Hydrophilic/hydrophobic block copolymers as proton exchange membranes (PEMs) has become an emerging area of research in recent years. Three series of hydrophilic/hydrophobic, fluorinated/sulfonated multiblock copolymers were synthesized and characterized in this thesis. These copolymers were obtained through moderate temperature (~100°C) coupling reactions, which minimize the ether-ether interchanges between hydrophobic and hydrophilic telechelic oligomers via a nucleophilic aromatic substitution mechanism. The hydrophilic blocks were based on the nucleophilic step polymerization of 3,3′-disulfonated, 4,4′-dichlorodiphenyl sulfone with an excess 4,4′-biphenol to afford phenoxide endgroups. The hydrophobic (fluorinated) blocks were largely based on decafluoro biphenyl (excess) and various bisphenols. The copolymers were obtained in high molecular weights and were solvent cast into tough membranes, which had nanophase separated hydrophilic and hydrophobic regions. The performance and structure-property relationships of these materials were studied and compared to random copolymer systems. NMR results supported that the multiblock sequence had been achieved. They displayed superior proton conductivity, due to the ionic proton conducting channels formed through the self-assembly of the sulfonated blocks. The nano-phase separated morphologies of the copolymer membranes were studied and confirmed by atomic force microscopy. Through control of a variety of parameters, including ion exchange capacity and sequence lengths, performances as high, or even higher than those of the state-of-the-art PEM, Nafion, were achieved. / Ph. D.

Phosphorus-containing high performance polymers have been extensively studied during the last 10 years. These materials are of interest for a variety of optical and fire resistant properties, as well as for their ability to complex with the inorganic salts. This dissertation has focused on the nature of the phosphonyl group interactions with hydroxyl containing polymers, such as the poly(hydroxy ether)s. These may be considered linear models of epoxy resins and are also closely related to dimethacrylate (vinyl ester) matrix resins that are important for composite systems. It has been shown that bisphenol A poly(arylene ether phosphine oxide/sulfone) homo- or statistical copolymers are miscible with a bisphenol A-epichlorohydrin based poly(hydroxy ethers) (PHE), as shown by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC), infrared spectroscopy and , solid state cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS). These measurements illustrate the strong hydrogen bonding between the phosphonyl groups of the copolymers and the pendent hydroxyl groups of the PHE as the miscibility inducing mechanism. Complete miscibility at all blend compositions was achieved with as little as 20 mole% of phosphine oxide units in the poly(arylene ether) copolymer. Replacement of the bisphenol A moiety by other diphenols, such as hydroquinone, hexafluorobisphenol A and biphenol did not significantly affect blend miscibilities. Miscible polymer blends with PHE were also made by blending poly(arylene thioether phosphine oxide), and fully cyclized phosphine oxide containing polyimides based on (prepared from 2,2'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and bis(m-aminophenyl) methyl phosphine oxide (DAMPO)) or bis(m-aminophenyl) phenyl phosphine oxide). Additional research has focused on the influence of these materials on the property characteristics of vinyl ester matrix resins and has shown that the concentration of phosphonyl groups controls the homogeneity of both oligomers and the resulting networks. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fracture toughness measurements further confirmed the qualitative observations. Metal salts, such as CoCl2 and CuCl2 had earlier been demonstrated to form complexes/nanocomposites with phosphorus-containing poly(arylene ethers). It has been possible to prepare transparent films with 100 mol% of metal chlorides, based upon the phosphonyl groups. The films are transparent, unlike the opaque polysulfone control systems. FTIR results suggested the formation of inorganic salt and polymer complexes at low concentrations. TEM showed homogeneous morphology at low concentrations and excellent dispersion even at high mole % of salts. Cobalt materials reinforce the basic poly(arylene ether)s to provide higher modulus values and influence positively the char yield generated after TGA experiments in air. The cobalt salt/BPADA-DAMPO polyimide composites also yield transparent films, implying very small dimensions. Silica-polymer nanocomposites were also produced by mixing commercial silica colloid/N,N-dimethylacetamide (DMAc) fine dispersions (~ 12 nm) with bisphenol A poly(arylene ether phenyl phosphine oxide). The dry films produced by solution casting are transparent and silica colloids are evenly dispersed (~ 12 nm) into the polymer matrix as shown by TEM. These nanocomposites increased char yield compared with the polymer control, suggesting their fire retardant character. In comparison, the silica/polysulfone hybrid films prepared by the same methods were opaque and the char yield was not improved. This different phase behavior has been explained to be due to the hydrogen bonding between phosphonyl groups and silanol hydroxyl groups on the surface of the nanosilica. / Ph. D.

