Three aromatic poly(arylene ether)s P2¡BP3¡BP4 were synthesized from bis(fluoride)4,4¡¨¡¨-Difluoro-3,3¡¨¡¨-bsi-trifluoromethyl-n¡¨-bisphenyl-[1,1¡¦;4¡¦,1¡¨;4¡¨,1¡¨¡¦;4¡¨¡¦,1¡¨¡¨]-quinquephenyl(n¡¨:2¡¨,3¡¨[G2];2¡¨,3¡¨,5¡¨[G3];2¡¨,3¡¨,5¡¨,6¡¨[G4]) with 4,4'-(9-Fluorenylidene)diphenol. The molecular weight of the polymer (Mw: 105-1.6¡Ñ105, PDI:1.5-2.2) was measured by gel permeation chromatography and the structure was confirmed by NMR spectra. Thermal stability was measured using Thermogravimetry and Thermomechanical Analysis. The polymer had a Td at 520¢J ~550¢J, and soft point at 310¢J. Young's modulus of polymer was (1.25-2.5Gpa). This polymer has high strength, modulus of elasticity, and thermal stability. The polymer consists of polyaromatic groups with bisfluoride monomer, (5, 6, 7 aromatic). We hypothesized that sulfonation of the polymer will exhibit high conductivity and great mechanical properties. Ion exchange capacities (IECs) were evaluated by acid¡Vbase titration. We sulfonated the polymer in order to apply to the proton exchange membrane fuel cell. The results showed after sulfonation of P4, IEC is 3.3(meq/g), and sulfonation of P2 showed that its proton conductivity is 75% more than Nafion117 at 80¢J with 0.28(S/cm). Keywords: proton exchange membrane, proton conductivity, Nafion, sulfonated, ion exchange capacity

Articulated rigid-rod polymers asPBI were synthesized via polycondensation reaction. Using 2-sulfoterephthalic acid and 5-sulfoisophthalic acid in different ratios for copolycondensation reaction making the fully conjugated rigid-rod backbone became articulated. Both rigid-rod and articulated rigid-rod were further derivatized using alkane sulfonated pendants and became water-soluble rigid-rod and articulated rigid-rod polyelectrolytes. Lithium salt doped cast films of the polyelectrolytes showed a root-temperature DC conductivity parallel to film surface (

This study utilized polycondensation reaction to synthesize fully conjugated rod-like polymer dihydroxy-PBI. Chemical derivatizations were applied to attach pendants of propane sulfonic coil for dihydroxy-PBI-PS and to attach aromatic phenylene ring with Li ionic moiety for dihydroxy-PBI-AS. The attachment of pendants for dihydroxy-PBI-PS was 42.27 % and for dihydroxy-PBI-AS was only for 0.04 % causing by stereo hindrance of this molecule. These polymers seemed to have good thermal stability. Dihydroxy-PBI started to show degradation at 467.8 oC and retained 60.5 wt. % at 800 oC. Derivatized dihydroxy- PBI-PS and dihydroxy-PBI-AS lost their pendants at 295.3 oC and 314.4 oC, respectively. Dihydroxy-PBI was cast into thin film. Upon doping with lithium salt of LiClO at 2.02 wt. %, dihydroxy-PBI cast film showed the highest room-temperature dc conductivity parallel to the film (£m¡ü) of 1.71 x 10-4 S/cm and perpendicular to the film (£m¡æ) of 1.49 x 10-5 S/cm. For dihydroxy-PBI-PS cast film, the highest conductivity was at 0.49 wt. % of LiClO4 with £m¡ü of 1.05 x 10-3 S/cm and £m¡æ of 1.05 x 10-4 S/cm. For dihydroxy-PBI-AS cast film, the highest conductivity was at 2.02 wt. % of LiClO4 with £m¡ü of 1.32 x 10-3 S/cm and £m¡æ of 2.26 x 10-5 S/cm. From scanning electron microscopy and wide-angle x-ray scattering, it was learned that cast films of dihydroxy-PBI and dihydroxy-PBI-AS had anisotropic layered structure parallel to the film, and that of dihydroxy-PBI-PS showed less of this anisotropy.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / VÃrias estratÃgias tÃm sido utilizadas para que materiais, quando em contato com sangue, possam reduzir a adsorÃÃo de proteÃnas do plasma e, consequentemente, a probabilidade de formaÃÃo de trombos. AlÃm disso, outro problema associado à a calcificaÃÃo, descrita como um processo de formaÃÃo de fosfato de cÃlcio, que à a causa primÃria de falhas em tecidos moles e implantes devido à deposiÃÃo destes sais. A quitosana e a carragenana sÃo dois polÃmeros que apresentam propriedades que os tornam promissores para utilizaÃÃo como biomateriais. A quitosana, em funÃÃo dos grupos amino em sua estrutura, pode promover a adesÃo plaquetÃria, sendo necessÃria uma modificaÃÃo quÃmica, como reaÃÃes de sulfonataÃÃo, que visam diminuir a adsorÃÃo de