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.

Bone is the second most transplanted tissue after blood and the need for bone graft materials continues to rise at an average annual growth rate of over 18%. An engineered bone substitute consisting of a bone-like extracellular matrix deposited on the internal pores of a resorbable biomaterial scaffold is postulated to stimulate normal bone remodeling when implanted in vivo. Part one of this engineering strategy, the deposition of bone-like extracellular matrix, can be achieved by the directed differentiation of progenitor cells such as bone marrow stromal cells (BMSCs). Part two of the engineering strategy, the biomaterial scaffold, can be fabricated with the appropriate mechanical properties using a synthetic polymer system with tunable properties like polyurethanes. Finally, BMSCs seeded within the biomaterial scaffold can be cultured in a perfusion flow bioreactor to stimulate osteoblastic differentiation and the deposition of bioactive factors. Using the three-part engineering strategy described, I hypothesize that the extracellular matrix produced by BMSCs can be modulated by two stimuli: the stiffness of the scaffold and perfusion flow. First, I propose that culturing BMSCs on polyurethane scaffolds with increasing stiffness will increase markers of osteoblastic differentiation. Secondly, I suggest that mechanically stimulating BMSCs with novel perfusion strategies will also increase markers of osteoblastic differentiation. In aim 1, a family of segmented degradable poly(esterurethane urea)s (PEUURs) were synthesized. The modulus of the PEUUR materials was systematically increased from 0.18 to 0.80 MPa by systematically increasing the molecular weight of the poly(ε-caprolactone) (PCL) soft segment from 1425 to 2700 Da. BMSCs were cultured on both rigid polymer films and on porous foam scaffolds to dissociate the effect of variation in polymer chemistry from the effect of scaffold modulus on cell phenotype. These studies demonstrated changes in osteoblastic differentiation as measured by prostaglandin E2 production, alkaline phosphatase activity (ALP) activity, and osteopontin gene expression. However, the increased levels of these phenotypic markers on the PCL 2700 material could not be attributed to scaffold chemistry or modulus. Instead, the differences may be related to polymer crystallinity or surface topography. In aim 2, novel dynamic perfusion strategies were used to investigate the influence of frequency on osteoblastic differentiation. BMSCs were seeded on porous foam scaffolds and exposed to both steady perfusion and pulsatile perfusion at 0.017, 0.050, and 0.083 Hz frequencies. The data presented here demonstrated that while some markers of osteoblastic phenotype such as ALP activity are enhanced by 0.05 Hz pulsatile flow over continuous flow, they are insensitive to frequency at low frequencies. Therefore, future studies will continue to investigate the effect of a larger range of frequencies. Additionally, fluid flow has also been shown to stimulate the deposition of bioactive factors such as BMP-2 and VEGF-A, and these growth factors are known to significantly enhance healing in bone defect models. Therefore, we plan to investigate the effect of dynamic flow strategies on the deposition of these bioactive factors. We propose that an engineered bone graft material containing a bone-like extracellular matrix and producing these growth factors will show more rapid formation of bone when implanted in vivo. / Ph. D.

