High molecular weight poly(phenylene sulfide sulfone) (PPSS) homo- and statistical copolymers have been reproducably synthesized using a known, but complex procedure utilizing 4,4'-dichlorodiphenyl sulfone (DCDPS), sodium hydrosulfide, sodium hydroxide, sodium acetate, and deionized water, in NMP at elevated reaction temperatures and pressure. The effect of these variations, e.g., reaction temperatures and times, molar ratios of H2O-to-NaSH, NMP-to-H2O, etc. were investigated. Optimized conditions were defined, which produced Tg as high as 222°C, very high refractive index (1.70), and tough/solvent resistant films could be prepared by melt fabrication. A two-stage decomposition mechanism in air was demonstrated by dynamic thermal gravimetric analysis. The melt stability of PPSS was improved by incorporating thermally stable endgroups, such as diphenyl sulfone, 4-chlorophenylphenyl sulfone, and t-butylphenoxide. The chemical structures of the endgroups were confirmed by 13C and 1H NMR spectra. Compared with mercaptide endcapped PPSS, the new systems showed higher initial degradation temperatures (2% and 5% weight loss), higher char yield at 650°C in air and a more stable melt viscosity at 300°C. A greatly simplified synthesis of both homo and copolymers has been successfully developed using the new A-A or A-B type thiol-functional monomers, such as bis-(4-mercaptophenyl) sulfone, 4-chloro-4'-mercaptodiphenyl sulfone and 4-chloro-4'-mercapto benzophenone, instead of sodium hydrosulfide. A series of high molecular weight triphenyl phosphine oxide and/or diphenyl ketone containing PPSS copolymers were subsequently synthesized from the bis-(4-mercaptophenyl) sulfone by reaction with 4,4'-dichlorodiphenyl sulfone, bis-(4-fluorophenyl) phenyl phosphine oxide, and 4,4'-difluorobenzophenone in DMAc in the presence of K2CO3 at 160°C. The new phosphine oxide containing PPSS copolymers were completely amorphous, showed improved solubility in common organic solvents and exhibited very high char yields in air at 750°C. Surface (XPS) analysis results suggested that the phosphorus moieties in the polymer backbone can form phosphate-like layers on the polymer surface which protects the inner materials from further decomposition in air at high temperatures. The diphenyl ketone containing PPSS copolymers showed very high char yields at 750°C in a nitrogen atmosphere, compared to sulfide sulfone homopolymer and phosphine oxide containing copolymers, possibly because of higher bond energies. Semi-crystalline poly(phenylene sulfide ketone) homopolymers and sulfone containing copolymers with sulfone/ketone mole ratio (S : K) < 25 : 75 were synthesized by a novel base catalyzed self-polycondensation of 4-chloro-4'-mercaptodiphenyl sulfone and/or 4-chloro-4'-mercapto benzophenone in N-cyclohexyl-2-pyrrolidinone (CHP) at 290°C. Amorphous copolymers with S : K ratios > 25 : 75 were prepared in DMAc at 160°C. These materials exhibited an increase in glass transition temperature with increasing sulfone content. TGA and micro cone calorimetry analyses showed that the semi-crystalline materials with high ketone content had much higher char yields and significantly lower heat release rate and total heat release, compared to the poly(phenylene sulfide sulfone) and poly(pheylene sulfide) controls. / Ph. D.