The objectives of this research were to study the gas transport properties of proton exchange membranes (PEM), namely disulfonated poly(arylene ether sulfone) (BPSH-35), post sulfonated diels-alder poly(phenylene) (SDAPP), and poly(perfluoro sulfonic acid) (Nafion). The O2 gas permeabilities were found to be lower in BPSH and SDAPP as compared to poly(perfluoro sulfonic acid) because of difference in Tg (TgBSPH= 250 oC, TgSDAPP= 330 oC versus TgNafion=150 oC). Higher Tg polymers have a more rigid, inflexible polymer segments causing a reduction in gas permeability. In comparison to SDAPP, BPSH has a lower O2 gas permeability because of the bulky side groups in the SDAPP backbone. O2 sorption measurements were carried out both under non-humidified and humidified conditions as a function of relative humidity and temperature at a normal PEM operating pressure of 1 atm. Under non-humidified conditions, BPSH, SDAPP, and Nafion 112 exhibited Henry's Law sorption, consistent with dilute dissolution of O2 into the polymer matrix. The enthalpies of sorption were calculated to determine the interaction of O2 with each membrane. The sorption enthalpies in BPSH and SDAPP increased with increasing pressure indicating the formation of more O2-O2 interactions. The enthalpies in Nafion 112 were relatively constant with increasing pressure. In the presence of moisture, the sorption behavior changed from Henry's Law to Type IV sorption behavior, which is common in hydrophilic polymers. The SDAPP membrane was found to have the highest percent wet O2 mass uptake because of a higher number of sulfonic acid groups interacting with the water/O2 system. Finally the O2 sorption for various porous catalyst powders, consisting of platinum supported on carbon was measured in the non-humidified and humidified state. The catalysts were found to have Knudsen diffusion in the non-humidified state with 20 wt% Pt-C having the largest O2 sorption. In the humidified state, the highest O2 mass uptake was achieved with 40 wt% Pt-C. These results are explained in terms of the trade-off between catalyst dispersion and catalyst size. Furthermore, O2 sorption measurements were utilized for membrane electrode assemblies containing 40 wt% Pt-C and hot pressed at 210 oC for BPSH-35 (25 and 80K) and Nafion 112 membranes. The same sorption behavior occurred in the MEAs as in the neat membrane, but at a lower capacity. This is because the electrode introduces a more tortuous path to the gas molecules permeating across the membrane. / Ph. D.

Poly(arylene ether sulfone)s (PAES) are important commercial polymers and have been extensively studied due to their excellent thermal and mechanical properties. However, some applications are still limited when good solvent resistance and low thermal expansion coefficient are required. There has been a continuous interest in developing new PAES based on new monomers or polymer modifications to obtain new properties or to enhance existing properties. In this dissertation, the synthesis, characterization and structure-property relationship of new 1,4-cyclohexylene ring containing PAESs were comprehensively studied. Different polymerization techniques were used to synthesize polymers with different segmental lengths. The monomer, 4,4'-[trans-1,4-cyclohexanebis(methylene)] bisphenol (CMB), was synthesized and fully characterized. Based on 4,4′-dihydroxy-p-terphenyl (DHTP), 4,4′-dihydroxybiphenyl (DHBP) and the CMB monomer, homopolymer and random copolymers of PAES were prepared with high molecular weights and high glass transition temperatures. Dynamic mechanical analysis (DMA) on these polymers showed multiple sub-Tg relaxations. A large increase in the ultimate elongation was obtained with the CMB and DHTP containing sample, which could be due to the strong sub-Tg relaxations observed from the DMA results. A series of four acid chloride monomers were synthesized and polymerized with phenol terminated PAES oligomers. Solution polymerization and pseudo-interfacial polymerization techniques were used to prepare both bisphenol-A (bis-A) based and DHBP based PAES oligomers. With the incorporation of the trans-1,4-cyclohexylene units, decreases in the glass transition temperatures were observed from both the bis-A based and the DHBP based polymers. However, melting transitions were only observed in the DHBP based trans-1,4-cyclohexylene containing PAESs. Crystallinity was confirmed by differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). A mechanical property study of the high molecular weight trans-1,4-cyclohexylene containing polymer samples showed moderate ultimate elongation enhancements. A series of PAES-polyester multiblock copolymers were synthesized with both solution method and melt polymerization. In the solution method, phenol terminated PAES oligomers and the acid chloride terminated poly(1,4-cyclohexylenedimethylene terephthalate) (PCT) oligomers were presynthesized and coupled in solution. The molecular weights of the polymer products obtained from the solution method were limited by solubility issues. Melt phase polymerization was employed to obtain high molecular weight polymers. Hydroxy ethoxy terminated PAES oligomers were synthesized and polymerized with 1,4-cyclohexanedimethanol (CHDM) and dimethyl terephthalate (DMT) in the melt. Polymers with high molecular weights were obtained. Tensile test results suggested that the mechanical properties of these polymers were dominated by the PAES components with polyester contents up to 20 wt%. Melting transitions were observed from polymers with higher polyester contents, and these polymers exhibited limited solubility in common organic solvents. / Ph. D.

