet N, Gebel G, Pineri M (2001) Soluble sulfonated naphthalenic polyimides as materials for proton exchange membranes. Polymer 42:359

    Article  CAS  Google Scholar 

  14. Miyatake K, Asano N, Watanabe M (2003) Synthesis and properties of novel sulfonated polyimides containing 1,5-naphthylene moieties. J Polym Sci Part A: Polym Chem 41:3901

    Article  CAS  Google Scholar 

  15. Yin Y, Fang JH, Watari T, Tanaka K, Kita H, Okamoto K (2004) Synthesis and properties of highly sulfonated proton conducting polyimides from bis(3-sulfopropoxy)benzidine diamines. J Mater Chem 14:1062

    Article  CAS  Google Scholar 

  16. Xiao GY, Sun GM, Yan DY, Zhu PF, Tao P (2002) Synthesis of sulfonated poly(phthalazinone ether sulfone)s by direct polymerization. Polymer 19:5335

    Article  Google Scholar 

  17. Xiao GY, Sun GM, Yan DY (2002) Polyelectrolytes for fuel cells made of sulfonated poly (phthalazinone ether ketone)s. Macromol Rapid Commun 23:488

    Article  CAS  Google Scholar 

  18. Chen YL, Meng YZ, Li XH, Hay AS (2005) Poly(phthalazinone ether ketone) ionomers synthesized via N–C coupling reaction for fuel cell applications. Macromolecules 38:10007

    Article  CAS  Google Scholar 

  19. Zhu XL, Liang YF, Pan HY, Jian XG, Zhang YX (2008) Synthesis and properties of novel H-bonded composite membranes from sulfonated poly(phthalazinone ether)s for PEMFC. J Membrane Sci 312:59

    Article  CAS  Google Scholar 

  20. Ma XH, Shen LP, Zhang CJ, Xiao GY, Yan DY, Sun GM (2008) Sulfonated poly(arylene thioether phosphine oxide)s copolymers for proton exchange membrane fuel cells. J Membrane Sci 310:303

    Article  CAS  Google Scholar 

  21. Ma XH, Zhang CH, Xiao GY, Yan DY (2008) Synthesis and characterization of sulfonated poly(phthalazinone ether phosphine oxide)s by direct polycondensation for proton exchange membranes. J Polym Sci Part A: Polym Chem 46:1758

    Article  CAS  Google Scholar 

  22. Asensio JA, Borros S, Gomez-Romero P (2002) Proton-conducting polymers based on benzimidazoles and sulfonated benzimidazoles. J Polym Sci Part A: Polym Chem 40:3703

    Article  CAS  Google Scholar 

  23. Qing SB, Huang W, Yan DY (2005) Synthesis and characterization of thermally stable sulfonated polybenzimidazoles obtained from 3,3′-disulfonyl-4,4′-dicarboxyldiphenylsulfone. J Polym Sci Part A: Polym Chem 43:4363

    Article  CAS  Google Scholar 

  24. Xiao LX, Zhang HF, Scanlon E, Ramanathan LS, Choe EW, Rogers D, Apple T, Benicewicz BC (2005) High-temperature polybenzimidazole fuel cell membranes via a sol–gel process. Chem Mater 17:5328

    Article  CAS  Google Scholar 

  25. Jannasch P (2005) Fuel cell membrane materials by chemical grafting of aromatic main-chain polymers. Fuel Cells 5:248

    Article  CAS  Google Scholar 

  26. Kim JD, Honma I (2005) Anhydrous solid state proton conductor based on benzimidazole/monododecyl phosphate molecular hybrids. Solid State Ionics 176:979

    Article  CAS  Google Scholar 

  27. Yang HH (1989) Aromatic heterocyclic polymers. In: Aromatic high-strength fibers. Wiley, New York, pp 833–842

    Google Scholar 

  28. Arnold C (1979) Stability of high-temperature polymers. J Polym Sci Part D: Macromol Rev 14:265

    Article  CAS  Google Scholar 

  29. Ebara K, Shibasaki Y, Ueda M (2003) Photosensitive poly(benzoxazole) based on precursor from diphenyl isophthalate and bis(o-aminophenol). Polymer 44:333

