Polylactide homopolymers with pendent carboxylic acid functional groups have been designed and synthesized to be studied as magnetite nanoparticle dispersion stabilizers. Magnetic nanoparticles are of interest for a variety of biomedical applications including magnetic field-directed drug delivery and magnetic cell separations. Small magnetite nanoparticles are desirable due to their established biocompatibility and superparamagnetic (lack of magnetic hysteresis) behavior. For in-vivo applications, it is important that the magnetic material be coated with biocompatible organic materials to afford dispersion characteristics or to further modify the surfaces of the complexes with biospecific moieties. The acid-functionalized silane endgroup was utilized as the dispersant anchor to adsorb onto magnetite nanoparticle surfaces and allowed the polylactide to extend into various solvents to impart dispersion stability. The homopolymers were complexed with magnetite nanoparticles by electrostatic adsorption of the carboxylates onto the iron oxide surfaces, and these complexes were dispersible in dichloromethane. The polylactide tailblocks extended into the dichloromethane and provided steric repulsion between the magnetite-polymer complexes. The resultant magnetite-polymer complexes were further incorporated into controlled-size nanospheres. The complexes were blended with poly(ethylene oxide-b-D,L-lactide) diblock copolymers to introduce hydrophilicity on the surface of the nanospheres with tailored functionality. Self-assembly of the PEO block to the surface of the nanosphere was established by utilizing an amine terminus on the PEO to react with FITC and noting fluorescence. / Ph. D.

Ce travail a permis de démontrer que l’électrofilage, ainsi que l’électronébulisation, sont des méthodes faciles et efficaces de préparation de complexes entre des polymères et des petites molécules. En effet, la plupart des méthodes de préparation de complexes donnent des mélanges inhomogènes à cause de la cristallisation cinétiquement favorisée des petites molécules. Or, un mélange inhomogène peut être très difficile à caractériser. Dans ce travail, l’électrofilage a été utilisé pour la première fois avec succès pour obtenir des nanofils de complexe entre le poly(oxyde d’éthylène) (PEO) et le NaSCN (PEO-NaSCN) ainsi qu’entre le PEO et l’hydroquinone. L’électronébulisation a été utilisée pour obtenir du complexe entre la polycaprolactone (PCL) et l’urée. L’électrofilage n’était pas possible pour le système PCL-urée parce que la solubilité n’était pas suffisante pour atteindre la viscosité minimale requise pour l’électrofilage. L’électronébulisation peut donc complémenter l’électrofilage et rendre la technique applicable à encore plus de systèmes. Les systèmes ont été caractérisés par spectroscopie infrarouge (FT-IR), par diffraction de rayons X (XRD), par calorimétrie différentielle à balayage (DSC) et par microscopies optique et électronique à balayage. / This work has allowed to show that electrospinning, as well as electrospraying, are easy and efficient methods for preparing complexes between polymers and small molecules. Most complex preparation methods yield inhomogeneous mixtures because of the kinetically favoured crystallization of small molecules. An inhomogeneous mixture can be very difficult to characterize. In this work, electrospinning was used for the first time to obtain nanofibres of complexes between poly(ethylene oxide) (PEO) and NaSCN (PEO-NaSCN) as well as between PEO and hydroquinone. Electrospraying was used to obtain a complex between polycaprolactone (PCL) and urea. Electrospinning was not possible for the PCL-urea system because the solubility was not sufficient to attain the minimal viscosity required for electrospinning. Electrospraying can thus be used as a complementary technique to electrospinning, making this approach applicable to a much wider range of systems. The systems were characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and microscopy (optical and scanning electronic microscopy).