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. / Ph. D.

The following studies describe the synthesis and properties of a family of poly(arylene ether ketone)s which are well known to have good thermal stability, mechanical durability, and other film properties. These poly(arylene ether ketone)s were functionalized with fluorine, oxidized, blended, and crosslinked to increase performance with focus on materials for polymeric capacitors and gas separation membranes. There is a need for polymeric capacitors with improved energy storage density and thermal stability. In this work, the affect of polymer molecular structure and symmetry on Tg, breakdown strength, and relative permittivity was investigated. A systematic series of four amorphous poly(arylene ether ketone)s was compared. Two of the polymers had symmetric bisphenols while the remaining two had asymmetric bisphenols. Two contained trifluoromethyl groups while the other two had methyl groups. The symmetric polymers had Tg's of approximately 160 °C while the asymmetric polymers showed higher Tg's near 180 °C. The symmetric polymers had breakdown strengths near 380 kV/mm at 150 °C. The asymmetric counterparts had breakdown strengths near 520 kV/mm even at 175 °C, with the fluorinated polymers performing slightly better in both cases. The non-fluorinated polymers had higher relative permittivities than the fluorinated materials, with the asymmetric polymers being better in both cases. Two amorphous, high glass transition, crosslinkable poly(arylene ether)s for gas purification membranes have been studied. The polymers were polymerized via step growth and contained tetramethyl bisphenol F and either 4,4'-difluorobenzophenone or 4,4'-dichlorodiphenylsulfone. The benzylic methylene group in tetramethyl bisphenol F can undergo oxidation reactions and crosslinking with UV light. The polymers were oxidized under two different conditions, one by chemical treatment using oxone and KBr and one by elevated thermal treatment in air. Thermogravimetric analysis, 1H-NMR and attenuated total reflectance Fourier transform infrared spectroscopy revealed the progress of the thermal oxidation reactions. Both polymers produced tough, ductile films and gas transport properties of the non-crosslinked linear polymers and crosslinked polymer was compared. Crosslinking was performed by irradiating polymer films for one hour on each side in air under a 100W high intensity, long-wave UV lamp equipped with a 365-nm light filter. The O2 permeability of tetramethyl bisphenol F containing non-crosslinked poly(arylene ether ketone) was 2.8 Barrer, with an O2/N2 selectivity of 5.4. Following UV crosslinking, the O2 permeability decreased to 1.8 Barrer, and the O2/N2 selectivity increased to 6.2. Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) is a commercial polymer that is utilized for gas separation membranes. It has a relatively high free volume with high gas permeabilities but suffers from low gas selectivities. In this study, PPO polymers with number average molecular weights of 2000, 6000, 17,000, 19,000 and 22,000 were synthesized and blended with a poly(arylene ether ketone) synthesized from bisphenol A and difluorobenzophenone (BPA-PAEK) to make UV-crosslinkable films. The ketone and benzylic methylene groups on the BPA-PAEK and the PPO polymers respectively formed crosslinks upon exposure to broad wavelength UV light. The crosslinked blends had increased selectivities over their linear counterparts. DSC thermograms showed that the blends with all but the lowest molecular weight PPO had two Tg's, thus suggesting that two phases were present, one high in PBA-PAEK and the other high in PPO composition. The PBA-PAEK blend with the 2000 Mn PPO showed only one Tg between the two control polymers. Despite the immiscibility of these films, the gel fractions after UV exposure were high. Gel fractions as a function of the amount of the 22,000 Mn PPO were explored and did not show any significant change. UV spectroscopy of the individual components and the blends showed that more broad wavelength light was transmitted through the PPO component, so it was reasoned that films that was high in PPO composition crosslinked to deeper depths. The O2/N2 permeabilities and selectivities were measured for the linear and crosslinked films. Between the 33/67, 67/33, and 90/10 22k PPO/BPA PAEK crosslinked blended films, the 90/10 PPO/BPA PAEK gained the most selectivity and maintained a larger amount of its permeability. In comparison to commercial gas separation polymers, the non-crosslinked 33/67 22,000 Mn PPO/BPA PAEK blend outperformed polysulfone and cellulose acetate with a 2.45 degree of acetylation. Overall, we were able to blend a small amount of BPA PAEK with the commercially used PPO to create a mechanically robust crosslinked polymer film. / Ph. D.

