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Research efforts have focused on synthesis of linear, long-chain branched, and novel crosslinked polyesters for applications spanning from pressure sensitive adhesives to biomedical applications. Altering polymer topology and functionality using different synthetic strategies was enabled tailoring the thermomechanical, rheological, and adhesive properties of polyesters. The synthesis and characterization of linear, long-chain branched, and crosslinked networks are described focusing on the structure-property relationships. Aliphatic low-Tg polyesters with linear and long-chain branched topology were synthesized using melt polycondensation for pressure sensitive adhesive applications. Relationships between molecular weight, polymer composition, and adhesive performance were investigated. Melt rheological studies and the characterization of adhesive properties indicated that adhesive performance was enhanced with increasing molecular weight. Moreover, a series of long-chain branched low-Tg polyester were investigated to determine the influence of branching and molecular weight. Tailoring the degree of branching enabled the control of rheological and adhesive properties. Characterization of adhesive properties revealed that long-chain branched polymers displayed an enhanced cohesive strength. In addition, utilization of different comonomer compositions allowed tailoring thermal and adhesive properties of low-Tg polyesters over a wide range. Biodegradable networks were synthesized for the first time using base-catalyzed Michael addition of acetoacetate functionalized polyesters with acrylates. Linear and star-shaped poly(caprolactone) (PCL) oligomers with different molecular weights were functionalized and crosslinked. Thermomechanical properties were evaluated as a function of precursor molecular weight and crosslink density. The glass transition temperature and the extent of crystallinity of the networks were dependent on the molecular weight of the PCL segment. Moreover, dynamic mechanical analysis (DMA) indicated that molecular weight of the oligomeric precursors influenced the plateau modulus of the networks as a result of the differences in crosslink density of the networks. In addition, covalently crosslinked networks were synthesized from Michael addition reaction of acetoacetate-functional oligomeric poly(trimethylene succinate)s and poly(trimethylene adipate)s with neopentylglycol diacrylate. The oligomeric polyesters with telechelic hydroxyl functionality were synthesized from renewable monomers, adipic acid, succinic acid, and 1,3-propanediol using melt polycondensation. The molecular weights of the precursors were varied systematically to probe the influence of molecular weight on thermomechanical properties of the networks. The extent of crystallinity and mechanical properties were dependent on the molecular weight of the oligomeric polyester precursors which also controlled crosslink density. Moreover, Michael addition chemistry was utilized to crosslink low-Tg polyesters to improve cohesive strength for PSA applications. In order to determine the influence of temperature and catalyst levels, crosslinking reactions were monitoring using measurement of loss and storage moduli during the reaction. Networks having different levels of gel fractions were investigated to elucidate the influence of degree of crosslinking on thermomechanical and adhesive properties of low-Tg polyesters. / Ph. D.

Current research efforts have focused on the synthesis of novel, segmented, cross-linked networks and thermoplastics for emerging technologies. Tailoring macromolecular structures for improved mechanical performance can be accomplished through a variety of synthetic strategies using step-growth polymerization. The synthesis and characterization of novel Michael addition networks, ionene families, and ion-containing polyurethanes are described, with the underlying theme of fundamentally investigating the structure-property relationships of novel, segmented macromolecular architectures. In addition, it was discovered that both covalent and electrostatic crosslinking play an important role in the mechanical properties of all types of polymers described herein. Novel cross-linked networks were synthesized using quantitative base-catalyzed Michael chemistry with acetoacetate and acrylate functionalities. These novel synthetic strategies offer unique thermo-mechanical performance due to the formation of a multiphase morphology. In order to fundamentally elucidate the factors that influence the kinetics of the Michael addition reaction a detailed analyses of model compounds were conducted in the presence of an in-situ IR spectrometer to optimize reaction conditions using statistical design of experiments. Networks were then prepared based on these optimized conditions. The mechanical performance was evaluated as a function of molecular weight between crosslink points. Furthermore, the incorporation of hydrogen bonding within the monomer structure enhanced mechanical performance. The changes in morphological, thermal, and mechanical properties evaluated using dynamic mechanical analysis (DMA) and tensile behavior are described. In addition, the use of preformed urethane segments provides a safer method for incorporating hydrogen bonding functional groups into macromolecules. In order to compare the thermomechanical and morphological properties of ion-containing polyurethanes to non-charged polyurethanes, poly(tetramethylene oxide)-based polyurethanes containing either a novel phosphonium diol or 1,4-butanediol chain extenders were prepared using a prepolymer method. The novel phosphonium polyurethane was more crystalline, and it was presumed that hydrogen bonding in the non-charged polyurethane restricted polymer mobility, and reduced PTMO crystallinity, and hydrogen bonding interactions were significantly reduced due to the presence of phosphonium cations. These results correlated well with mechanical property analysis. The phase separation and ionic aggregation were demonstrated via wide-angle X-ray scattering, small-angle X-ray scattering, scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy during STEM imaging, as described herein. In addition, a novel polyurethane containing imidazolium cations in the hard segment was synthesized and behaved very similarly to the phosphonium cation-containing polyurethane. Ammonium ionenes, which contain quaternary nitrogen in the macromolecular repeating unit, have many potential uses in biomedical applications. They offer interesting coulombic properties, and the charge density is easily controlled through synthetic design. This property makes ionenes ideal polyelectrolyte models to investigate the influence of ionic aggregation on many physical properties. Ammonium ionenes were prepared via the Menshutkin reaction from 1,12-dibromododecane and 1,12-bis(N,N-dimethylamino)dodecane. The absolute molecular weights were determined for the first time using an on-line multi-angle laser light scattering (MALLS) in aqueous size exclusion chromatography (SEC). Tensile testing and DMA were used to establish structure-property relationships between molecular weight and mechanical properties for a series of 12,12-ammonium ionenes. Furthermore, degradation studies in the presence of base support the possibility for water-soluble coatings with excellent mechanical durability that are amenable to triggered depolymerization. A novel synthetic strategy was utilized to prepare chain extended 12,12-ammonium ionenes containing cinnamate functional groups. In the presence of UV light, the polymers chain extended, and the resulting ionenes possessed enhanced thermomechanical properties and increased molecular weight. In addition, the novel synthesis of imidazolium ionenes was demonstrated, and the charge density was tuned for appropriate applications using either low molecular weight segments or oligomeric precursors. The change in charge density had a profound role in imidazolium ionene thermal and mechanical behavior. / Ph. D.

