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.

Crosslinking is an effective technique for increasing the salt rejection of water purification membranes and the selectivity of gas separation membranes. An abundance of monomers, telechelic oligomers, and novel polymers were synthesized for use as separation membranes. These materials were often imbued with crosslinking functionalities to increase their performance during testing at the University of Texas-Austin. Crosslinking of sulfonated poly(arylene ether sulfone) oligomers was studied systematically with regard to end-group functionality, polymer composition, and polymer hydrophilicity. Sulfonated bisphenol A based poly(arylene ether sulfone) random copolymers were synthesized with reactive amine endgroups and further functionalized with a tetra-epoxy resin, acryloyl chloride, phenylethynyl phthalic anhydride, and maleic anhydride. The reaction between amine terminated oligomers and a tetra-epoxy produced large, ductile membranes with gel fractions approaching 99%, the highest reported for crosslinked sulfonated polysulfone oligomers. This crosslinking reaction was studied by synthesizing two series of oligomers, one based on a bisphenol A monomer and the other based on a 4,4’-biphenol monomer. Both series were synthesized with 40, 50 and 60% degrees of sulfonation, so that hydrophilicity and composition could be studied with regard to water purification properties. All six oligomers were produced with a gel fraction exceeding 90%, and the membranes were evaluated at the University of Texas-Austin. The crosslinked oligomers demonstrated relatively constant salt rejection across a range of hydrophilicity values, which proved that crosslinking restricted the large amount of swelling that non-crosslinked sulfonated polysulfones undergo. The crosslinked oligomers had the best water purification properties reported for sulfonated polysulfone, with similar water permeabilities and an order of magnitude higher selectivity (Pw/Ps = 1.69 ± 0.13 x 103) than analogous linear copolymers (Pw/Ps = 3.67 ± 0.53 x 102). An additional series of linear sulfonated copolymers were also synthesized based upon a hydroquinone bisphenol, which also had superior water purification properties (1.06 ± 0.06 L μm m-2 h-1 bar-1, Pw/Ps = 2.44 ± 0.15 x 103) compared to previously synthesized linear copolymers. Poly(arylene ether)s were also investigated for use as gas separation membranes. A poly(arylene ether ketone) and poly(arylene ether sulfone) were both synthesized with moieties capable of oxidation and/or photocrosslinking through benzylic hydrogen abstraction by an excited ketone. The polymers produced tough, ductile films. Gas transport properties of the linear polymers and crosslinked polymer were compared. The O2 permeability of one exemplary non-crosslinked poly(arylene ether) was 2.8 Barrer, with an O2/N2 selectivity of 5.4. Following UV crosslinking, the O2 permeability decreased to 1.8 Barrer, and the O2/N2 selectivity increased to 6.2. / Ph. D.

This dissertation describes a general synthetic platform for segmented polymers that have main-chain reversible linkages based on cyclopentadiene-maleimide Diels-Alder chemistry. Research in the area of thermally reversible (self-healing) polymers has been an ever-expanding area of interest in the current scientific literature. However most of the emphasis has been on systems containing furan-maleimide linkages. While inexpensive and synthetically accessible, furan chemistry is mostly limited to crosslinked and hyperbranched architectures due to its relatively weak binding with maleimides at suitable propagation temperatures. Following a general review of the literature in this area (Chapter 1) the first stage of our research (Chapter 2) entails the synthesis of 2-substituted hydroquinones, which are needed as monomers in the later stages. The novelty of our hydroquinone synthesis stems from the use of allylic and other alkenyl ethers as the source of the ring substituent, and from the utilization of catalytic hydroboration to improve atom-efficiency. We showed that hydroquinones with widely varying functionality can be prepared efficiently by our method; these findings were published in the journal Tetrahedron in 2018. The second stage (Chapter 3) involves the use of the new hydroquinones in step-growth syntheses of hydroquinone-terminated telechelic and chain-extension of these telomers via Diels-Alder chemistry to form segmented polymers having thermally reversible linkages. The novelty of our approach rests with the use of cyclopentadiene-maleimide chemistry for the linkages, while the overall physical properties such as the glass transition temperature were established by using well-defined aromatic polymers — poly(ether ether ketones) or PEEK and poly(aryl ether sulfones) or PAES — as segments. This approach represents an important departure from earlier work in our group in which reversible linkages were present in every repeat unit of a step-growth Diels-Alder polymer that showed thermal reversibility in solution but not in the bulk, owing to glass transition temperatures that were too high. Using scratch-healing and mechanical (tensile) tests, we show that our new segmented polymers exhibit self-healing characteristics that are competitive with or superior to previously reported systems based on different Diels-Alder chemistry. The third stage (Chapter 4) aims to explore new application areas for some of the more novel functionalized hydroquinones reported in Chapter 2. First we developed an efficient synthesis of a PAES derivative bearing 5-phenoxypentyl groups on the hydroquinone moiety. Then we showed that the 5-phenoxy group can be cleanly cleaved, post-polymerization, to afford a PAES having 5-bromopentyl substituents. The promise of our method rests with the potential of the pendant electrophiles to undergo reactions with nucleophilic reagents to post-modify these polymers further. As proof of concept, we showed that substitution of the pendant bromides with furfuryloxy groups enabled thermally reversible crosslinking with a bis-maleimide reagent to form a polymeric material that demonstrates partial scratch healing. Finally we are exploring the synthesis of new ion-containing polymers by substituting the pendant bromides with tertiary amines. / PHD / This dissertation describes a new synthetic approach to polymeric materials that can heal themselves (for example, repair small cracks that may have formed due to stress or aging) simply by heating the damaged area. Our approach uses a thermally reversible chemical reaction (called the Diels-Alder reaction) to connect several shorter polymer segments into longer chains. Upon heating, the segments can come apart, diffuse into and through the damaged area, and then rejoin. The first chapter is a review of background in the published literature as well as previous not-yet-published work in our laboratory. The second chapter describes the creation of new building-block molecules (monomers) that will help control the temperature range necessary to induce self-healing after incorporation into the polymer segments. The third chapter details the process of forming the segments, the incorporation of self-healing functionalities on the ends of the segments, the joining of the segments into longer polymeric chains, and the testing of all of the physical properties of these new materials, including their self-healing capabilities. The fourth chapter represents a preliminary study of a new method of preparing ion-containing polymers. The latter materials have potential use in various membrane technologies including fuel cell devices for the harnessing of renewable energy.

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