Proton exchange membrane fuel cells (PEMFCs) have been extensively studied as clean, sustainable and efficient power sources for electric vehicles, and portable and residential power sources. As one of the key components in PEMFC system, proton exchange membranes (PEMs) act as the electrolyte that transfers protons from the anode to the cathode. The state-of-art commercial PEM materials are typically based on perfluorinated sulfonic acid containing ionomers (PFSAs), represented by DuPont's Nafion®. Despite their good chemical stability and proton conductivity at high relative humidity (RH) and low temperature, several major drawbacks have been observed on PFSAs, such as high cost, high fuel permeability, insufficient thermo-mechanical properties above 80°C, and low proton conductivity at low RH levels. Therefore the challenge lies in developing alternative PEMs which feature associated ionic domains at low hydration levels. Nanophase separated hydrophilic-hydrophobic block copolymer ionomers are believed to be desirable for this purpose Three series of hydrophobic/hydrophillic, partially fluorinated/sulfonated multiblock copolymers were synthesized and characterized in this thesis. The hydrophilic blocks were based upon the nucleophilic step polymerization of 3, 3′-disulfonated, 4, 4′-dichlorodiphenyl sulfone (SDCDPS) with an excess 4, 4′-biphenol (BP) to afford phenoxide endgroups. The partially fluorinated hydrophobic blocks were largely based on 4, 4′-hexafluoroisopropylidenediphenol (6F-BPA) and various difluoro monomers (excess). These copolymers were obtained through moderate temperature (~130-150°C) coupling reactions, which minimize the ether-ether interchanges between hydrophobic and hydrophilic telechelic oligomers via a nucleophilic aromatic substitution mechanism. The copolymers were obtained in high molecular weights and were solvent cast into tough membranes, which had nanophase separated hydrophilic and hydrophobic regions. The performance and structure-property relationships of these materials were studied and compared to random copolymer systems. NMR results supported that the multiblock sequence had been achieved. They displayed superior proton conductivity, due to ionic, proton conducting channels formed through the self-assembly of the sulfonated blocks. The nano-phase separated morphologies of the copolymer membranes were studied and confirmed by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). Through control of a variety of parameters, including ion exchange capacity and sequence lengths, performances as high, or even higher than those of the state-of-the-art PEM, Nafion®, were achieved. Another series of semi-crystalline hydrophobic poly(ether ether ketone)-hydrophilic sulfonated poly(arylene ether sulfone) (PEEK-BPSH100) multiblock copolymers was first synthesized and characterized. However due to their semi-crystalline structure, PEEK blocks are insoluble in most organic solvents at relatively low reaction temperatures, which prevents the coupling reaction between PEEK and BPS100. In order to facilitate the synthesis and processing, removable bulky ketimine was introduced to synthesize amorphous pre-oligomers poly(ether ether ketimine) (PEEKt). The synthetic procedure first involves the synthesis of hydrophobic poly(ether ether ketimine)-hydrophilic sulfonated poly(arylene ether sulfone) (PEEKt-BPS100) multiblock pre-copolymers via coupling reactions between phenoxide terminated hydrophilic BPS100 and fluorine terminated hydrophobic PEEKt blocks. The membranes cast from PEEKt-BPS100 were boiled in 0.5M sulfuric acid water solution to hydrolyze the amorphous PEEKt blocks to semi-crystalline PEEK blocks and acidify BPS100 blocks to BPSH100 blocks simultaneously. FT-IR spectra clearly showed the successful hydrolysis and acidification. The proton conductivity, water uptake and other membrane properties of the acidified semi-crystalline PEEK-BPSH100 membranes were then evaluated and compared with those of the state-of-the-art PEM, Nafion®. / Ph. D.

