Two novel classes of siloxane containing, organic-inorganic block copolymers were prepared using different synthetic approaches. The first copolymers were alternating poly(arylene ether phosphine oxide)-poly(dimethylsiloxane) systems, prepared via oligomeric silylamine-hydroxyl reactions. Secondly, segmented nylon 6,6-poly(dimethylsiloxane) block copolymers were synthesized via a non-aqueous adaptation of the "nylon 6,6 salt" hydrolytic polyamidization, using bis(aminopropyl) dimethylsiloxane oligomer as a co-reactant. Three series of "perfectly" alternating block copolymers were produced from well characterized hydroxyl-terminated poly(arylene ether phosphine oxide) and dimethylamine-terminated poly(dimethylsiloxane) oligomers, in order to investigate both block length and chemical composition effects. Copolymerization in chlorobenzene resulted in high molecular weight materials capable of forming optically clear, nanophase separated films, which displayed unusual morphologies and good mechanical strength. Thermal gravimetric analysis showed high thermo-oxidative stability and increasing char yield with increasing siloxane content. Additional thermal and mechanical investigations provided evidence of selective phase mixing, particularly at shorter block lengths. Surface analysis showed an enrichment of the siloxane blocks at the air-polymer interface in comparison to the bulk state. This behavior increased in proportion to the length of the parent siloxane oligomers. Evaluation of selected optical properties, e.g., refractive indices, revealed linear trends resulting in values of compositionally weighted averages. Conversely, a series of nylon 6,6-siloxane copolymers were produced from the polycondensation of preformed propylamine-terminated poly(dimethylsiloxane)s, solid nylon 6,6 salt and a corresponding amount of adipic acid to afford siloxane-amide semi-crystalline copolymers with siloxane content ranging from 10 to ~45 wt%. The characterization of high molecular weight and covalent siloxane-amide linkages was hindered by insolubility. For example, crystallinity of the nylon 6,6 precluded the use of common solution techniques, while the susceptibility of the siloxane blocks towards ionic redistribution prevented the use of strongly acidic solvents. However, development of a novel analytical technique using solid state 13C NMR and liquid-solid extraction provided evidence for the presence of covalent bonding between the dissimilar oligomer chains. Thermal gravimetric analysis of resultant copolymers revealed an increase in char yield with increasing siloxane content, a preliminary indicator of increased fire resistance, which was supported by subsequent qualitative Bunsen burner observations. Differential scanning calorimetry showed retention of the polyamide crystalline melt with levels of siloxane incorporation of up to 45 weight %. In conclusion, two novel classes of polydimethylsiloxane containing block copolymers have been successfully synthesized, despite the complications created as a result of the polar/non-polar interactions developed between a semi-inorganic polydimethylsiloxane and the hydrocarbon based polyarylene ethers and nylon 6,6. / Ph. D.

Over 30% of the world's population does not have access to safe drinking water, and the need for clean water spans further than just for human consumption. Currently, we use freshwater for growing agriculture, raising livestock, generating power, sanitizing waste, mining resources, and fabricating consumer goods. With that being said, the world is beginning to feel pressure from the excessive freshwater withdrawal compared to the current freshwater supply. This water stress is causing a water crisis. Places including Australia, South Africa, and California in the United States, just to name a few, are beginning to run out of fresh water to support daily societal demands. This is a phenomenon that is indiscriminately observed in all ranges of economically and politically developed countries and environments. However, it is important to note that less politically and economically developed countries especially those in arid climates, experience higher water stress than countries without such qualities. With only 2.5% of the world's water being freshwater and 30% of it being accessible as either ground or surface water, freshwater is a scarce resource, especially with the growing population and society's demand for water. Since the remaining 97.5% of water is composed of either brackish or seawater (saline water sources), one way to overcome the water stress would be to convert saline water into freshwater. As a result, various desalination techniques have been developed in the last 80 years that employ either membrane technology or temperature alterations to desalinate either brackish or seawater. One of the fastest growing methods for producing freshwater is reverse osmosis. Reverse osmosis uses an externally applied pressure, in the form of a cross flow back pressure, to overcome the osmotic pressure produced by the saline gradient across a semi-permeable membrane. The semi permeable membrane commercially consists of an interfacially polymerized aromatic polyamide thin film composite with a polysulfone porous backing that allows water to pass through while barring the transport of salt ions. This research focuses on the development of sulfonated poly(arylene ether sulfone) derivatives with differing amounts of sulfonation and with the ions