Synthesis and characterization of photosensitive poly(imide sulfonates) for fuel cell application

Abstract

The novel sulfonated polyimide membranes were successfully synthesized by thermal imidization with monomers of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4′-diaminodiphenyl ether-2,2′-disulfonic acid (SODA) and 3,3′-diaminochalcone (3DAC). Photosensitive chalcone moiety was introduced to the main chain of copolymers, and the photocrosslinking of resulting copolymer in aqueous electrolyte was attempted. A series of sulfonated copolyimide precursors containing chalcone functional groups in the main chain were prepared with different sulfonation degrees by controlling the molar ratio of SODA, 6FDA and 3DAC. The polymer membranes were prepared from these sulfonated aromatic precursors by solution casting and subsequent thermal imidization. The crosslinking with UV irradiation was attempted in the presence or absence of distilled water. The characterizations of the resulting membrane such as the ion-exchange capacity, water absorption and ionic conductivity were performed with respect to the copolymer compositions and the photocrosslinking conditions.

Keywords

sulfonated polyimide / photosensitive / chalcone / polymer electrolyte membrane / fuel cell

References

[1] Thomas S, Zalbowitz M Fuel Cells-Green Power[M], 1999

[2] Fang J, Guo X, Harada S, . Novel Sulfonated Polyimides as Polyelectrolytes for Fuel Cell Application. 1. Synthesis, Proton Conductivity, and Water Stability of Polyimides from 4,4′-Diaminodiphenyl Ether-2,2′-Disulfonic Acid[J]. Macromolecules, 2002, 35(24): 9 022-9 028.

[3] Ye X, Bai H, Winston WS Synthesis and Characterization of New Sulfonated Polyimides as Proton-exchange Membranes for Fuel Cells[J]. J. Membr. Sci., 2006, 279(1–2): 570-577.

[4] Guo X, Fang J, Watari T, . Novel Sulfonated Polyimides as Polyelectrolytes for Fuel Cell Application. 2. Synthesis and Proton Conductivity of Polyimides from 9,9-Bis(4-aminophenyl)fluorene-2,7-Disulfonic Acid[J]. Macromolecules, 2002, 35(17): 6 707-6 713.

[5] Bishop M T, Karasz F E, Russo PS, . Solubility and Properties of Poly(aryl-ether-ketone) in Strong Acids[J]. Macromolecules, 1985, 18(1): 86-93.

[6] Jin X, Bishop MT, Ellis TS, . A Sulfonated Poly(aryl-etherketone)[J]. Br. Polym. J., 1985, 17: 4-10.

[7] Shibuya N, Porter RS Kinetics of PEEK Sulfonation in Concentrated Sulfuric Acid[J]. Macromolecules, 1992, 25(24): 6 495-6 499.

[8] Jia L, Xu X, Zhang H, . Sulfonation of Poly(ether ether ketone) and Its Effects on Permeation Behavior to Nitrogen and Water Vapor[J]. J. Appl. Polym. Sci., 1996, 60(8): 1 231-1 237.

[9] Trotta F, Drioli E, Moraglio G, . Sulfonation of Polyetheretherketone by Chlorosulfuric Acid[J]. J. Appl. Polym. Sci., 1998, 70(3): 477-482.

[10] Noshay A, Robeson LM Sulfonated Polysulfone[J]. J. Appl. Polym. Sci., 1976, 20: 1 885-1 903.

[11] Johnson B C, Yilgor I, Tran C, . Synthesis and Characterization of Sulfonated Poly(arylene ether sulfones)[J]. J. Polym. Sci., Part A: Polym. Chem., 1984, 22(3): 721-737.

[12] Lufrano F, Squadrito G, Patti A, . Sulfonated Polysulfone as Promising Membranes for Polymer Electrolyte Fuel Cells[J]. J. Appl. Polym. Sci., 2000, 77(6): 1 250-1 257.

[13] Nolte R, Ledjeff K, Bauer M, . Partially Sulfonated Poly(arylene ether sulfone) -a Versatile Proton Conducting Membrane Material for Modern Energy Conversion Technologies[J]. J. Membr. Sci., 1993, 83(2): 211-220.

[14] Meng YZ, Tjong SC, Hay AS, . Synthesis and Proton Conductivities of Phosphonic Acid Containing Poly-(arylene ether)s[J]. J. Polym. Sci., Part A: Polym. Chem., 2001, 39(19): 3 218-3 226.

[15] Faure S, Aldebert P, Mercier R, . Sulphonated Polyimides Membranes Prepared with Them and a Fuel Cell Device that Includes These Membranes[P], 1996

[16] Faure S, Cornet T, Gebel G, . Proceeding of Second International Symposium on New Materials for Fuel Cell and Modern Battery Systems[C], 1997 818

[17] Xing P, Robertson G P, Guiver M D, . Sulfonated Poly(aryl ether ketone)s Containing the Hexafluoroisopropylidene Diphenyl Moiety Prepared by Direct Copolymerization as Proton Exchange Membranes for Fuel Cell Application[J]. Macromolecules, 2004, 37(21): 7 960-7 967.

[18] Genies C, Mercier R, Sillion B, . Stability Study of Sulfonated Phthalic and Naphthalenic Polyimide Structures in Aqueous Medium[J]. Polymer, 2001, 42(12): 5 097-5 105.

[19] Küver A, Potje-Kamloth K Comparative Study of Methanol Crossover across Electropolymerized and Commercial Proton Exchange Membrane Electrolytes for the Acid Direct Methanol Fuel Cell[J]. Electrochim. Acta, 1998, 43(16–17): 2 527-2 535.

[20] Pourcelly G Conductivity and Selectivity of Ion Exchange Membranes: Structure-correlations[J]. Desalination, 2002, 147(1–3): 359-361.

[21] Feng K, Tsushima M, Matsumoto T, . Synthesis and Properties of Novel Photosensitive Polyimides Containing Chalcone Moiety in the Main Chain[J]. J. Polym. Sci., Part A: Polym. Chem., 1998, 36(5): 686-698.

[22] Jang W, Lee C, Sundar S, . Thermal and Hydrolytic Stability of Sulfonated Polyimide Membranes with Varying Chemical Structure[J]. Polym. Degrad. Stab., 2005, 90(3): 431-440.

[23] Helmer MF, Osan F, Schneller A, . Polymer Electrolyte Membrane and Process for the Production Thereof[P], 1995

[24] Bonnet B, Jones DJ, Roziere J, . Hybrid Organic-inorganic Membranes for a Medium Temperature Fuel Cell[J]. J. New Mater. Electrochem. Syst., 2000, 3(2): 87-92.