No description available.

Nanophase-separated hydrophilic-hydrophobic multiblock copolymers are promising proton exchange membrane (PEM) materials due to their ability to form various morphological structures which enhance transport. Four arylene chlorides monomers (2,5-Dichlorobenzophenone and its derivatives) were first successfully synthesized from aluminum chloride-catalyzed, Friedel-Crafts acylation of benzene and various aromatic compounds with 2,5-dichlorobenzoyl chloride. These monomers were then polymerized via Ni (0)-catalyzed coupling reaction to form various high molecular weight substituted poly(2,5-benzophenone)s. Great care must be taken to achieve anhydrous and inert conditions during the reaction. A series of poly(2,5-benzophenone) activated aryl fluoride telechelic oligomers with different block molecular weights were then successfully synthesized by Ni (0)- catalyzed coupling of 2,5-dichloro-benzophenone and the end-capping agent 4-chloro-4'-fluorobenzophenone or 4-chlorophenly-4′-fluorophenyl sulfone. The molecular weights of these oligomers were readily controlled by altering the amount of end-capping agent. These telechelic oligomers (hydrophobic) were then copolymerized with phenoxide terminated disulfonated poly (arylene ether sulfone)s (hydrophilic) by nucleophilic aromatic substitution to form novel hydrophilic-hydrophobic multiblock copolymers. A series of novel multiblock copolymers with number average block lengths ranging from 3,000 to 10,000 g/mol were successfully synthesized. Two separate Tgs were observed via DSC in the transparent multiblock copolymer films when each block length was longer than 6,000 g/mol (6k). Tapping mode atomic force microscopy (AFM) also showed clear nanophase separation between the hydrophilic and hydrophobic domains and the influence of block length, as one increased from 6k to 10k. Transparent and creasable films were solvent-cast and exhibited good proton conductivity and low water uptake. These PAES-PBP multiblock copolymers also showed much less relative humidity (RH) dependence than random sulfonated aromatic copolymers BPSH 35 in proton conductivity, with values that were almost the same as Nafion with decreasing RHs. This phenomenon lies in the fact that this multiblock copolymer possesses a unique co-continuous nanophase separated morphology, as confirmed by AFM and DSC data. Since this unique co-continuous morphology (interconnected channels and networks) dramatically facilitates the proton transport (increase the diffusion coefficient of water), improved proton conductivity under partially hydrated conditions becomes feasible. These multiblock copolymers are therefore considered to be very promising candidates for high temperature proton exchange membranes in fuel cells. / Ph. D.