placed at different structural positions. Previously, such materials were tested as potential high performance fuel cell membranes, but they are also of interest as potential high performance water desalination membranes, specifically for reverse osmosis. Two different methods were used to synthesize the sulfonated polysulfone derivatives: direct polymerization and post-modification of a non-sulfonated active polysulfone. The polysulfones from direct polymerization incorporated specialty sulfonated monomers, which were stoichiometrically controlled during the polymerization. Sulfonated polysulfones that were synthesized from post sulfonation incorporated biphenol and hydroquinone monomer units randomly throughout the polysufone backbones. These units could be sulfonated selectively because of their activation towards electrophilic aromatic substitution with sulfuric acid. Each of the polymers were cast into films ranging between 20-100 microns in thickness and tested for water uptake, hydrated uniaxial tensile properties, crossflow water and salt transport properties, and for crosslinked samples, gel fractions. The water uptakes from all the polysulfones were tuned by the degree of sulfonation or disulfonation present in the polymer. This was either controlled via the presence of a sulfonated monomer or a monomer that was active toward electrophilic aromatic substitution after polycondensation of the polysulfone. All polymers exhibited increases in their water uptake as the degree of sulfonation increased. We also observed a decreasing trend in the hydrated mechanical properties of the films for all the high molecular weight linear polymers as the water uptake was increased. The directly polymerized sulfonated polysulfones were found to have high hydrated elastic moduli ranging between 400 and 1000 MPa, while the post sulfonated counterparts (with either hydroquinone or biphenol incorporated in their structures) exhibited elastic moduli ranging between 1000 and 1500 MPa. It is important to note that the structures of the polymers were slightly different from one another because of the technique used to synthesize them. Thus, the increases in hydrated moduli among polymers synthesized via different routes may have influences from differences in chemical structures. Some of the polymers with higher degrees of sulfonation were synthesized as amine terminated oligomers with varying controlled molecular weights. The two targeted molecular weights were 5 and 10 kDa. Those oligomers were then crosslinked with a tetra-functional epoxide agent. The increases in sulfonation allowed for increases in water uptake and in theory, the water throughput through the sulfonated polysulfone membrane. Decreases in hydrated mechanical performance of the crosslinked networks with increasing degrees of sulfonation were also observed, similar to their high molecular weight linear counterparts. The directly polymerized crosslinked networks had salt permeabilities that plateaued at 70% disulfonation for both the 5 and 10 kDa polymers. Thus, we expect disulfonation content greater than 70% would lead to higher water throughput without significant increases in salt transport. / Doctor of Philosophy / A worldwide shortage of freshwater is becoming more problematic by each passing day. The World Health Organization and the United Nation's World Water Assessment Program predict that by 2025, 50-66% of the world's population will be living in a water-stressed area. This includes any area that experiences higher clean water withdrawals than are available. This includes but is not limited to areas that are politically unstable, technologically disadvantaged, resource deficient, located in arid climates, and highly populated. To put this further into perspective, only 2.5% of the available water on earth is freshwater. Freshwater typically has low concentrations of dissolved salts that are safe for human consumption and use. Of the available freshwater, only 30% of it is actually accessible for use through either surface or groundwater reservoirs, making the amount of clean water available for usage already a scarce resource. On the other hand, 97.5% of the world's water is composed of saline water reservoirs in the form of brackish and seawater. Through harnessing, seawater and removing the excess dissolved salt ions, the salt water can be converted to freshwater. Two major methods have been developed to remove the dissolved ions from water through either membrane filtration or thermal phase changes. One of the fastest growing membrane filtration techniques used worldwide is reverse osmosis. Reverse osmosis refers to the use of applied pressure across a semipermeable membrane to desalinate saline water. The semipermeable membrane prevents the migration of salt ions through the membrane while allowing transport of water. This work has focused on developing new polymers that can increase the overall efficiency of water desalination. Different types of high performance sulfonated polysulfone derivative polymers were synthesized and used to make membranes that were subsequently tested for performance. Relationships between the polymer structure, process, and properties were quantified through different analytical techniques. This study showed how the properties of sulfonated polysulfone membranes may be manipulated depending on structural modifications and processing to increase both the material's water throughput and salt rejection.