Este trabalho apresenta um estudo sobre a síntese e propriedades do copolímero poli(l,l-lactídeo-stat-e-caprolactona)-bloco-poli(óxido de etileno)-bloco-poli(l,l-lactideostat-e-caprolactona). Poli(óxido de etileno) de massa molar 20.000 u.m.a. e poli(óxido de etileno) modificado, preparado a partir de poli(glicol etilênico) de massa molar 4.000 u.m.a., foram selecionados para o processo da síntese. A reação foi feita pela polimerização por abertura de anel em massa a 120ºC usando octoanato de estanho como iniciador. A composição química de cada amostra foi determinada com auxílio de RMN-1H e RMN-13C e suas propriedades mecânicas foram verificadas e comparadas utilizando análises térmicas como DMTA, DSC, TG e a aplicação da MEV como análise complementar. A observação pelas fotos de MOLP permitiu a visualização do comportamento de nucleação dos copolímeros e as características de sua cristalinidade. Seu grau de cristalinidade e as fases cristalinas foram identificados por difração de raios X (WAXS). A biocompatibilidade do material também foi examinada pela cultura de células. Os resultados de caracterização indicam o sucesso da copolimerização, as propriedades elastoméricas e, sua não citotoxidade comprovaram a possibilidade do uso destes copolímeros como biomateriais. Contudo, o tempo prolongado de reação e baixa incorporação do monômero lactídeo ainda são questões a serem melhoradas para a viabilização do copolímero como material de implante na área biomédica. / This work includes the study of the synthesis and characterization of the copolymer poly(l,l-lactide-stat-e-caprolactone)-b-PEG-b-poly(l,l-lactide-stat-e-caprolactone). Poly (ethylene oxide) with molar weight 20.000 and poly(ethylene oxide) modified, prepared from poly(ethylene oxide) with molar weight 4000 have been selected for this synthesis process. The reaction was done by ring-opening bulk polymerization, using stannous octoate as initiator at 120ºC. The chemical composition of samples were determined by 1H-NMR and 13C-NMR and their mechanical properties were verified using thermal analyses like DMTA, DSC and TG. Scanning electron microscopy (SEM) was applied as a complementary analysis. The pictures of polarizing optical microscopy showed us the copolymer\'s nucleation behaviors and their respective crystallization. The degrees of crystallinity and phase of copolymers were determined by WAXS. The biocompatibility of the copolymer was examined by cell cultivation test. The result of these analyses above indicated the success of synthesis. Their rubbery properties and non-toxicity allowed their application as biomaterial. However, the long reaction time and low incorporation of monomer of lactide might to be improved to increase its potential use in biomedical area in the future.

Made available in DSpace on 2014-12-17T15:42:03Z (GMT). No. of bitstreams: 1 CyprianoGTN.pdf: 2726336 bytes, checksum: 398151afa4a714a39af458b59a347ead (MD5) Previous issue date: 2008-05-09 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Two methodologies were proposed to obtain micro and macroporous chitosan membranes, using two different porogenic agents. The methodologies proved to be effective in control the porosity as well as the pore size. Thus, microporous membranes were obtained through the physical blend of chitosan and polyethylene oxide (PEO) on an 80:20 (m/m) ratio, respectively, followed by the partial PEO solubilization in water at 80 ◦C. Macroporous chitosan membranes with asymmetric morphology were obtained using SiO2 as the porogenic agent. In this case, chiotsan-silica ratios used were 1:1, 1:3 and 1:5 (m/m). Membranes characterization were carried out by SEM (scanning electronic microscopy), X-ray diffraction, Fourier Transform Infrared Spectroscopy (FTIR), Thermal analysis (TG, DTG , DSC and DMTA). Permeability studies were performed using two model drugs: sodium sulfamerazine and sulfametoxipyridazine. By transmission FTIR it was possible to confirm the complete removal of SiO2. The SEM images confirmed the porous formation for both micro and macroporous membranes and also determined their respective sizes. By thermal analysis it was possible to show differences related with water sorption capacity as well as thermal stability for both membranes. DTG and DSC allowed evidencing the PEO presence on microporous membranes. The absorbance x time curves obtained on permeability tests for micro and macroporous membranes showed a linear behavior for both drugs in all range of concentration used. It was also observed, through P versus C curves, an increase in permeability of macroporous membranes according to the increase in porosity and also a decrease on P with increase in drug concentration. The influences of the drug molecular structure, as well as test temperatures were also evaluated / Duas metodologias foram propostas para a obten??o de membranas macro e microporosas de quitosana, utilizando dois diferentes agentes formadores de poros. As metodologias mostraram-se eficientes no controle da porosidade e do tamanho dos poros gerados. Deste modo, membranas microporosas foram obtidas atrav?s de mistura f?sica da quitosana com o poli(?xido de etileno) (PEO), na propor??o 80:20 (m/m), respectivamente, seguido da solubiliza??o parcial do PEO em ?gua a 80 ◦C, e membranas macroporosas de quitosana com morfologia