Cellulose nanomaterials (CNMs) have been widely studied for their potential as sustainable fillers in polymer nanocomposites, optical responsiveness in suspensions and thin films, and their orientation-dependent liquid crystalline behavior in suspensions. Cellulose nanocrystals (CNCs) have seen a particular prominence due to their versatility across a breadth of applications. The unique structure of CNCs, represented as nanoscale rods with a slight twist, provides for their self-assembly into liquid crystalline phases when their concentration is increased and can be used to generate iridescent materials with tunable wavelengths. Further, CNCs are often used as fillers in nanocomposites, due to their high single crystal Young's modulus, achieving vast enhancements in stiffness when incorporated above a critical concentration where a percolating network is formed. The breadth of applications for CNCs strongly depend not only on their crystalline structure, but crucially on the interactions between particles. These interactions are well-known, yet a complete understanding to enable the full exploitation of the properties attainable in CNC-based materials is lacking. The principal emphasis of this dissertation lies in further improving our comprehension of the interactions between CNCs across a variety of applications such that their full potential can be achieved. A review of the current research of CNC-based materials is provided to guide the discussion herein. Interparticle interactions are studied in aqueous suspensions of CNCs in evaporating sessile droplets. This system provides a complex interrelationship between mass, heat, and momentum transport which collectively provide a change in the local CNC concentration as a function of time. CNC interactions can be controlled throughout the evaporation process as a result of these local concentration variations. We implement a novel approach using time-resolved polarized light microscopy to characterize the evolution of these particle interactions via the orientation of CNCs as a function of CNC concentration and droplet volume. Ultimately, boundary interactions at the leading edge of the contact line during evaporation was found to drive a cascade of local CNC interactions resulting in alignment post-deposition. Computational analysis evaluated the influence of evaporation-induced shear flow during evaporation. Orientation was found to be independent of the bulk fluid flow, corroborating the importance of interparticle interactions on the ensuing alignment of CNCs. Characterization of an evaporating droplet of initially liquid crystalline suspension of CNCs verified the simulations which predicted that orientation was not coupled with entrainment. Finally, the multiple modes of orientation showed that local control over CNC properties can be realized through governance of the interactions between CNCs. The interactions of CNCs in polymer nanocomposites were also studied for the development of smart materials which can adapt their properties in response to external stimuli. A well-known example of this phenomena is found when CNCs are introduced as fillers in thermoplastic polyurethanes (TPUs) above a critical concentration required to achieve percolation. The interactions between CNCs in the percolating network provide a strong enhancement to the modulus of these materials. However, these materials soften upon exposure to water following the disruption of inter-CNC hydrogen bonding by the diffusing water molecules, as prevailing theories suggest. CNCs simultaneously enhance water transport into hydrophobic matrices. Thus, a complete understanding of the interrelationship between the mass transport and mechanical performance can facilitate the development of humidity sensing or shape memory materials which operate as a result of the interactions between CNCs inside of a polymer matrix. Despite an increase in the equilibrium water uptake with increasing CNC concentration, a decrease in the apparent diffusivity of water within the nanocomposites was observed as a result of swelling of the bulk polymer. Additionally, we developed a modification to the commonly used percolation model to predict the time-dependent evolution of storage modulus during water-induced softening. We found that the solvent mass transport can be directly coupled to the mechanical integrity of the percolating network of CNCs by evaluating the hydrogen bonding state of the network as a function of time. Finally, a novel nanocomposite filler comprised of CNCs and 2,2,6,6- tetramethylpiperidine 1-oxyl (TEMPO) oxidized cellulose nanofibrils (TOCNFs) was prepared through solution casting to improve the mechanical performance of the individual reinforcements alone. The physical interaction length is increased by incorporating CNMs of different length scales resulting in increased tensile strength and elongation. Further, the morphology, evaluated with polarized light microscopy, atomic force microscopy, and simulated with dissipative particle dynamics, revealed the combined fillers exhibit a cooperative enhancement between CNMs. Characterization of the crystallinity through x-ray diffraction confirmed the interactions occur primarily between the crystalline domains of each material. Accordingly, the combination of CNMs resulted in nanocomposite fillers which can be implemented such that the weak interfaces with polymer matrices can be bridged with fillers providing reinforcement over a broader length scale. / Doctor of Philosophy / Cellulose nanocrystals (CNCs) are sustainable and biorenewable nanoparticles derived from cellulose. These materials have been widely studied and are commonly used among a plethora of applications such as in reinforcing fillers in polymer nanocomposites, optically responsive materials that can be used in packaging or anti-counterfeiting technologies, as well as in suspension modifiers for skin care products. These techniques tune the interactions between individual CNCs to modify the behavior of the bulk material. The specific interactions are well-known, yet a complete understanding of the influence of these interactions resulting in the utility of CNC-based materials in various applications is lacking. The principal emphasis of this dissertation lies in further improving our comprehension of the interactions between CNCs across a variety of applications such that their full potential can be achieved. Interactions between CNCs were investigated in three systems comprising of a range of typical use cases for CNC-based materials. The behavior of CNCs was examined in evaporating droplets of aqueous suspensions. These materials exhibited a change in orientation in the final deposit which is dependent on variations in local CNC concentration during drying. These concentration changes describe the relative strength of interactions between CNCs which ultimately influences the final alignment of these materials. Further, these interactions provide a pathway to deposit a controlled orientation of CNCs on a substrate which can be utilized for optically responsive materials or serve as templates for other orientation-dependent materials. CNCs were also incorporated into a thermoplastic polyurethane (TPU) matrix to provide increased stiffness. In these composites, water preferentially interacts with CNCs preventing the nanoparticles from interacting with one another. As water is absorbed, these materials soften as a result of the reduced interactions between CNCs. We investigated the influence of dynamically changing CNC interactions on the mechanical performance of these materials during water absorption and developed an analytical model to describe the observed softening behavior. Finally, CNCs were combined with 2,2,6,6- tetramethylpiperidine 1-oxyl oxidized cellulose nanofibers (TOCNFs) and cast into thin films. The mechanical properties of these differently sized, yet chemically similar, nanoparticles were compared as a function of CNC composition. A cooperative enhancement of the ultimate tensile strength and elongation was observed at low CNC loadings where CNCs and TOCNFs were found to self-organize during casting in a mutually beneficial manner.