Polysaccharides are known as among the most abundant natural polymers on the Earth. As this class of material is usually renewable, biodegradable, biocompatible in many contexts and environmentally friendly, it is of great interest to use these benign polymers to design and prepare materials, especially for applications with green and biomedical purposes. In this dissertation we will discuss novel pathways to two different types of polysaccharide-based materials: block copolymers and hydrogels. Block copolymers are composed of two or even more covalent bonded polymer blocks that have quite distinct properties. Synthesis of polysaccharide-based block copolymers is an attractive and challenging research topic, opening up promising application potential and requiring advances in polysaccharide regio- and chemoselectivity. Herein, we report two independent approaches to prepare these interesting and potential useful materials. In one approach, trimethyl cellulose was modified regiospecifically at the reducing end anomeric carbon to create an ω-unsaturated alkyl acetal by solvolysis with an ω-unsaturated alcohol. Then, olefin cross-metathesis, a known versatile and mild tool for polysaccharide chemical modification, was used to couple the trimethyl cellulose block with various polymer blocks containing acrylates. To demonstrate the method, trimethyl cellulose-b-poly(tetrahydrofuran), cellulose-b-poly(ethylene glycol), and cellulose-b-poly(lactic acid) were synthesized by this coupling strategy. In another approach, we introduced a simple and novel method to prepare dextran-based block copolymers. In this strategy, N-bromosuccinimide (NBS)/triphenyl phosphine (PPh3) was chosen to regioselectively brominate the only primary alcohol of linear unbranched dextran. The resulting dextran, bearing a terminal C-6 bromide, was coupled with several amine terminated polymers via SN2 substitution to obtain block copolymers, including dextran-b-polystyrene, dextran-b-poly(N-isopropylacrylamide) and dextran-b-poly(ethylene glycol). Dextran-b-poly(N-isopropylacrylamide) exhibits thermally-induced micellization as revealed by dynamic light scattering, forming micelles with 155 nm diameter at 40 °C. Dextran-b-polystyrene film was analyzed by small angle X-ray scattering, suggesting the existence of microphase separation. This dissertation also introduces a novel, simple and effective strategy to prepare polysaccharide-based hydrogels. Hydrogels are typically crosslinked hydrophilic polymers that have high water affinity and no longer dissolve in water. Polysaccharide-based hydrogels are of great interest to for biomedical applications due to their benefits including biocompatibility, polyfunctionality, and biodegradability. Recently the Edgar group has discovered that chemoselective oxidation of oligo(hydroxypropyl)-substituted polysaccharides impairs ketone groups at the termini of the oligo(hydroxypropyl) side chains. These ketones can condense with amines to form imines, leading hydrogel formation., Based on this concept, we prepared oxidized hydroxypropyl polysaccharide/chitosan hydrogels. This class of all-polysaccharide hydrogels exhibits a series of interesting properties such as tunable moduli (300 Pa to 13 kPa), self-healing, injectability, and high swelling ratios. To further explore imine-crosslinked hydrogels, we designed thermally responsive hydrogels by using a Jeffamine, a polyethylene oxide-b-polypropylene oxide-b-polyethylene oxide triblock copolymer with two terminal amines. As the Jeffamine has a lower critical solution temperature, oxidized hydroxypropyl cellulose/Jeffamine hydrogels display moduli that are tunable by controlling the temperature. / Doctor of Philosophy / Polysaccharide are natural polymers that are among the most abundant polymers on Earth. It is greatly in society's interest to extend the scope of their applications, due to the benign nature of polysaccharides. This dissertation mainly focuses on two polysaccharides: cellulose and dextran. Cellulose is a long linear polymer of linked glucose molecules. As cellulose is sustainable, biodegradable, non-toxic, affordable and accessable for chemical modification, it is a suitable polymer for biomedical and environmentally friendly application. Dextran is also a polymer chain made up only of glucose but connected with each other differently from cellulose by, bacterial fermentation, and it may be lightly branched. It is biocompatible in many situations and is biodegradable both in vivo and in the environment, thus it has been investigated for drug delivery and many other medical applications. Using these two polysaccharides, we designed and prepared two quite different classes of materials: block copolymers and hydrogels. Block copolymers consist of two or more different types of polymer blocks connected by strong covalent bonds. As block copolymerization enables construction of a single polymer comprising segments with distinct properties, it is appealing to synthesize a block copolymer which preserves the properties of natural polymers coupled to very different polymers, such as polyolefins (e.g. the polyethylene that is used for milk bottles). In order to prepare polysaccharide-based block copolymers, we developed two different synthetic routes to end-functionalize methyl cellulose and dextran , and these resulting products were used to prepare two independent series of polysaccharide-based block copolymers via combination (in other words, sticking the polysaccharide and, e.g., the polyethylene together end to end). This study confirms the feasibility of this method to make methyl cellulose-based and dextran-based block copolymers. We expect these classes of materials will have significant potential in applications including drug delivery, as compatibilizers for polymer blends of materials that otherwise cannot be mixed (polyolefin/polysaccharide), membrane and adhesive. Hydrogels are crosslinked polymer networks with high water affinity, and they have been heavily investigated in the field of tissue engineering, drug delivery, agriculture and 3D printing. Polysaccharide-based hydrogels are attractive materials for these applications because they are biocompatible, biodegradable and have polyfunctionality. However, any use of toxic small molecules to crosslink the hydrogels diminishes their usefulness in biomedical applications. In this work, we demonstrate a simple, green and efficient method for preparation of all-polysaccharide-based hydrogels. The starting materials, oxidized hydroxypropylpolysaccharide, were simply prepared by using household bleach (NaOCl) as the oxidation reagent. We discovered that oxidized hydroxypropyl polysaccharides readily form hydrogels with hydrophilic amine-containing polymers like chitosan (a natural polysaccharide that comes from shells of crustaceans like crabs or shrimp) and Jeffamines, affording interesting properties including tunable stiffness, self-healing, injectability, and responsiveness to acidity and temperature. We expect that this new class of hydrogel will be very promising for biomedical-related applications.