assim?trica foram obtidas utilizando um agente inorg?nico gerador de poros (SiO2). Neste caso, as propor??es quitosana-s?lica utilizadas foram 1:1, 1:3 e 1:5 (m/m). A caracteriza??o das membranas foi realizada atrav?s de microscopia eletr?nica de varredura (MEV), difra??o de raios X (DRX), espectroscopia de absor??o na regi?o do infravermelho (FTIR), an?lise t?rmica (TG, DTG, DSC e DMTA) e do estudo de sua permeabilidade utilizando-se dois f?rmacos modelos (sulfamerazina de s?dio e sulfametoxipiridazina). Atrav?s da t?cnica de FTIR em pastilha de KBr foi poss?vel confirmar, nas membranas macroporosas, a retirada completa do gerador de poros (SiO2). As imagens obtidas com o MEV confirmam a forma??o dos poros, tanto para as microporosas quanto para as macroporosas e determinam os seus respectivos tamanhos. Atrav?s das an?lises de TG, DTG e DSC foi poss?vel mostrar as diferen?as na capacidade de reten??o de ?gua para todas as membranas e suas estabilidades t?rmicas. As an?lises de DTG e DSC permitiram tamb?m evidenciar a presen?a de PEO nas membranas microporosas. As curvas Absorb?ncia ? Tempo obtidas a partir dos ensaios de permeabilidade, para as membranas micro e macroporosas, apresentaram um comportamento linear para ambos os f?rmacos e em todas as concentra??es utilizadas. Foi observado tamb?m, atrav?s da curva P ? C, um aumento na permeabilidade das membranas de acordo com o aumento da porosidade, bem como uma diminui??o desta com o aumento da concentra??o (C) dos f?rmacos modelo. Fatores tais como a influ?ncia da estrutura do f?rmaco e o efeito da temperatura tamb?m foram avaliados

The aim of this thesis work is to study the physico-chemical properties of poly(ethylene oxide), PEO, based brush polymers both in solution and at solid/aqueous interfaces. The importance of studying the surface properties of brush polymers can be related to a broad spectrum of interfacial-related applications such as colloidal stability, lubrication, detergency, protein repellency to name a few. In many applications it is desirable to form brush-like structures through simple physisorption. In this context the surface properties of PEO based brush polymers differing in molecular architecture were studied, using ellipsometry and surface force apparatus (SFA), to gain some understanding regarding the effect of molecular architecture on the formation of brush structures. The molecular architecture was varied by varying the charge/PEO ratio along the backbone. This study demonstrates that the formation of a brush structure at solid/aqueous interface is due to interplay between the attraction of the backbone to the surface and the repulsions between the PEO side chains. An optimal balance between the two antagonistic factors is required if one aims to build a well-defined brush structure at the interface. In this study the brush-like structures are formed when 25-50% of the backbone segments carry poly(ethylene oxide) side chains. Scattering techniques such as light and neutron reveal that these brush polymers are stiff-rods up to a charge to PEO ratio of 75:25. These stiff PEO brush polymer easily replace the more flexible linear PEO at the silica/water interface, the reason being that the entropy loss on adsorption is smaller for the brush polymer due to its stiff nature.  Polymer-surfactant systems play a ubiquitous role in many technical formulations. It is well known that linear PEO, which adopts random coil conformation in aqueous solution, interact strongly with the anionic surfactant, Sodium Dodecyl Sulphate (SDS). It is of interest to study the interaction between SDS and brush PEO owing to the fact that the PEO side chains have limited flexibility as compared to the linear PEO.  The interaction between brush PEO and the anionic surfactant SDS in solution are studied using different techniques such as NMR, tensiometry, SANS and light scattering. The main finding of this study is that the interaction is weaker compared to the linear PEO-SDS interactions which poses an interesting question regarding the role of chain flexibility in polymer-surfactant interactions. / QC 20100813

Ce travail a permis de démontrer que l’électrofilage, ainsi que l’électronébulisation, sont des méthodes faciles et efficaces de préparation de complexes entre des polymères et des petites molécules. En effet, la plupart des méthodes de préparation de complexes donnent des mélanges inhomogènes à cause de la cristallisation cinétiquement favorisée des petites molécules. Or, un mélange inhomogène peut être très difficile à caractériser. Dans ce travail, l’électrofilage a été utilisé pour la première fois avec succès pour obtenir des nanofils de complexe entre le poly(oxyde d’éthylène) (PEO) et le NaSCN (PEO-NaSCN) ainsi qu’entre le PEO et l’hydroquinone. L’électronébulisation a été utilisée pour obtenir du complexe entre la polycaprolactone (PCL) et l’urée. L’électrofilage n’était pas possible pour le système PCL-urée parce que la solubilité n’était pas suffisante pour atteindre la viscosité minimale requise pour l’électrofilage. L’électronébulisation peut donc complémenter l’électrofilage et rendre la technique applicable à encore plus de systèmes. Les systèmes ont été caractérisés par spectroscopie infrarouge (FT-IR), par diffraction de rayons X (XRD), par calorimétrie différentielle à balayage (DSC) et