High levels of ionizing radiation are known to cause degradation and/or cross-linking in polymers. Lower levels of ionizing radiation, such as x-rays, are commonly used in the treatment of cancers. Material characterization has not been fully explored for polymeric materials exposed to therapeutic radiation levels. This study investigated the effects of therapeutic radiation on three porous scaffolds: polycaprolactone (PCL), polyurethane (PU) and gelatin. Porous scaffolds were fabricated using solvent casting and/or salt leaching techniques. Scaffolds were placed in phosphate buffered saline (PBS) and exposed to a typical cancer radiotherapy schedule. A total dose of 50 Gy was broken into 25 dosages over a three-month period. PBS was collected over time and tested for polymer degradation through high performance liquid chromatography (HPLC) and bicinchoninic acid (BCA) protein assay. Scaffolds were characterized by changes in microstructure using Scanning Electron Microscopy (SEM), and crystallization using Differential Scanning Calorimetry (DSC). Additionally, gelatin ε-amine content was analyzed using Trinitrobenzene Sulfonic Acid Assay (TNBSA). Gelatin scaffolds immersed in PBS for three months without radiation served as a control. Each scaffold responded differently to radiation. PCL showed no change in molecular weight or microstructure. However, the degree of crystallinity decreased 32% from the non-irradiated control. PU displayed both changes in microstructure and a decrease in crystallinity (85.15%). Gelatin scaffolds responded the most dramatically to radiotherapy. Samples were observed to swell, yet maintain shape after exposure. As gelatin was considered a tissue equivalent, further studies on tissues are needed to better understand the effects of radiotherapy. / Master of Science

This project addresses two main subjects of moisture-cure polyurethane (PUR) wood adhesives: wood/PUR interactions and structure-property behavior emphasizing on weather durability. For these purposes, one simplified model PUR (MPUR) and three more commercially significant PURs (CPURs) with different hard segment contents were prepared. Separately, an early side project involved the synthesis of a 13C and 15N double-labeled polymeric methylenebis(phenylisocyanate) (pMDI) resin; this was used for the solid-state NMR characterization of isocyanate cure chemistry in wood bondline. MPUR and a CPUR were employed to investigate whether wood/adhesive interactions influence PUR properties. Wood interactions significantly altered PUR hard/soft domain size distribution (atomic force microscopy, AFM), thermal transition temperatures (dynamic mechanical analyses, DMA), and urethane/urea hydrogen bonds (Fourier transform infrared spectroscopy, FTIR). The effects of hard segment content on properties of PUR prepolymers, and cured PURs (films and wood composites) were studied. Hard segment content largely influenced the PURs’ molecular weights, viscosity, penetration, thermal transitions, and hard segment hydrogen bonds, but only slightly altered the dry (unweathered) bondline toughness. Three accelerated weathering procedures were developed to evaluate CPUR bondline weather durability through mode-I fracture testing. Both hard segment content and weathering conditions were found to significantly influence the bondline weather durability. Among these weathering procedures, only one (VPSS) was able to effectively distinguish weather durability of PUR adhesives, and therefore it was selected for detailed structure-weather durability studies. PUR weather durability was found to correlate with its moisture sensitivity and hard segment softening temperature; both were provided by water-submersion DMA. Much attention was directed to the investigation of weather-induced PUR molecular changes. FTIR studies provided evidences of post-cure, hydrolytic degradation, and variation of urethane/urea hydrogen bonds. DMA presented weathering effects on PUR thermal properties. Special efforts have been made to correlate these analytical results with PUR weather durability. A 13C and 15N double-labeled pMDI resin was synthesized and used for solid-state NMR characterization of isocyanate cure chemistry in wood bondline, particularly to detect the evidence of urethane formation. Rotational echo double resonance (REDOR) NMR clearly revealed the formation of urethane linkages, but largely overestimated their content. / Ph. D.