Every year, millions of people contract antibiotic-resistant bacterial infections, and tens of thousands die from infection-related complications in the United States alone. Bacterial infections are one of the leading causes of death worldwide, especially in healthcare institutes such as hospitals and nursing homes where people are more susceptible to infection and complications. Bacteria can cause infections in any part of the body and often interact with sugar molecules on the surface of cells; once bacteria are attached, the cells stop functioning properly. When a bacterial infection is suspected, samples from the patient's blood or urine are taken to confirm the diagnosis. If the bacterial infection is sever enough, patients are treated with broad-spectrum antibiotics before the type of bacteria is known, and once it has been identified they are given antibiotics that target the specific bacterial strain. The high death rate associated with bacterial infections is largely due to the emergence of antibiotic-resistant bacterial strains. Although antibiotic resistance is present in some naturally occurring bacterial strains, misuse and over-prescription of antibiotics have accelerated the process. To combat the ever-growing threat of antibiotic-resistant bacteria, antibacterial polymers have been developed. Antibacterial polymers prevent bacterial infections by either killing the bacteria themselves or by preventing them from interacting with the body altogether This dissertation primarily focuses on using sugar-containing polymers to prevent bacterial growth. These materials may potentially be used as a replacement for or supplement to traditional antibiotics. / Doctor of Philosophy / All living cells possess a coating of glycomaterials on, or as critical components of their cell walls. Bacteria, including invasive bacterial pathogens, are no exception and have cell walls comprised of peptidoglycans. Glycomaterials on cell surfaces play a role in critical biological processes such as molecular recognition, cellular interaction, infection, and inflammation. Traditional antibiotic remediations are becoming less effective in treating bacterial infections due to the emergence of antibiotic-resistant strains. The formation of biofilms, an extracellular coating composed of polysaccharides, contributes to the antibiotic resistance of bacteria. The development of novel antibiotics is extremely costly and often unsuccessful, with billions in investment often producing zero new drugs. As a result, antibacterial polymers have been investigated as they are comparatively less expensive and offer unique characteristics to combat bacterial infections. Polymers with inherently antibacterial properties, or those that can be conjugated with antibacterial compounds, offer a replacement for traditional antibiotic remediation. To investigate the role of glycomaterials in antibacterial activity, a series of sugar-containing norbornene homopolymers were prepared and evaluated for their antibacterial activity. Protected glycomonomers consisting of galactose, glucose, N-acetyl glucose, and mannose were prepared in a two- or three-step synthesis by first appending an acrylate to the anomeric carbon through Koenigs-Knorr-type chemistry. After generation of the -anomer, the norbornene carboxylate was prepared by the Diels-Alder reaction of the acrylate with cyclopentadiene. Homopolymers with molecular weights ranging from 25–250 KDa were synthesized using ring-opening metathesis polymerization (ROMP) catalyzed by Grubbs 3rd generation catalyst, and subsequently deprotected to reveal the sugar-norbornene. While the galactose polymers showed no bacterial inhibition, those composed of glucose, N-acetyl glucose, or mannose prevented the growth of Escherichia coli (E. coli) and were effective at concentrations as low as 1.25 mg mL-1. Some strains of pathogenic bacteria, such as Clostridioides difficile (formerly known as Clostridium difficile), interfere with the normal cell functions by indirect means, producing toxins that adversely interact with the surrounding tissue. To sequester the toxins produced by C. difficile before they cause damage to the gastrointestinal (GI) tract, polymers containing the -gal epitope, a naturally occurring trisaccharide, were also prepared. The -gal epitope possessing a propyl azide handle at the anomeric carbon was prepared in a 15-step reaction, followed by reaction with an alkyne-functionalized polymer resin using copper-catalyzed azide-alkyne Huisgen cycloaddition. After global deprotection and thorough washing to remove residual copper from the glycomaterial, cell viability studies showed >80% cell survival. While these materials showed good cell viability, the rigorous synthesis of -Gal and the affinity of the polymer scaffolding for copper was a deterrent to further toxin-binding studies. Non-biological surfaces are also often susceptible to bacterial colonization and fouling. Although such materials may be modified to impart antimicrobial properties, their modification may also be a detriment to other key physical properties. To investigate the tradeoffs between material properties and functionalization, we synthesized a series of poly(arylene ether)s from monomers that possessed a modifiable handle and differed only in the pattern of leaving group on the aromatic ring. These polymers were further modified using post-polymerization thiol-ene reactions to evaluate the effect of the side-chains on the material's properties. The regioisomer incorporated into the polymer was found to influence its thermal properties irrespective of the installed functional group, suggesting that new functionality can be incorporated into these polymers without adversely impacting their physical properties.

