Title page for ETD etd-04252001-180802


Type of Document Dissertation
Author Mecham, Jeffrey B.
URN etd-04252001-180802
Title Direct Polymerization Of Sulfonated Poly(arylene ether) Random Copolymers And Poly(imide)Sulfonated Poly(arylene ether) Segmented Copolymers: New Candidates For Proton Exchange Membrane Fuel Cell Material Systems
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
McGrath, James E. Committee Chair
Anderson, Mark R. Committee Member
Dillard, John G. Committee Member
Shultz, Allan R. Committee Member
Wolfe, James F. Committee Member
Keywords
  • Sulfonic Acid Sites
  • Poly(arylene ether)
  • Random Copolymer
  • Poly(imide)
  • Direct Copolymerization
  • Segmented Copolymer
  • Proton Exchange Membrane
Date of Defense 2001-04-23
Availability unrestricted
Abstract
Commercially available 4,4’-dichlorodiphenylsulfone (DCDPS) was successfully disulfonated with fuming sulfuric acid to yield 3,3’-disodiumsulfonyl-4,4’-dichlorodiphenylsulfone (SDCDPS). Subsequently, DCDPS and SDCDPS were systematically reacted with 4,4’-biphenol under nucleophilic step polymerization conditions to generate a series of high molecular weight, film-forming, ductile, ion conducting copolymers. These were converted to the acid form and investigated as proton exchange membranes for fuel cells. Hydrophilicity increased with the level of sulfonation. However, water sorption increased gradually until about 50 mole percent SDCDPS was incorporated, and thereafter showed a large increase to yield water soluble materials for the 100% SDCDPS system. Atomic force microscopy (AFM) confirmed that the morphology of the copolymers displayed continuity of the hydrophilic phase at 60 mole percent SDCDPS. Conductivity measurements in the 40-50 mole percent SDCDPS range, where excellent mechanical strength was maintained, produced values of 0.1 S/cm or higher which were comparable to the control, Nafion™. These compositions also show a high degree of compatibility with heteropolyacids such as phosphotungstic acid. These inorganic compounds provide a promising mechanism for obtaining conductivity at temperatures well above the boiling point of water and membrane compositions containing them are being actively pursued.

The water soluble 100% SDCDPS system was further investigated by successfully functionalizing the endgroups to afford aromatic amines via appropriate endcapping with m-aminophenol. Oligomers and polymers from 5-30 kg/mole number average molecular weight were synthesized and well characterized by NMR spectroscopy, endgroup titrations and size exclusion chromatography. The diamino-telechelic sulfonated segment was reacted with several dianhydrides and diamines to produce multiblock, hydrophobic polyimide-hydrophilic sulfonated polyarylene ether copolymers. Both ester-acid and amic acid synthesis routes were utilized in combination with spin-casting and bulk imidization. A series of tough, film-forming segmented copolymers was prepared and characterized. AFM measurements demonstrated the generation of quite well defined, nanophase-separated morphologies which were dependent upon composition as well as aging in a humid environment. Characterizations of the segmented copolymers for conductivity, and water and methanol sorption were performed and comparisons to state-of-the-art perfluorinated Nafion™ systems were made. It is concluded that the segmented or block systems have the potential to enhance certain desirable PEM characteristics in fuel cells, particularly those related to swelling, retention of mechanical strength at elevated temperatures, and critical adhesion issues in membrane electrode assemblies.

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