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A series of modified poly(arylene ether sulfone)s (PAES) incorporating hexafluoroisopropylidene units and co-monomers, bisphenol A (BA), 4,4′-dihydroxyterphenyl (DHTP) and triptycene-1,4-hydroquinone (TPDH), were synthesized using a polyetherification synthetic method. These thermoplastic PAES were copolymerized with the elastomer, polydimethylsiloxane (PDMS) to form segmented block copolymers. The segmented block copolymers with diverse PAES structures were studied and investigated for their thermal, tensile, and morphological properties. These multiphase segmented block copolymer materials have the potential to impart useful combinations of optical transparency, thermal stability, and enhanced tensile properties, and enhanced environmentally resistant properties for various high impact, high performance applications. In Chapter 2, hexafluoroisopropylidene bisphenol PAES (BAF PAES) segmented block copolymers containing various volume fraction of PDMS were synthesized. Analysis of the segmented block copolymer films by atomic force microscopy (AFM) and small angle x-ray scattering (SAXS) show the materials are microphase separated. Further analysis of the BAF PAES segmented block copolymers by transmission electron microscopy (TEM) show an increased morphological order with decreasing PDMS content, with lamellar morphologies formed at higher or near equal PAES and PDMS volume fractions. Comparatively, the morphological properties of the BAF PAES segmented block copolymers are considerably different from the isopropylidene bisphenol PAES (BA PAES) segmented block copolymer of similar PDMS volume percents. In this document, segmented block copolymers prepared from BA PAES incorporating 4,4′-dihydroxyterphenyl (DHTP) and triptycene-1,4-hydroquinone (TPDH) co-monomers were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR). Films of these materials, prepared from THF solution, were tested for thermal and tensile properties. These materials provide higher thermal stabilities over the BA PAES segmented block copolymers with thermal degradation ranging 380–435 °C under nitrogen at 5%-wt. loss. Similarly, the PAES incorporating co-monomers gave higher Tg (200 °C) than the BA PAES (183 °C) synthesized in our labs. Previously synthesized BA PAES segmented block copolymers showed plastic to elastomeric tensile properties upon increasing addition of PDMS content. These new segmented block copolymers, incorporating co-monomers, provided comparable results with the reported BA PAES segmented block copolymers analogues. The last research topic discussed in this dissertation covers the preparation of blends from 5% of segmented block copolymer and 95% of Udel®, donated by Solvay Advanced Polymers. The preparation of blends from the segmented block copolymers containing random copolymers led to materials with higher moduli than Udel® as observed by dynamic mechanical analysis (DMA). Tensile measurements performed by Instron also show the blends have high moduli, though no changes in the tensile elongation comparable to Udel®. / Ph. D.

This dissertation describes the past and recent progress in proton exchange membranes (PEM) for fuel cells. In particular the synthesis and characterization of materials for advanced alternative PEM were studied with an emphasis on structure-property and structure-property-performance relationships. The focus has included firstly a one-step synthesis and characterization of 3,3'-disulfonated 4,4'-dichlorodiphenyl sulfone comonomer. The procedure developed is adaptable for industrial-scale commercialization efforts. Secondly, the synthesis of aromatic nitrile containing poly (arylene ether sulfone) random copolymers was demonstrated. Various levels of disulfonation allowed the membrane characteristics to be investigated as a function of the membrane ion exchange capacity. The results favorably compare with the current state-of-the-art (Nafion™), particularly for direct methanol systems (DMFC). Thirdly, the mechanically and thermooxidatively stable copolymer membranes were blended with heteropolyacids producing nanocomposites which have potential in higher temperature fuel cell applications. Lastly, the basic PEM parameters such as water uptake, proton conductivity, and methanol permeabilities were controlled and presented as tunable properties as a function of molecular structure. This was achieved by in-situ control of chemical composition. The direct methanol fuel cell performance (DMFC) was much better than Nafion™. Hydrophobic surface properties of the membranes were improved by partial fluorination which made the Nafion™ bonded electrodes more compatible with the partially fluorinated copolymer membranes. The influence of surface enrichment had two important roles in increasing both initial and long term performance tests. The surface fluorine provided lower contact resistance and lower water uptake. The former was important for the initial tests and the latter provides for better long term performances. A delamination failure mechanism was proposed for the hydrocarbon membrane electrode assemblies (MEA) due to the large difference between water uptake of the catalyst layer and membrane and this was verified by a reduction in high frequency resistance (HFR) for the partially fluorinated systems. This thesis has generated the structure-property and structure-property-performance relationships which will provide direction for the development of next generation (PEM) materials. / Ph. D.