Sulfonated poly(arylene ether sulfone)s can exhibit several ideal features as potential desalination membranes for reverse osmosis applications, including chlorine resistance, low surface fouling, and high water flux. However, this class of polymer membranes has suffered from two major drawbacks that jeopardize effective levels of salt rejection in order to achieve high water flux. In mixed salt feed sources, monovalent salt rejection decreases when divalent cations such as Ca2+ bind with the anionic sulfonate groups to cause charge screening, and this can lead to too much salt passage for the membranes to be competitive with interfacially produced polyamides. Sulfonate fixed charge concentration must be high enough for sufficient membrane water uptake to obtain high membrane water flux, but if the water uptake is too high, this permits increased salt passage. The research described in this dissertation attempts to address both of these challenges through the design of a sulfonated monomer that strategically spaces the ionic groups along the polymer backbone chains to inhibit divalent ion binding. Free radical crosslinking further tunes the hydrated free volume in the RO membranes. A mono-sulfonated comonomer, sodium 3-sulfonate-4,4'-dichlorodiphenylsulfone (ms-DCDPS), was synthesized by stoichiometrically controlled electrophilic aromatic sulfonation of 4,4'-dichlorodiphenylsulfone (DCDPS). HPLC-UV revealed complete isolation of ms-DCDPS free of by-products after the 1st recrystallization and 1H NMR analysis confirmed the structure. A standard calibration curve was developed to accurately determine the leftover quantity of excess NaCl that was used for precipitation during the work-up procedures. A series of linear sulfonated poly(arylene ether sulfone)s with varying ms-DCDPS incorporation was synthesized. 1H NMR confirmed the structure of the polymers and size-exclusion chromatography confirmed that the intended molecular weights were achieved. The copolymers were cast into dense films and the mechanical and transport properties were measured in their fully hydrated states. Tensile tests revealed mechanically robust, tough membranes with glassy elastic moduli and high strains at break. The dense membrane prepared from sulfonated poly(arylene ether sulfone) with 51% of the repeat units sulfonated had NaCl rejection = 99.3% measured at 400 psi and 2000 ppm NaCl with a water permeability coefficient of 0.57 x 10-6 cm2/s. The salt rejection remained greater than 99% when a mixed salt feed source containing Ca2+ in the 0-200 ppm range together with the 2000 ppm NaCl was introduced. Crosslinked mono-sulfonated oligomers were synthesized with targeted molecular weights by utilizing stoichiometric quantities of monomers with the desired degrees of sulfonation, and the endgroups were functionalized with tetrafluorostryene. These end-functionalized sulfonated oligomers were crosslinked by both thermal and UV free radical methods in the presence of initiators without any additional crosslinking agents. Reaction conditions were thoroughly investigated and optimized to produce highly crosslinked membranes that yielded gel fractions greater than 87%, as measured by solvent extraction in dimethylacetamide. The hydrated crosslinked membranes were tested for both mechanical and transport properties, and the results were compared to their linear membrane counterparts. Crosslinking decreased the hydrated free volume and reduced water uptakes when compared to linear sulfonated membranes. Tensile tests of the fully hydrated crosslinked membranes showed good mechanical properties. The transport properties of a dense UV crosslinked membrane prepared with a 10,000 g/mol oligomer having 50% of the repeat units sulfonated was tested under RO cross-flow conditions at 400 psi and 2000 ppm NaCl in the feed. The membrane demonstrated a salt rejection = 98.4% with a water permeability coefficient of 0.49 x 10-6 cm2/s. / Doctor of Philosophy / Billions of individuals across the world lack clean, affordable drinking water, and the unavailability of fresh drinking water can be attributed to both physical and economic reasons. Several techniques have been utilized to produce potable water for human consumption that include both water desalination and recycling procedures. Water desalination is a process that allows for purifying salt contaminated water into drinking water. The two major desalination processes involve either distillation or passage through polymer membranes. Distillation separates water from salt by heating liquid water to form a gas, and collecting the vapor as condensate while impurities remain in the heated bulk material. Polymer membranes separate impurities through filtration where membranes allow water to pass through a physical barrier while rejecting the unwanted contaminants, including salt. Reverse osmosis desalination is the most common membrane separation process. Reverse osmosis membranes are comprised of either short-chain crosslinked oligomers or long-chain linear polymers. Commercial reverse osmosis membranes are largely poly(amide)s where a thin film is formed in an interfacial reaction. The membranes allow for almost quantitative salt rejection with high water fluxes. But, these membranes degrade over time from periodic cleaning with chlorine disinfectants. This dissertation primarily focuses on the implementation of an alternative polymer membrane material known as a mono-sulfonated polysulfone that strategically distributes the fixed sulfonate charged groups along the polymer backbone. Theses reverse osmosis mono-sulfonated polysulfones display comparable salt rejection with better chemical resistance than commercial poly(amide)-based membranes, and could potentially offer a replacement in the market.