This dissertation explores the way for late 20th century poets use form in their work as means to map, encounter, witness to, and struggle with various kinds of silences. It explores the work of Louise Glȕck, M. Nourbese Philip, Jorie Graham, and Michael Palmer. / Published version / Doctor of Philosophy in English / In the conversion to current Word and PDF formats, pagination has changed slightly from the original document.

Ion-containing macromolecules continue to stimulate new opportunities for emerging electro-active applications ranging from high performance energy devices to water purification membranes. Progress in polymer synthesis and engineering now permit well-defined, ion-containing macromolecules with tunable morphologies, mechanical performance, ion conductivity, and 3D structure in order to address these globally challenged technologies. Achieving tailored chemical compositions with high degrees of phase separation for optimizing conductivity and water adsorption remains a constant synthetic challenge and presents an exciting opportunity for engineering sophisticated macromolecular architectures. This dissertation will introduce unprecedented charged polymers using conventional free radical and anionic polymerization to incorporate ionic functionalities based on phosphonium cations. This new class of copolymers offers unique properties with ionic functionality for tailorable electro-active performance. / Ph. D.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal. / Nous avons exploré et exploité un nouveau type d'addition de Michael des nitroalcanes pour la synthèse des pipéridines et pipéridinones diversifiés, substitués par des aminés et des alcools. Nous avons démontré l'efficacité et la facilité de l'addition conjuguée des nitroalcanes aux amides cycliques a,P-insaturés, et étudié la stéréosélectivité de l'addition. A l'aide de cette réaction, nous avons généré une série de pipéridinones diversifiées, des acides a-aminés, des nitrocyclopropanes et une nouvelle classe de pipéridines substituées par des amines et des alcools. Finalement, nous avons développé une méthode simple et efficace pour l'addition conjuguée des nitroalcanes afin d'obtenir des alkylamines substituées. / The goal of this study was to synthesize novel piperidine and piperidinones with aminomethyl and hydroxymethyl appendages, to be used as probes, scaffolds or mimics. We have demonstrated the efficiency and practicality of nitroalkane conjugate Michael addition to a,p-unsaturated lactams while studying the effects of different nitroalkane substitutents on the stereoselectivity. The noteworthy features of this approach are its operational simplicity, the efficiency of the nitroalkane conjugate addition, and the facile preparation of 2- and 4-substituted 6-oxo-piperidinones.

Yes / Improved synthetic conditions allow preparation of TMSCCl3 in good yield (70 %) and excellent purity. Compounds of the type NBu4X [X=Ph3SiF2 (TBAT), F (tetrabutylammonium fluoride, TBAF), OAc, Cl and Br] act as catalytic promoters for 1,4‐additions to a range of cyclic and acyclic nitroalkenes, in THF at 0–25 °C, typically in moderate to excellent yields (37–95 %). TBAT is the most effective promoter and bromide the least effective. Multinuclear NMR studies (1H, 19F, 13C and 29Si) under anaerobic conditions indicate that addition of TMSCCl3 to TBAT (both 0.13 M ) at −20 °C, in the absence of nitroalkene, leads immediately to mixtures of Me3SiF, Ph3SiF and NBu4CCl3. The latter is stable to at least 0 °C and does not add nitroalkene from −20 to 0 °C, even after extended periods. Nitroalkene, in the presence of TMSCCl3 (both 0.13 M at −20 °C), when treated with TBAT, leads to immediate formation of the 1,4‐addition product, suggesting the reaction proceeds via a transient [Me3Si(alkene)CCl3] species, in which (alkene) indicates an Si⋅⋅⋅O coordinated nitroalkene. The anaerobic catalytic chain is propagated through the kinetic nitronate anion resulting from 1,4 CCl3− addition to the nitroalkene. This is demonstrated by the fact that isolated NBu4[CH2=NO2] is an efficient promoter. Use of H2C=CH(CH2)2CH=CHNO2 in air affords radical‐derived bicyclic products arising from aerobic oxidation. / Engineering and Physical Sciences Research Council (EPSRC) Grant EP/K000578/1.