The corrosion of the drinking water distribution system is a serious problem in the United States. The annual cost to repair damages related to corrosion for public utilities in the United States are estimated at $22 billion. Polyurethane can be used as an in situ pipe liner which reduces the overall cost to rehabilitate water mains. Polyurethane is gaining popularity as a drinking water pipe liner. Not much is known about the effects of polyurethane to reline potable pipes. Polyurethane has only recently begun to be approved by the U.S. Environmental Protection Agency for use in drinking water piping, although it has been used in the United Kingdom since 1999. The American National Standards Institute/National Sanitation Foundation 61 Drinking Water System Components â Health Effects (ANSI/NSF 61) for pipe and pipe liners was used to investigate changes in water quality in contact with polyurethane lining material. In addition, the exposure time was extended to 30 days and odor analysis was performed. Polyurethane coupons were placed in headspace free borosilicate glass vessels with a surface area to volume ratio of 0.39. The water was pH 8 and comprised of salts: MgSO₄, NaHCO₃, CaSO₄, CaC1₂, Na₂SiO₃ and KNO₃ in a ratio typical of standard drinking water. Three types of disinfectant were used: no disinfectant, chlorine and monochloramine. The water was removed, sampled and replaced on days 1, 2, 4, 9, 11, 14, 15, 19, 21 and 30. The sample water was tested for pH, temperature, total organic carbon concentration (TOC), disinfectant residual, ammonia concentration as N-NH₃, hardness as combined Ca and Mg concentrations, alkalinity and temperature on days when the sample water was changed. Total solids (TS), odor, trihalomethanes (THMs), haloacetic acids (HAAs), and semivolatile organic carbons (SVOCs) were tested on days 1, 4, 9, and 14. The polyurethane lining had major impacts on pH, odor and haloacetic acids throughout the 30 day experiment. A 2-3 pH unit decrease to pH 6 was constant for all conditions tested. Odor panelists described the odor for both chlorinated and monochloraminated waters as "chlorinous" and either pleasant as "sweet chemical" or putrid as "locker room" . Haloacetic acids were formed and increased in concentration (by approximately 30 µg/L, which is half the US EPA regulated value of 60 µg/L). Trihalomethane formation was not seen. Total organic carbon leached from the polyurethane liners reached 0.65 mg/L above background on day 1 but by day 15 was only >0.1 mg/L above background. Chlorine and monochloramine were consumed by the polyurethane and increased exposure time leads to decreased disinfectant residual. It is important for water utilities to know how a lining material will affect the water quality. It has been shown that other polymeric lining materials have impacted the disinfection by-products as well as producing odor. Water treatment facilities are responsible for the water quality throughout the infrastructure and with Environmental Protection Agency regulations becoming stricter they cannot afford to not know the impact of polymeric lining materials in their system. / Master of Science

This research concerns the development and characterization of methylene bis (p-cyclohexyl isocyanate/butanediol) (HMDI/BD) based polyurethanes used in connection with surface-active anti-microbial polyurethanes. Previously studied polyurethanes having an isophorone diisocyanate/butanediol (IPDI/BD) hard block contaminated water during dynamic contact angle (DCA) analyses. This contamination by unknown species confounds results from biocidal studies and jeopardizes the use of the polyurethane as a matrix polyurethane. By contrast, polyurethanes with methylene bis (p-cyclohexyl isocyanate)/butanediol hard block showed no contamination during DCA analysis. For this reason, further study of HMDI/BD/PTMO polyurethanes was conducted. HMDI/BD polyurethanes were synthesized with 15-50wt% hard block and a soft block of PTMO-2000 or PTMO-1000 where PTMO-2000 is poly (tetramethylene oxide) with a molecular weight of 2000g/mol and PTMO-1000 has a molecular weight of 1000g/mol. Characterization was performed with FT-IR and 1H NMR spectroscopy to verify polyurethane composition as well as hard block percentage. Thermal characterization was performed with modulated differential scanning calorimetry (MDSC). From MDSC, the glass transition temperatures of the soft and