In this dissertation, two approaches were taken to design aqueous dispersible or soluble high performance ion containing polymers to be used as composite system interfacial modifiers and processing aids. In the first approach, thermally stable pyridine containing poly(ary/ene ether)s were designed which could be ionized by protonation in acidic aqueous media. A novel pyridine containing bisphenol monomer, 2,6-(p-hydroxyphenoxy)pyridine, was synthesized and utilized as a monomer for the synthesis of these pyridine moiety containing, high performance polymers containing sulfone, sulfoxide, phosphine oxide, ketimine, and ketone moieties. These pyridine containing poly(arylene ether)s can function as electrostatic stabilizers, but not as the more efficient steric stabilizers. ThE: second approach endeavored to form controlled molecular weight poly(ether-irTlides) via water soluble poly(amic acid) salt precursors. In this approach controlled molecular weight poly(amic acid)s were synthesized, and treated with stoichiometric quantities of tertiary or quaternary ammonium bases to form poly(amic acid) salts. The imidization conditions, and chemistry of the conversion of the poly(amic acid) salts to imide were studied, with the aim of maintaining the targeted molecular weight distribution and properties analogous to a control polyimide. For the above mentioned aqueous dispersion prepregging process, it is required that the matrix resin be in the form of small uniform particles capable of penetrating the interstices of a tight carbon fiber weave. Sub ~lm dimension poly(ether ether ketone) (PEEK) particles useful for aqueous dispersion prepregging were prepared on a large scale by precipitation from high temperature solvent, quantitatively purified, and shown to display properties analogous to the commercial precursor material. In the final chapter of this dissertation, the synthesis and characterization of a polyolefin macromer, and it's incorporation into a polyester is detailed. These macromers, and the graft polymers resulting, have applicability in the area of polymer blend compatibilization. / Ph. D.

Several types of novel proton exchange membranes which could be used for both direct methanol fuel cells (DMFCs) and hydrogen/air fuel cells were investigated in this work. One of the main challenges for DMFC membranes is high methanol crossover. Nafion, the current perfluorosulfonic acid copolymer benchmark membrane for both DMFCs and hydrogen/air fuel cells, shows very high methanol crossover. Directly copolymerized disulfonated poly(arylene ether sulfone)s copolymers doped with zirconium phosphates and phenyl phosphonates were synthesized and showed a significant reduction in methanol permeability. These copolymer/inorganic nanocomposite hybrid membranes show lower water uptake and conductivity than Nafion and neat poly(arylene ether sulfone)s copolymers, but in some cases have similar or even slightly improved DMFC performance due to the lower methanol permeability. These membranes also show advantages for high temperature applications because of the reinforcing effect of the filler, which helps to maintain the modulus of the membrane, allowing the membrane to maintain proton conductivity even above the hydrated glass transition temperature (Tg) of the copolymer. Sulfonated zirconium phenyl phosphonate additives were also synthesized, and membranes incorporating these materials and disulfonated poly(arylene ether sulfone)s showed promising proton conductivity over a wide range of relative humidities. Single-Tg polymer blend membranes were studied, which incorporated disulfonated poly(arylene ether sulfone) with varied amounts of polybenzimidazole. The polybenzimidazole served to decrease the water uptake and methanol permeability of the membranes, resulting in promising DMFC and hydrogen/air fuel cell performance. / Ph. D.