par microscopies optique et électronique à balayage. / This work has allowed to show that electrospinning, as well as electrospraying, are easy and efficient methods for preparing complexes between polymers and small molecules. Most complex preparation methods yield inhomogeneous mixtures because of the kinetically favoured crystallization of small molecules. An inhomogeneous mixture can be very difficult to characterize. In this work, electrospinning was used for the first time to obtain nanofibres of complexes between poly(ethylene oxide) (PEO) and NaSCN (PEO-NaSCN) as well as between PEO and hydroquinone. Electrospraying was used to obtain a complex between polycaprolactone (PCL) and urea. Electrospinning was not possible for the PCL-urea system because the solubility was not sufficient to attain the minimal viscosity required for electrospinning. Electrospraying can thus be used as a complementary technique to electrospinning, making this approach applicable to a much wider range of systems. The systems were characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and microscopy (optical and scanning electronic microscopy).

In the present work, we have undertaken a structural study of PS-b-PEO single crystals to elucidate the influence of the state of the PS block on crystallization from dilute solution and on subsequent thermal annealing at elevated temperature. It is noteworthy that the interest in these systems has been recently renewed in the perspective of using them as a model of grafted amorphous brushes with variable grafting density. Indeed, during crystallization of PEO, the amorphous block, i.e. PS, is rejected from the crystal accumulating on its basal surfaces. Since the crystal thickness formed during isothermal crystallization is a sharply selected value, the grafting density of the resulting PS brush is also well defined. Therefore by varying the crystal thickness one can obtain the PS brushes with grafting density varying in a broad range.In our study, a combination of reciprocal and direct-space techniques such as SAXS/WAXS and AFM was employed. While AFM experiments were performed on isolated single crystals, the SAXS investigation was carried out on oriented mats of single crystals slowly sedimented from the "mother" solution. In this case, the one-dimensional two-phase system model was used for the data interpretation where the thickness of the amorphous (La) and crystalline (Lc) layers are conventionally determined following the correlation fonction and interface distribution fonction approaches.

Este trabalho apresenta um estudo sobre a síntese e propriedades do copolímero poli(l,l-lactídeo-stat-e-caprolactona)-bloco-poli(óxido de etileno)-bloco-poli(l,l-lactideostat-e-caprolactona). Poli(óxido de etileno) de massa molar 20.000 u.m.a. e poli(óxido de etileno) modificado, preparado a partir de poli(glicol etilênico) de massa molar 4.000 u.m.a., foram selecionados para o processo da síntese. A reação foi feita pela polimerização por abertura de anel em massa a 120ºC usando octoanato de estanho como iniciador. A composição química de cada amostra foi determinada com auxílio de RMN-1H e RMN-13C e suas propriedades mecânicas foram verificadas e comparadas utilizando análises térmicas como DMTA, DSC, TG e a aplicação da MEV como análise complementar. A observação pelas fotos de MOLP permitiu a visualização do comportamento de nucleação dos copolímeros e as características de sua cristalinidade. Seu grau de cristalinidade e as fases cristalinas foram identificados por difração de raios X (WAXS). A biocompatibilidade do material também foi examinada pela cultura de células. Os resultados de caracterização indicam o sucesso da copolimerização, as propriedades elastoméricas e, sua não citotoxidade comprovaram a possibilidade do uso destes copolímeros como biomateriais. Contudo, o tempo prolongado de reação e baixa incorporação do monômero lactídeo ainda são questões a serem melhoradas para a viabilização do copolímero como material de implante na área biomédica. / This work includes the study of the synthesis and characterization of the copolymer poly(l,l-lactide-stat-e-caprolactone)-b-PEG-b-poly(l,l-lactide-stat-e-caprolactone). Poly (ethylene oxide) with molar weight 20.000 and poly(ethylene oxide) modified, prepared from poly(ethylene oxide) with molar weight 4000 have been selected for this synthesis process. The reaction was done by ring-opening bulk polymerization, using stannous octoate as initiator at 120ºC. The chemical composition of samples were determined by 1H-NMR and 13C-NMR and their mechanical properties were verified using thermal analyses like DMTA, DSC and TG. Scanning electron microscopy (SEM) was applied as a complementary analysis. The pictures of polarizing optical microscopy showed us the copolymer\'s nucleation behaviors and their respective crystallization. The degrees of crystallinity and phase of copolymers were determined by WAXS. The biocompatibility of the copolymer was examined by cell cultivation test. The result of these analyses above indicated the success of synthesis. Their rubbery properties and non-toxicity allowed their application as biomaterial. However, the long reaction time and low incorporation of monomer of lactide might to be improved to increase its potential use in biomedical area in the future.