hard block for polyurethanes with PTMO-2000 as the soft block were -80°C and 86°C, respectively. For corresponding polyurethanes containing PTMO-1000 as the soft block, the measured Tgs for the soft and hard segments were -55°C and 65°C, respectively. The disparity between the respective soft and hard segment Tgs of these polyurethanes of differing soft block molecular weights is due to increased phase mixing that causes an increase in soft block Tg and a decrease in hard block Tg for the PTMO-1000 polyurethanes. From dynamic contact angle analyses of HMDI/BD/PTMO polyurethanes, the advancing and receding contact angles gradually decreased with each cycle but approached 80° and 60°, respectively. Results from force-distance curves with flamed glass slides obtained before and after immersion of the polyurethane coatings indicated that no water contamination occurred. Tensile tests demonstrated that hard block percentage, soft block molecular weight, and the amount of chain extender influences mechanical properties. For example, increasing hard block weight percentage increases the modulus. HMDI/BD(30)/PTMO-2000 (PU-1), HMDI/BD(25)/PTMO-2000, (PU-2) and HMDI/BD(35)/PTMO-2000 (PU-10) exhibited the best elastomeric properties. As the final outcome, lack of contamination and good mechanical properties made PU-2 and PU-9 (HMDI/BD(50)/PTMO-1000) suitable candidates as polyurethane matrices for polymer surface modifier evaluation.

Este trabalho tem como objetivo o desenvolvimento de uma tecnologia para a atenuação do impacto provocado pelo passivo ambiental gerado por pneus inservíveis, conjuntamente ao desenvolvimento de novos materiais compostos para uso na construção.Os pneus têm uma estrutura física especial, com grande resistência e durabilidade, mesmo ao término de sua vida útil e, por isso, sua deposição em aterros sanitários é inadequada, já que eles não permitem compactação, tornando-se favoráveis para a criação de agentes causadores de enfermidades e oferecem grandes riscos de incêndios, o que acarreta sérios danos ao meio ambiente. A tecnologia desenvolvida utilizou a borracha de pneus inservíveis, após serem picados por processo mecânico, segundo diferentes tamanhos, para a composição de produtos de baixo custo e utilizáveis na construção civil em elementos construtivos, placas de amortecimento sonoro e de revestimento de pisos para edificações, sinalização horizontal em vias públicas, absorvedores de impacto em estradas,etc. O agente de aglomeração utilizado foi a resina poliuretânica derivada do óleo de mamona (Ricinus communis), uma fonte renovável, que também apresenta estabilidade física e química, e um excelente desempenho como aglomerante. O composto obtido foi testado com relação à durabilidade, às propriedades mecânicas como resistência à compressão e tração, módulo de elasticidade e fluência por meio da termo análise, demonstrando resultados satisfatórios e confirmada sua aplicação em vários campos da construção civil. / The objective of this work is to develop a technology for the impact attenuation caused by the passive environmental generated by scrap tires, jointly to the development of new composites for being used in construction. The tires have a special physical structure, with great resistance and durability, also in the term of their useful life, therefore, their deposit in landing fields are inadequate, once they do not allow compacting, becoming favorable for the creation of causes of diseases and they offer great fires risks, what causes serious damages to the environment. The developed technology used the rubber of useless tires, after being fragmented by mechanic process, according to different sizes, for the composition of products of low cost to be used in the civil construction in constructive elements, noise reduction plates and lining of floors for constructions, horizontal signaling in public ways, impact insulating in highways, and so on. The agent of mass used was the polyurethane resin, derived of the castor oil (Ricinus communis), a renewable source that also presents physical and chemical stability, and a good bonding behavior. The obtained composite was tested in relation to durability behavior, mechanical properties which the compression forces and tension, and also its modulus of elasticity and creep by use of thermo analisys, demonstrated satisfactory results and confirmed its application in a many fields of the civil construction.