proteÃnas plasmÃticas. A presenÃa de grupos sulfato na carragenana pode contribuir para a obtenÃÃo de superfÃcies com propriedades antitrombogÃnicas sem a necessidade de modificaÃÃo quÃmica da estrutura. A formaÃÃo de complexos polieletrolÃticos (PECs) alia a biocompatibilidade superior da quitosana com a densidade de carga da carragenana, gerada pela presenÃa dos grupos sulfato. Esse trabalho teve por objetivo estudar os efeitos da calcificaÃÃo e da trombogenicidade de filmes de quitosana e carragenana caracterizando-os atravÃs de tÃcnicas de microscopia e espectroscopia, assim como realizar estudo de revestimento de superfÃcie metÃlica utilizando estes polÃmeros. Observou-se uma diminuiÃÃo nos efeitos de calcificaÃÃo para as blendas de quitosana e carragenana e nos filmes sulfonatados (Ca/P 0,11 ou ausÃncia de fÃsforo), reduzindo a formaÃÃo e deposiÃÃo de sais de cÃlcio quando comparados com a quitosana natural (Ca/P 2,78). Ensaios de adesÃo plaquetÃria mostraram melhoria das superfÃcies de quitosana quando modificadas pela sulfonataÃÃo, ou quando misturadas com carragenana, apresentando adesÃo, em mÃdia, de 1 a 2 plaquetas/0,01 mmÂ, contra a formaÃÃo de trombos em filme de quitosana. No ensaio de revestimento, a modificaÃÃo da superfÃcie metÃlica foi evidenciada pela alteraÃÃo da quantidade percentual de carbono e oxigÃnio na composiÃÃo quÃmica da superfÃcie quando comparado o aÃo eletropolido bruto e apÃs a inserÃÃo da quitosana. As sucessivas mudanÃas sofridas pelo Ãngulo de contato reforÃam o sucesso do grafting dos polÃmeros, atravÃs da formaÃÃo de uma camada hidrofÃlica tanto para quitosana natural quanto para a sulfonatada. Pelos resultados obtidos, pode-se inferir que a quitosana sulfonatada e as blendas de quitosana/carragenana mostram-se promissoras para serem utilizadas como biomateriais em contato com sangue. / Various strategies have been proposed to reduce the plasma proteins adsorption and consequently the probability of thrombus formation on materials when contacted with blood. Furthermore, another problem associated with biomaterials is the calcification process, which is described as calcium phosphate formation, which is the primary cause of failures in soft tissues and implants. Chitosan and carrageenan are two polymers that show properties that make them promising for use as biomaterials. Chitosan, due to amino groups in its structure, may promote platelet adhesion, being necessary to perform a chemical modification on it, such as sulfonation reactions, in order to reduce plasma protein adsorption. The presence of sulfate groups in carrageenan structure may contribute to obtain surfaces with antithrombogenic properties without the need of chemical modification on its structure. The formation of polyelectrolyte complexes (PECs) combines the high biocompatibility of chitosan with the charge density of carrageenan, generated by the presence of sulfate groups. This work aimed to study the effects of calcification and thrombogenicity of chitosan and carrageenan films, characterizing them by microscopy and spectroscopy techniques. We also conducted the study of metal surfaces coating using these polymers. A reduction in the effects of calcification for chitosan and carrageenan blends and for sulfonated chitosan films (Ca/P 0.11 or phosphate absence) was observed, reducing the formation and deposition of calcium salts when compared with pristine chitosan (Ca/P 2.78). Assays of platelet adhesion for chitosan surfaces when modified by sulfonation reaction or when blended with carrageenan, showed adhesion on average of 1 to 2 platelets/0.01mm2 against thrombus formation on chitosan film. For the coating essays, the modification on metal surface was characterized by the changing of carbon and oxygen percentage amount on the chemical composition surface, comparing the raw electropolished steel and grafted chitosan. The successive changes observed in the contact angle reinforce the success of the grafting of polymers, forming a hydrophilic layer both for pristine and sulfonated chitosan. From the results obtained, it can be inferred that the sulfonated chitosan and chitosan/carrageenan blends are promising for use as biomaterials in blood contact.