L’objectif de cette étude est la réalisation de séparateurs de batterie haute performance par extrusion. Ces électrolytes polymères solides nécessitent d’être perméables au courant ionique mais aussi isolants électrique, tout en étant résistants mécaniquement. Une des possibilités étudiée pour le renfort mécanique est la dispersion de charges nanométriques (whiskers de cellulose) dans un polymère. Les whiskers de cellulose sont des bâtonnets cristallins d’une longueur entre 100 et 300nm et d’un diamètre entre 5 et 20 nm. Lorsque ces charges sont dispersées de façon homogène, elles forment un réseau percolant, améliorant de cette façon le renfort mécanique de la matrice pour de faibles concentrations. Le but est donc de réaliser cette dispersion dans un polymère fondu par extrusion, en comparaison avec le procédé bien établi d’évaporation de solvant. Les difficultés principales viennent de l’agglomération des whiskers de cellulose via des liaisons hydrogènes et du milieu très concentré dans lequel ces charges doivent être dispersées. Ainsi, la première partie de l’étude est de déterminer le processus de préparation des whiskers de cellulose, limitant l'agglomération et permettant d’obtenir une suspension stable. Ce système stable est nécessaire pour la formation d'un réseau par évaporation de solvant. Une fois le protocole optimisé, la deuxième partie de l’étude porte sur la dispersion de ces whiskers dans la matrice fondue au mélangeur interne et en extrusion. Les mélanges et films obtenus sont caractérisés par analyse en rhéologie dynamique, analyse thermique et analyse mécanique. Une dégradation de la matrice ainsi qu’une orientation des whiskers sont observées. Pour contourner ces contraintes, plusieurs alternatives sont utilisées. La première consiste à adsorber un copolymère sur les whiskers ; cette méthode augmente l’effet hydrodynamique mais aucun réseau n’est obtenu. La deuxième alternative est l’utilisation d’un polymère de faible masse molaire, permettant de diminuer la viscosité du mélange et par conséquent de limiter l’orientation des charges. Cette voie permet la formation d’un réseau percolant, tout en évitant la dégradation de la matrice dans l’extrudeuse. La troisième alternative utilise un copolymère de faible masse molaire synthétisé à partir d’un monomère porteur de doubles liaisons. La faible masse molaire permet de diminuer la cristallinité du séparateur et donc d’améliorer les performances ioniques à basse température. Les doubles liaisons permettent une réticulation assurant la tenue mécanique du film / The aim of this study is to produce high-performance battery separators through extrusion. These solid polymer electrolytes should be permeable to ionic current but electrically insulating, all the while maintaining sufficient mechanical resistance. To this end, the dispersion of nanometrics fillers (cellulose whiskers) in a polymer is studied. Cellulose whiskers are crystalline sticks, with a length between 100 and 300 nm and a diameter between 5 and 20 nm. It is well known that a homogeneous dispersion of these fillers allows a percolating network, improving the mechanical reinforcement of the matrix at low concentrations. The goal is to carry out this dispersion in molten polymer through extrusion, as opposed to the well-established solvent evaporation process. The main difficulties are the aggregation of cellulose whiskers which occurs through hydrogen bonding and the concentrated medium in which these fillers are dispersed. The first part of the study is to determine the optimum process to prepare cellulose whiskers in order to limit aggregation and thus obtain a stable aqueous suspension. This stable system is necessary to obtain a percolating network in the polymer matrix through solvent evaporation. Once the protocol optimised, the second part of the study focuses on the dispersion of these whiskers in the molten matrix using both the internal mixer and the extruder. Blends and films are characterized by dynamical rheology analysis, thermal analysis and mechanical analysis: a degradation of the matrix and an orientation of the whiskers are observed. To by-pass these issues, several alternatives are used. The first one involves the adsorption of a copolymer on the whiskers. This method increases the hydrodynamic effect; however no percolation network is obtained. The second alternative is to use a low molar mass polymer. This leads to a decreased polymer viscosity which limits the orientation of the fillers, allowing the percolating network to form and prevents polymer degradation. The third way uses a copolymer with a low mass molar, synthesized from a monomer which carries double bonds. The low molar mass allows the decrease of the separator crystallinity thus improving the ionic performances at low temperatures. The double bonds can crosslink under UV light, which enhances the mechanical strength of the film