The results described in this dissertation have demonstrated several alternative proton exchange membranes (PEM) for hydrogen-air and direct methanol fuel cells (DMFC) that perform as well or better than the state of the art Nafion perfluorosulfonic acid membrane. Direct aromatic nucleophilic substitution polycondensations of disodium 3,3′ S-disulfonate-4,4′ S-difluorodiphenylsulfone (SDFDPS), 4,4′ S-difluorodiphenylsulfone (DFDPS) (or their chlorinated analogs, SDCDPS, DCDPS) and 4,4′ S-thiobisbenzenethiol (TBBT) in the presence of potassium carbonate were investigated. Electrophilic aromatic substitution was employed to synthesize the SDFDPS or SDCDPS comonomers in high yields and purity. High molecular weight disulfonated poly(arylene thioether sulfone) (PATS) copolymers were easily obtained using the SDFDPS monomers, but in general, slower rates and a lower molecular weight copolymer was obtained using the analogous chlorinated monomers. Tough and ductile membranes were solution cast from N,N-dimethylacetamide for both series of copolymers. The degrees of disulfonation (20-50%, PATS 20-50) were controlled by varying the ratio of disulfonated to unsulfonated comonomers. Composite membranes were prepared by homogeneous solution blending the copolymers with phosphotungstic acid (PTA) in dimethylacetamide (DMAc). The composite PATS membranes exhibited moderate PTA molecule water extraction after acidification treatments performed at either room or boiling temperatures. The membranes containing HPA showed improved conductivity at high temperatures (120 °C) and low relative humidities when compared to the pure copolymers. Molecular weight of the copolymers plays a critical role in the overall copolymer physical behavior. It is well known that molecular weight has an enormous impact on practically all of the physical properties of polymeric systems. This dissertation discusses the influence of molecular weight on the characteristics of a specific family of PEM PATS copolymers. This study elucidated that the lower molecular weight materials did indeed behave differently than the higher molecular weight copolymers. Specifically, the water uptake and permeability to methanol decreased with increasing molecular weight. Furthermore, the fully hydrated mechanical properties also improved with molecular weight. The synthesis and fabrication of 45 mole percent disulfonated poly(arylene ether phenyl phosphine oxide diphenyl sulfone) terpolymer-heteropolyacid (HPA) composite membranes and membrane electrode assemblies were chosen for detailed investigation. A series of 45 mole percent disulfonated biphenol-based poly(arylene ether phenyl phosphine oxide diphenyl sulfone) terpolymers (BPSH45-PPO) were also synthesized by nucleophilic aromatic substitution polymerizations. The level of disulfonation was constant at 45 mole percent providing a compromise between high conductivity at low humidity and reasonable mechanical properties in liquid water. The amounts of 4,4′-difluorodiphenyl phenyl phosphine oxide comonomer incorporated into the terpolymer backbone were precisely controlled from 0-50 mole percent relative to the 4,4′-dihalodiphenyl sulfone. Phosphine oxide moieties were employed to enhance the interactions with the PTA relative to the pure copolymer. The composite BPSH45-PPO membranes exhibited lower HPA molecule water extraction after acidification at room and boiling temperatures, which was ascribed to the strong hydrogen and polar interactions between the phosphine oxide moiety and functional groups on the HPA. The membranes containing HPA displayed improved conductivity at high temperatures and low relative humidities when compared to the pure terpolymer samples. The increase of proton conductivity was attributed to the water retention characteristics of the HPA molecules, which allowed enhanced mobility of the protons even at lower humidification levels, providing superior hydrogen-air fuel cell performance. The effect of hexafluoroisopropylidene bisphenol (6FBP) incorporation into 45 mole percent disulfonated poly(arylene ether sulfone) copolymers was investigated. This novel series of directly disulfonated poly(arylene ether sulfone) copolymers with various mole ratios of the 6FBP were synthesized in high molecular weight. The levels of fluorination within the statistically random copolymer architecture were varied from 0-100 mole percent using 6FBP and the correct stoichiometric amount of 4,4′-biphenol. The 6FBP monomer was introduced to decrease the water swelling and improve bonding characteristics with Nafion-bonded electrodes. Indeed, water uptake decreased with increasing incorporation of the 6FBP monomer into the terpolymer. This suggested that the hydrophobic fluorinated material aided in water repulsion of the system. Proton conductivity decreased slightly as the amount of fluorination increased, which was interpreted to be due to the decrease in the ion-exchange capacity. High temperature hydrogen/air fuel cell experiments indicated better Nafion-bonded electrode adhesion for the partially fluorinated materials, as depicted by high temperature (120 °C) and low humidity (50% RH) hydrogen-air fuel cell performance. Investigations into polymeric electromechanical transducers were based on poly(arylene sulfone) ion-exchange membranes bonded between two conductive metal layer electrodes. Imposed deformations and small electric fields allowed similar explorations of both sensing and actuation applications. These copolymers produced larger sensitivities than the benchmark Nafion systems, which was interpreted as being due to their higher hydrated moduli. Methodologies for better defining the morphology of the electrodes were identified to enhance the capacitance and effective interfacial area of the conductive electrodes. The new procedures afforded major improvements to performance and transduction. Transducer actuation at lower frequencies was improved by employing a new direct assembly electrode fabrication technique that suggested a strong correlation between the capacitance and charge motion. / Ph. D.