Synthèse de nouveaux WPU (waterborne polyurethane) cationiques à partir du caoutchouc naturel (NR), et évaluation de leurs propriétés adhésives pour des surfaces de type cuir. Ces WPU ont été obtenus par réaction du caoutchouc liquide hydroxy téléchélique (HTNR), de toluene-2,4-diisocyanate (TDI), N-methyl diethanol amine (NMDEA, en tant qu’émulsifiant) et d’éthylène glycol (EG, extenseur de chaîne). Ces structures biosourcés sont développés comme alternatives aux WPU issus des ressources fossiles à fort impact environnemental. Les effets de cinq paramètres ont été étudiés, à savoir la quantité d'émulsifiant (de 0 à 2,25 mole), celle d’éthylène glycol (de 0 à 3 moles), le Mn du HTNR (de 100 à 3000 g/mole), l'indice NCO (de 100 à 150) et le taux d’époxydation des HTNR précurseurs (de 0 à 30%). Il a été en outre démontré que la stabilité des dispersions aqueuses pour les formulations optimales dépassait les 10 mois. La géométrie des particules dispersées a été étudiée, démontrant un aspect sphérique et une taille à l'échelle nanométrique. Ainsi, plusieurs facteurs ont été étudiés pour évaluer les propriétés adhésives optimales sur bandes de cuir (Mn, pourcentage d’'époxyde). Des tests standard (Peel test et Lap Shear test) ont été utilisés et les valeurs obtenues comparées avec celles issus de formulations adhésives commerciales avec ou sans solvants. Au bilan, une formulation optimale a été déterminée (Mn = 3000 g/mole, LR epoxydation = 10%, NMDEA 5.67%wt, NCO index de 100 et 1 mole d’EG) avec cuisson préalable des systèmes à 70°C. Ce WPU a montré une force d’'adhésion supérieure à toutes les formulations commerciales testées. / Novel cationic waterborne polyurethane (cWPU) based on natural rubber (NR) have been prepared by the polymerization reaction of hydroxyl telechelic natural rubber (HTNR), toluene-2,4-diisocyanate (TDI), N-methyl diethanol amine (NMDEA, as emulsifier), and ethylene glycol (EG, chain extender). The polyol structures have been developed as alternative to produce cWPUs derived from a renewable resource. The effects of five parameters were studied – amount of NMDEA (0 – 2.25 mole), amount of EG (0 – 3 mole), molecular weight of HTNR (~1000 – 3000 g/mole), NCO index (100 – 150), and epoxide content on eHTNR soft segment (0 – 30%). The appearance of cWPU dispersion was milky-blue with long shelf life time, more than 10 months. Particle of prepared cWPU were spherical shape in the nano range size. The adhesive properties of cWPUs on the real leather surface, taking into account of the different molecular weights of HTNR and different degree of epoxide content on HTNR, were tested by lap shear test and 180 degree peel test and compared with commercial adhesives. Overall, to balance the stability and adhesive strength, the best conditions for preparing cWPU adhesive for leather application in this study was from the composition of HTNR3000 with epoxide content of 10%, NMDEA 5.67%wt, NCO index of 100 and 1 mole of EG. in condition of curing at 70 °C. In comparison to non-solvent based and solvent based commercial adhesives, the adhesive strengths of these synthesized cWPU adhesive were superior.

In this work, hyperbranched aromatic polyesters-polyphenols based on 4,4-bis(4’ hydroxy¬phenyl)pentanoic acid (BHPPA) were prepared and, according to the authors knowledge, for the first time tested as precursors for polyurethane bulk resins and coatings. Comparison of poly-BHPPA with competing products The materials prepared in this work show better properties than their aliphatic polyester-polyol analoga based on 2,2-bis-(hydroxymethyl)propanoic acid (BHMPA). Especially, the solubility of poly-BHPPA in organic solvents is better and poly-BHPPAs also do not tend to microphase separation during their reaction with isocyanates, in contrast to poly-BHMPAs. The poly-BHPPA and the polyurethane networks made from them display higher Tg values than analogous poly- BHMPA compounds. Because of the high Tg of the reacting and final systems, curing must occur at elevated temperatures (90°C) in order to avoid undercure. The lower reactivity of phenolic OH groups prevents the reaction from being too fast at that temperature. A drawback of the polyurethanes based on the aromatic polyesters-polyols prepared is the lower thermal stability of their urethane bonds, if compared to aliphatic urethanes. An interesting possibility for future investigations would be the modification of the BHPPA monomer in order to change the OH functionality from phenolic to aliphatic OH, e.g. by replacement of the phenolic OH by hydroxymethyl or hydroxyethyl groups (requires a strong modification of the monomer synthesis) or simpler by reacting the phenolic OH of BHPPA with a suitable reagent like oxirane, which would lead to groups like O-CH2-CH2-OH