Poly(arylene ether sulfone)s are high-performance engineering thermoplastics that have been investigated extensively over the past several decades due to their outstanding mechanical properties, high glass transition temperatures (Tg), solvent resistance and exceptional thermal, oxidative and hydrolytic stability. Their thermal and mechanical properties are highly suited to a variety of applications including membrane applications such as reverse osmosis, ultrafiltration, and gas separation. This dissertation covers structure-property-performance relationships of poly(arylene ether sulfone) and poly(ethylene oxide)-containing random and segmented copolymers for reverse osmosis and gas separation membranes. The second chapter of this dissertation describes synthesis of disulfonated poly(arylene ether sulfone) random copolymers with oligomeric molecular weights that contain hydrophilic and hydrophobic segments for thin film composite (TFC) reverse osmosis membranes. These copolymers were synthesized and chemically modified to obtain novel crosslinkable poly(arylene ether sulfone) oligomers with acrylamide groups on both ends. The acrylamide-terminated oligomers were crosslinked with UV radiation in the presence of a multifunctional acrylate and a UV initiator. Transparent, dense films were obtained with high gel fractions. Mechanically robust TFC membranes were prepared from either aqueous or water-methanol solutions cast onto a commercial UDEL® foam support. This was the first example that utilized a water or alcohol solvent system and UV radiation to obtain reverse osmosis TFC membranes. The membranes were characterized with regard to composition, surface properties, and water uptake. Water and salt transport properties were elucidated at the department of chemical engineering at the University of Texas at Austin. The gas separation membranes presented in chapter three were poly(arylene ether sulfone) and poly(ethylene oxide) (PEO)-containing polyurethanes. Poly(arylene ether sulfone) copolymers with controlled molecular weights were synthesized and chemically modified to obtain poly(arylene ether sulfone) polyols with aliphatic hydroxyethyl terminal functionality. The hydroxyethyl-terminated oligomers and α-ω-hydroxy-terminated PEO were chain extended with a diisocyanate to obtain polyurethanes. Compositions with high poly(arylene ether sulfone) content relative to the hydrophilic PEO blocks were of interest due to their mechanical integrity. The membranes were characterized to analyze their compositions, thermal and mechanical properties, water uptake, and molecular weights. These membranes were also evaluated by collaborators at the University of Texas at Austin to explore single gas transport properties. The results showed that both polymer and transport properties closely related to PEO-content. The CO2/CH4 gas selectivities of our membranes were improved from 25 to 34 and the CO2/N2 gas selectivity nearly doubled from 25 to 46 by increasing PEO-content from 0 to 30 wt.% in polyurethanes. Chapter four also focuses on polymers for gas separation membranes. Disulfonated poly(arylene ether sulfone) and poly(ethylene oxide)-containing polyurethanes were synthesized for potential applications as gas separation membranes. Disulfonated polyols containing 20 and 40 mole percent of disulfonated repeat units with controlled molecular weights were synthesized. Poly(arylene ether sulfone) polyols and α,ω-hydroxy-terminated poly(ethylene oxide) were subsequently chain extended with a diisocyanate to obtain polyurethanes. Thermal and mechanical characterization revealed that the polyurethanes had a phase-mixed complex morphology. / Ph. D.