Semicrystalline thermoplastic polyimides based upon bis(4-aminophenoxy)benzene and related "triphenyl ether" diamines were synthesized via the classical two step amic acid route. More specifically, polyimides were derived from para linked 1,4-bis(4-aminophenoxy)benzene, or TPEQ (triphenyl ether diamine- hydroquinone) and its meta isomer 1,3-bis(4-aminophenoxy)benzene, or TPER (triphenyl ether diamine-resorcinol). The reaction of these diamines with rigid or semi-rigid dianhydrides such as pyromellitic dianhydride (PMDA), biphenyl dianhydride (BPDA), and oxydiphthalic anhydride (ODPA) yields very thermally stable semi-crystalline polymers which have excellent resistance to organic liquids. Amorphous polyimides could be derived from hexafluoroisopropylidene-linked diphthalic anhydride (6FDA), but these systems were not extensively investigated. Importantly, molecular weight characterization of the semicrystalline systems at the soluble amic acid stage was successful by employing hydrodynamic volume calibrated, viscosity detector size exclusion chromatography (SEC). The experimental values were found to be within the targeted <M_n> range of 20-30,000 g/mole. Polyimide powders derived from these ether diamines were prepared by solution imidization at 180°C, to afford about 70% imidized structures as judged by dynamic thermal gravimetric analysis (TGA), before crystallization/precipitation occurred. Relatively small particle sizes ranging from 2 to 25 μm in size were generated, which would be appropriate for thermoplastic polymer matrix composites prepared by powder processing. All specimens showed excellent thermooxidative stability, consistent with the aromatic imide structure. The molecular design of the aromatic polyetherimide repeat unit was critical for the successful utilization of these semicrystalline high performance materials. The metba-linked TPER system when combined with the thermally stable s-biphenyl dianhydride (BPDA) produced a melting endotherm, T_m, at about 395°C, which was well within the thermal stability limitations of organic materials, i.e., less than or approximately 450°C. It was also demonstrated to be important to quantitatively endcap both ends of the chains at about 20-30,000 <M_n> with non-reactive phthalimide groups to achieve appropriate melt viscosities and good melt stability. This was done by off-setting the stoichiometry in favor of the diamine, reacting with a calculated amount of phthalic anhydride and imidizing in bulk above the Tg (≈210°C) at 300°C. These considerations allowed for remarkable melt stability in nitrogen at 430°C for at least 45 minutes, and importantly, repeated recrystallizations from the melt to afford tough, ductile semicrystalline films with excellent solvent resistance. If the macromolecular chains were not properly endcapped, it was demonstrated that viscosity increased rapidly at 430°C, suggesting reactions such as transimidization involving terminal amine end groups with in-chain imide segments and/or other side reactions, which quickly inhibited recrystallization, probably by reducing molecular transport processes. In contrast, polyimides based upon the more rigid para-linked TPEQ did not demonstrate melt or flow characteristics below 400°C, and degraded around the T_m at about 470°C! The less thermally stable TPEQ-ODPA based polyimide did melt around 409°C, and lower molecular weight samples, e.g., 10,000 M_n, recrystallized from the melt after short melt times, but cast films were brittle. It was hypothesized that the weak link may be the relatively electron rich arylene ether bond derived from the ODPA dianhydride. Several alkylated derivatives of TPER were synthesized in good yield by the reactions of alkylated resorcinol precursors with p-fluoronitrobenzene to produce dinitro compounds, which were subsequently reduced. These model diamines were then used to synthesize polyimides by the classical two step route. As expected, few of the polyimides derived from BPDA and these diamines displayed melting transitions (T_m), probably because of poor chain packing. However, they could have potential as new thermally stable membrane materials. Several amorphous polyimides prepared from 1,3-bis(p-aminophenoxy)-4-hexylbenzene were soluble in selected common organic solvents and could be cast into flexible films. / Ph. D.