in the place of the phenolic OH. Such a BHPPA modification should in turn yield modified “poly-BHPPA” polycondensates, which would combine the advantages of poly-BHPPA with those of aliphatic OH precursors of polyurethanes. Poly-BHPPA synthesis Hyperbranched polymers of the 4,4-bis-(4’-hydroxyphenyl)pentanoic acid (BHPPA) were synthesized successfully by the catalyzed (by dibutyltin diacetate) polycondensation of BHPPA. The products obtained were oligomers with number average molecular weight ranging from 1800 to 3400 g/mol (polymerization degree of ca. 6 to 12), displaying a first moment of functionality in the range 7 to 14. Such products were good OH precursors for the preparation of polyurethane coatings, because higher functional polymers would gel at low conversions. The analysis of the functional groups (determination of acid and hydroxyl numbers) and the 1H-NMR and the 13C-NMR spectroscopy were found to be good methods for the determination of molecular weights. The polydispersity of the poly-BHPPA products was in the range 3.5 to 6. Their degree of branching was found to be in the range 0.36 to 0.47. Poly-BHPPA containing aliphatic polyols as core monomers were also prepared successfully. Difunctional and trifunctional core monomers usually reached a full conversion of their OH groups, while the tetra- and hexafunctional core monomers were converted only to 89%. In all these products however, a considerable amount, usually even a majority, of the polymer molecules were core free. The poly-BHPPA products prepared displayed relatively high glass transition temperatures, in the range of 84°C to 114°C, obviously due to interactions between the phenol groups and to hydrogen bridging. The thermal stability of these products was also high, with decomposition occurring near 350°C (at a heating rate of 10°C / min) Kinetics investigations of the poly-BHPPA reactivity towards isocyanates The poly-BHPPA are polyphenols and were expectedly found to react significantly slower with isocyanates than aliphatic alcohols. The reactivity of poly BHPPA was also found to be somewhat lower than that of the monofunctional, low molar-mass 4 ethylphenol. Hexamethylene diisocyanate trimer, Desmodur N3300, was found to be more reactive than hexamethylene diisocyanate (HDI) or butyl isocyanate in all experiments, possibly due to a substitution effect. The substitution effect can be explained by a change of microenvironment caused by conversion of isocyanate group and OH group into urethane groups. The reactions of low-molecular-mass alcohols or phenols with low molecular weight isocyanates followed well the 2nd order kinetics, while the reactions of poly-BHPPA with isocyanates show deviations from ideal 2nd order kinetics at higher conversions. All the kinetics experiments were carried out under catalysis by dibutyltin dilaurate. This catalyst inhibits the undesired reaction of isocyanate groups with moisture. It was also found that the catalysis was necessary to reach reasonable curing times for poly-BHPPA based polyurethane networks. The uncatalyzed systems reacted extremely slowly. Preparation of polyurethane networks from poly-BHPPA The poly BHPPA products prepared were used successfully as OH functional precursors of polyurethane networks. The networks prepared contained only very low sol fractions. Acetone and also ethylene diglycol dimethylether (diglyme) were found to be good swelling solvents for the networks prepared, while methyl propyl ketone was a much poorer solvent and aromatic compounds like toluene or xylene practically did not swell the poly BHPPA based polyurethanes. The networks prepared contain a relatively high amount of cyclic bonds, 40 to 50% in the finally cured state, which is an expected result for systems with precursors of high functionality and with small distances between the functional groups. The temperature of glass transition (Tg) of the networks prepared (ranging from 68°C to 126°C) depends of the poly BHPPA precursor used: it increases with increasing molecular mass and with increasing core functionality. The choice of the isocyanate crosslinker also influences Tg: the networks made from HDI show higher Tg values, than networks made from the same poly BHPPA but crosslinked with Desmodur N3300 (Tri HDI). The urethane bonds in the networks prepared start to decompose near 140°C. The easier degradation of PU with aromatic urethane bonds is a disadvantage in comparison with aliphatic polyurethanes, whose decomposition starts at 200°C. The surfaces of polyurethane coatings prepared are smooth, displaying a roughness of ca. 20-25 nm, and relatively hydrophilic: the contact angle with water was found to be near 80°. The prepared networks are also relatively hard, possessing the Shore D hardness of 70.