Polymers containing less than 10 mol % of ions (ionomers) have been studied in depth for their potential in producing polymers with tailored properties for specific applications. A small molar percentage of ions can be incorporated into a polymer to drastically enhance the properties of the polymer. An ionomer that has been studied is that of isoprene copolymerized with sodium styrene sulfonate (poly(I-co-NaSS)). Research has been performed relating to the synthesis and chemical characterization of the copolymers. However, an in depth study of the way the physical properties are affected by a change in ion concentration has not been presented. Thus, it is the goal of this thesis to synthesize a series of poly(I-co-NaSS) copolymers with varying levels of sulfonated styrene and characterize their physical properties. The poly(I-co-NaSS) polymers, containing a range of 1.15 to 4.74 mol % NaSS, were polymerized using free radical emulsion polymerization. The copolymer compositions were confirmed using combustion sulfur analysis. Dynamic light scattering indicated that large aggregates were present in solution. These aggregates were large enough that capillary intrinsic viscosities could not be measured. Small angle x-ray scattering (SAXS) and thermal analysis showed little change as the ion concentration was increased, while tensile, stress relaxation and adhesion properties were improved. The absence of changes in the SAXS patterns indicated that there was an absence of a well-defined ionic aggregate, while the mechanical properties showed evidence of electrostatic interactions. This can be at least partially attributed to ionic interactions on a smaller scale (doublets, triplets). / Master of Science / This research pertains to the creation of a series of polymers containing small amounts of ionic groups that allow tailoring the properties of the materials. The main component of the polymer is polyisoprene, which is also referred to as “natural rubber”. This material is elastic and can be used as a rubber (gloves) or can be manipulated to create a strong adhesive through addition of ionic groups. The polymers were synthesized with varying levels of ionic groups, creating a series of six polymers. These polymers were tested for their chemical composition (the chemical make-up of the polymers), morphological properties (their phase structure and self-assembly of the polymers on a nanometer to micron scale), and their mechanical properties (the strength, elasticity, and adhesive properties of the polymer). It was determined that in terms of the morphology, the polymer remained mostly unchanged as the ion content was increased, but the mechanical properties improved dramatically. As the concentration of ionic groups increased, the strength of the polymer as well as the adhesive properties of the polymer, also increased. Understanding the structure-property relationships of these copolymers can allow researchers to tailor their structures to fit a desired application.