This thesis research focused on the synthesis and characterization of disulfonated poly(arylene ether sulfone) hydrophilic-hydrophobic segmented and multiblock copolymers for application as proton exchange membranes (PEMs) in fuel cells or as reverse osmosis (RO) membranes for water desalination. The first objective was to demonstrate that synthesizing blocky copolymers using a one oligomer, two monomer segmented copolymerization afforded copolymers with similar properties to those which used a previous approach of coupling two preformed oligomers. A 4,4′-biphenol based hydrophilic block of disulfonated poly(arylene ether sulfone) oligomer of controlled number average molecular weight (Mn) with phenoxide reactive end groups was first synthesized and isolated. It was then reacted with a calculated amount of hydrophobic monomers, forming that block in-situ. Copolymer and membrane properties, such as intrinsic viscosity, tensile strength, water uptake, and proton conductivity, were consistent with those of multiblock copolymers synthesized via the oligomer-oligomer approach. The segmented polymerization technique was then used to synthesize a variety of other copolymers for PEM applications. The well known bisphenol phenolphthalein was explored as a comonomer for either the hydrophilic and hydrophobic blocks of the copolymer. Membrane properties were explored as a function of block length for both series of copolymers. Both series showed that as block length increases, proton conductivity increases across the entire range of relative humidity (30-100%), as does, water uptake. This was consistent with earlier research which showed that the water self-diffusion coefficient scaled with block length. Copolymers produced with phenolphthalein had higher tensile strength, but lower ultimate elongation than the 4,4′-biphenol based copolymers. Multiblock copolymers were also synthesized and characterized to assess their feasibility as RO membranes. A new series of multiblock copolymers was synthesized by coupling hydrophilic disulfonated poly(arylene ether sulfone) (BisAS100) oligomer with hydrophobic unsulfonated poly(arylene ether sulfone) (BisAS0) oligomer. Both oligomers were derived using 4,´-isopropylidenediphenol (Bis-A) as the bisphenol. Phenoxide-terminated BisAS100 was end-capped with decafluorobiphenyl and reacted at relatively low temperatures (~ 100 oC) with phenoxide-terminated BisAS0. Basic properties were characterized as a function of block length. The initial membrane characterization suggested these copolymers may be suitable candidates for reverse osmosis applications, and water and salt permeability testing should be conducted to determine desalination properties. The latter measurements are being conducted at the University of Texas, Austin and will be reported separately. / Ph. D.

Segmented copolymers are important polymers with attractive properties and wide applications. In this dissertation, segmented polyurethanes containing triptycene units and multiblock copolymers containing poly(arylene ether sulfone) (PAES) and poly(1,4-cyclohexyldimethylene terephthalate) (PCT) segments were synthesized and systematically studied. Investigation of the influence of the bulky triptycene structure on the morphologies and properties of segmented polyurethanes was carried out by using triptycene-1,4-hydroquinone bis(2-hydroxyethyl)ether (TD) as the chain extender. Segmented polyurethanes based on poly(tetramethylene glycol) (PTMG) of 1000 g/mol were synthesized using a two-step polymerization procedure. Hydroquinone bis(2-hydroxyethyl)ether (HQEE) was used for the purpose of comparison. Hard segments with different bulkiness and flexibility were prepared with hexamethylene diisocyanate (HDI) and 4,4'-methylenebis(phenyl isocyanate) (MDI), and HQEE or TD as chain extenders. The incorporation of bulky TD and less flexible MDI significantly inhibited hydrogen bonding based on the Fourier transform infrared (FTIR) results. In addition, the microphase separation was also disturbed by the bulky and less flexible hard segments with confirmation from tapping mode atomic force microscopy (AFM) and small angle X-ray scattering (SAXS). The flexible HDI can be used to overcome the bulkiness of triptycene, promote microphase separation, and enhance mechanical properties. Novel PTMG based soft segments containing triptycene units were also prepared with number average molecular weight (Mn) around 2500 g/mol. Then this soft segment was reacted with MDI and HQEE to prepare segmented polyurethanes. Soft segments such as hydroquinone (HQ) containing PTMG (Mn = 2100 g/mol), and pure PTMGs (Mn = 1000 and 2000 g/mol) were used for comparison. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) results demonstrated that triptycene units led to an increased glass transition temperature (Tg) and an elimination of the crystallization of the soft segments. The absence of strain hardening for the triptycene-containing sample suggested a suppressed strain induced crystallization of soft segments, which was also confirmed by the analysis of wide-angle X-ray diffraction (WAXD) on the films strained to 370 %. Crystallizable PCT segments were copolymerized with PAESs to enhance solvent resistance and mechanical properties. PAES oligomers (Mn = 2000 g/mol) were first synthesized, and then reacted with dimethyl terephthalate (DMT) and 1,4-cyclohexanedimethanol (CHDM). Weight percentages of PCT segments were gradually changed from 20 wt% to 80 wt%. With PCT content greater than 50 wt%, crystallinity was observed by DSC, DMA, and WAXD. The extent of crystallinity of the copolymers was dependent on the wt% of PCT. Furthermore, crystallization behavior of copolymers based on two CHDMs with different isomer ratios (cis/trans 30/70 and all trans) were studied. Due to their more symmetric structure, copolymers based on all trans CHDM exhibited a higher extent of crystallization. / Ph. D.