    Article  CAS  Google Scholar 

  30. Sakaguchi Y, Kitamura K, Nakao J, Hamamoto S, Tachimori H, Takase S (2001) Preparation and properties of sulfonated or phosphonated polybenzimidazoles and polybenzoxazoles. Polym Mater Sci Eng 84:899

    CAS  Google Scholar 

  31. Hilborn JG, Labadie JW, Hedrick JL (1990) Poly(aryl ether-benzoxazoles). Macromolecules 23:2854

    Article  CAS  Google Scholar 

  32. Holmes GA, Rice K, Snyder CR (2006) Ballistic fibers: a review of the thermal, ultraviolet and hydrolytic stability of the benzoxazole ring structure. J Mater Sci 41:4105

    Article  CAS  Google Scholar 

  33. So YH, Martin SJ, Owen K, Smith PB (1999) A study of benzobisoxazole and benzobisthiazole compounds and polymers under hydrolytic conditions. J Polym Sci Part A: Polym Chem 37:2637

    Article  CAS  Google Scholar 

  34. Kim YJ, Einsla BR, Tchachoua CN, McGrath JE (2005) Synthesis of high molecular weight polybenzoxazoles in polyphosphoric acid and investigation of their hydrolytic stability under acidic conditions. High Perform Polym 17:377

    Article  CAS  Google Scholar 

  35. Jackson PF, Morgan KJ, Turner AM (1972) Studies in heterocyclic chemistry. Part IV. Kinetics and Mechanisms for the hydrolysis of benzoxazoles. J Chem Soc Perkin Trans II 11:1582

    Article  Google Scholar 

  36. Werstiuk NH, Chen J (1989) Protium–deuterium exchange of benzo-substituted heterocycles in neutral D2O at elevated temperatures. Can J Chem 67:812

    Article  CAS  Google Scholar 

  37. Einsla BR, Kim YJ, Tchatchoua C, McGrath JE (2003) Disulfonated polybenzoxazoles for proton exchange membrane fuel cell applications. Abstr Pap Am Chem Soc 226:U391

    Google Scholar 

  38. Hsu SLC, Chang KC, Huang YP, Tsai SJ (2003) A novel synthesis method for the preparation of aromatic poly(imide benzoxazole) from trimellitic anhydride chloride and bis(o-aminophenol). J Appl Polym Sci 88:2388

    Article  CAS  Google Scholar 

  39. Li JH, Lee YM (2006) Synthesis and characterization of highly soluble poly(aryl ether ketonebenzoxazole) copolymers with hexafluoroisopropylidene moieties by direct copolymerization. Macromol Chem Phys 207:1880

    Article  CAS  Google Scholar 

  40. Hsiao SH, Yu CH (1998) Aromatic polybenzoxazoles bearing ether and isopropylidene or hexafluoroisopropylidene units in the main chain. Macromol Chem Phys 199:1247

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (No: 50303010), the Science and Technology Committee of Shanghai municipality (No: 065207065), and the National High Technical Research Development Program (No: 2002AA323040).

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, 200240, Shanghai, People’s Republic of China

    Ning Tan, Guyu Xiao & Deyue Yan

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  1. Ning Tan
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  2. Guyu Xiao
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  3. Deyue Yan
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Correspondence to Guyu Xiao or Deyue Yan.

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Tan, N., Xiao, G. & Yan, D. Synthesis and hydrolytic stability of soluble sulfonated polybenzoxazoles derived from bis(3-sulfonate-4-carboxyphenyl) sulfone. Polym. Bull. 62, 593–604 (2009). https://doi.org/10.1007/s00289-009-0042-2

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