Ion-containing segmented polyurethanes exhibit unique morphology and physical properties due to synergistic interactions of electrostatic, hydrogen bonding, and hydrophobic interactions. A fundamental investigation on a series of well-defined ion-containing polyurethanes elucidated the influence of charge placement, charge density, and soft segment structure on physical properties, hydrogen bonding, and morphologies. An unprecedented comparison of poly(ethylene oxide)(PEO)-based sulfonated polyurethanes containing sulfonate anions either in the soft segments or hard segments revealed that sulfonate charge placement dramatically influenced microphase separation and physical properties of segmented polyurethanes, due to altered hydrogen bonding and thermodynamic immiscibility between soft and hard segments. Moreover, studies on sulfonated polyurethanes with identical sulfonated hard segments but different soft segment structures indicated that soft segment structure tailored sulfonated polyurethanes for a wide range of mechanical properties. Sulfonated polyurethanes incorporated with ammonium-functionalized multi-walled carbon nanotubes (MWCNTs) generated novel polyurethane nanocomposites with significantly enhanced mechanical performance. Modification of MWCNTs followed a dendritic strategy, which doubled the functionality by incorporating two ammonium cations per acid site. Complementary characterization demonstrated successful covalent functionalization and formation of surface-bound ammonium salts. Upon comparison with pristine MWCNTs, ammonium-functionalized MWCNTs exhibited significantly enhanced dispersibility in both DMF and sulfonated polyurethane matrices due to good solvation of ammonium cations and intermolecular ionic interactions between anionic polyurethanes and cationic MWCNTs. Segmented polyurethanes containing sulfonated PEO-based soft segments and nonionic hard segments were incorporated with various contents of room temperature ionic liquid, 1-ethyl-3-methylimidazolium ethylsulfate (EMIm ES), to investigate the influence of ionic liquid on physical properties, morphologies, and ionic conductivity. Results indicated that EMIm ES preferentially located in the sulfonated PEO soft phase, leading to significantly enhanced ionic conductivity and well-maintained mechanical properties. These properties are highly desirable for electromechanical transducer applications. Electromechanical actuators fabricated with sulfonated polyurethane/IL composite membranes exhibited effective response under a low applied voltage (4 V). However, in the case of an imidazolium-containing segmented polyurethane with imidazolium ionic hard segments and hydrophobic poly(tetramethylene oxide) (PTMO) soft segments, EMIm ES selectively located into the imidazolium ionic hard domains, as evidenced with a constant PTMO soft segment glass transition temperature (Tg) and systematically reduced imidazolium hard segment Tg. Dielectric relaxation spectroscopy demonstrated that ionic conductivity of imidazolium-containing segmented polyurethanes increased by five orders of magnitude upon incorporation of 30 wt% EMIm ES. Imidazolium-containing sulfonated pentablock copolymers were also investigated to elucidate the influence of imidazolium counter cation structures on solution rheology, morphology, and thermal and mechanical properties. Combination of living anionic polymerization and post functionalization strategies provided well-defined sulfonated pentablock copolymers containing structured imidazolium cations in sulfonated polystyrene middle block. Varying alkyl substitute length on imidazolium cations tailored physical properties and morphologies of sulfonated pentablock copolymers. Results indicated that long alkyl substitutes (octyl and dodecyl) on imidazolium cations significantly influenced solution rheological behavior, morphology, and water uptake properties of sulfonated pentablock copolymers due to the altered characteristic of imidazolium cations. Imidazolium-containing sulfonated pentablock copolymers exhibited systematically tailored mechanical properties due to the plasticizing effect of alkyl substitutes. In addition, incorporation of ionic liquids into sulfonated pentablock copolymers further tailored their mechanical properties and ionic conductivity, which made these materials suitable for electromechanical transducer applications. All sulfonated pentablock copolymers were successfully fabricated into actuator devices, which exhibited effective actuation under a low applied voltage (4 V). / Ph. D.

No description available.

Providing sustainable supplies of water and energy is a critical global challenge. Polymer membranes dominate desalination and could be crucial to power generation applications, which include reverse osmosis (RO), nanofiltration (NF), forward osmosis (FO), pressure-retarded osmosis (PRO), electrodialysis (ED), membrane capacitive deionization (CDI), and reverse electrodialysis (RED). Improved membranes with tailored water and salt transport properties are required to extend and optimize these technologies. Water and salt transport structure/property relationships provide the fundamental framework for optimizing polymer materials for membrane applications. The water and salt transport and free volume properties of a series of sulfonated styrenic pentablock copolymers were characterized. The polymers' water uptake and water permeability increase with degree of sulfonation, and the block molecular weights could be used to tune water uptake, permeability, and selectivity properties. The presence of fixed charge groups, i.e., sulfonate groups, on the polymer backbone influence the material's salt transport properties. Specifically, the salt permeability increases strongly with increasing salt concentration, and this increase is a result of increases in both salt sorption and diffusivity with salt concentration. The data for the sulfonated polymers, including a sulfonated polysulfone random copolymer, are compared to those for an uncharged polymer to determine the influence of polymer charge on salt transport properties. The sulfonated styrenic pentablock copolymer permeability data are compared to literature data using the water permeability and water/salt selectivity tradeoff relationship. Fundamental transport property comparisons can be made using this relationship. The effect of osmotic de-swelling on the polymers and the transport properties of composite membranes made from sulfonated styrenic pentablock copolymers are also discussed. The sulfonated styrenic pentablock copolymers were exposed to multi-valent ions to determine their effect on the polymer's salt transport properties. Magnesium chloride permeability depends less on upstream salt concentration than sodium chloride permeability, presumably due to stronger association between the sulfonate groups and magnesium compared to sodium ions. Triethylaluminum was used to neutralize the polymer's sulfonic acid functionality and presumably cross-link the polymer. The mechanical, transport, and free volume properties of these aluminum neutralized polymers were studied. / text

Sulfonated porphyrins and phthalocyanines have been under consideration as microbicides, compounds which, when used in a topical formulation, can prevent transmission of the human immunodeficiency virus. Our studies have been directed toward the characterization of members of these classes. For the sulfonated phthalocyanines, matrix-assisted laser desorption/ionization (MALDI) mass spectrometry was helpful in determining the extent of sulfonation. We present the first report of spectroscopic characterization of a pentasulfonated phthalocyanine. Capillary electrophoresis data were sensitive to the concentration of the compounds (Chapter 1). Mass spectrometry was also very useful for establishing the extent of sulfonation in series of sulfonated porphyrins. Capillary electrophoresis was very useful in separating mixtures of these species. A study on sulfonation of a series of tetra(difluorophenyl)porphyrins showed that species with red-shifted Soret peaks were being formed. Data were consistent with an intramolecular sulfone bridge from the phenyl substituent to the porphyrin core. Sulfonation of the tetranaphthylporphyrins ring readily gave more than one sulfonic acid group per naphthyl side chain (Chapter 2). In cancer chemotherapy of solid tumors, it is desired to kill the tumor cells with minimal damage to the surrounding tissue. Brachytherapy seeds have been a considerable help in this regard for some tumors. In further developing approaches to selective tumor damage, we have evaluated a technique, Auger Electron Therapy (AET) in which one introduces a compound that is expected to bind to DNA, absorb the radiation, and then catalyze clustered DNA damage via release of a series of Auger electrons. We chose a series of metals (silver, indium, molybdenum, palladium, platinum, ruthenium, silver and zirconium) with appropriate energy levels to absorb an x-ray photon from the brachytherapy seed and used the tetracationic porphyrin 5,10,15,20-tetrakis(1-methylpyridinium-4-yl) porphyrin (TMPyP4) as a scaffold. The amount of clustered DNA damage was quantitated by a plasmid assay. Experiments evaluated the effect of buffer, concentration of glycerol, irradiation time, and concentration of the porphyrin. No metal studied gave significant double stranded (localized) DNA damage. Significant single stranded DNA damage was observed, however, in the order zirconium >> ruthenium > palladium > platinum > silver ~ indium (Chapter 3).

The proton exchange membrane fuel cells should have three major advantages: 1. micro-phase separation, 2. mechanical properties and 3. thermal stability. According to the recent literature and the material of core benzene ring poly (arylene ether)s studied by our group, this paper synthesize a series of the locally and densely sulfonated polymer. We use core benzene ring as the diol monomer and the containing CF3 groups as the fluorine monomer to synthesis poly (arylene ether)s via nucleophilic displacement reactions, and then use the different concentrations synthesized sulfonated polymer by sulfonic acid reaction. According to NMR¡¦s result we confirmed that the structure of synthetic materials is correct. By using GPC we get that the KP1, KP2, and KP3¡¦s molecular weight about 20000 (g/mol) ; The thermal stability up to 530OC for 5% loss in TGA under nithtrogen, to prove thisseries of polymer excellent thermal stability. After sulfonation, SKP1, SKP2 and SKP3¡¦s decomposition temperature decreased about 200OC ~ 250OC ranging with increasing degree of sulfonation. By DSC analysis, K1, K2 and K3 monomer's Tg followed up with the increase of the benzene ring number, however, the polymer does not have any apparent peak. About the Proton conductive, SKP2C IEC 2.23mequiv / g, water uptake 94%, the highest proton conductivity can be as high as 68.2 mS / cm, has been similar to Nafion 117 of 70 mS / cm.