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Um novo iniciador para metátese do tipo GH nitro-substituído [Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-5-NO2-C6H3)][OTf-]2 (3b) foi preparado. Os comprimentos de ligação e deslocamentos químicos foram comparáveis aos do iniciador 3a ([Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-C6H3)][OTf-]2), embora o substituinte NO2 na porção benzilideno resulte numa ligação Ru-O mais curta. A comparação entre os iniciadores do tipo GH e 5-NO2-GH indica que a substituição dos cloretos por pseudo-haletos resulta em maior polarização da ligação Ru=C e uma ligação Ru-O mais forte. O iniciador 3b e os iniciadores análogos do tipo GH [Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-]2 (3a) e [RuCl(1-CH3-4-CO2-Py+)(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-] (5a) foram usados para reações de ROMP em meio homogêneo e em meio bifásico líquido/líquido usando o líquido iônico [BDMIM+][BF4-] e tolueno. Os catalisadores foram ativos para a ROMP de monômeros a base de norborneno (NBE), cis-cicloocteno (COE) e diciclopentadieno (DCPD) em meio homogêneo com bons rendimentos. O catalisador mono-iônico 5a foi mais ativo que os catalisadores 3a e 3b. As reações de ROMP em meio bifásico permitiram a síntese de polímeros com baixos valores de IPD (1,2-2,4) e altos rendimentos. O uso de um agente de transferência de cadeia (ATC) gerou polímeros com baixo teor de metal (entre 10 e 80 ppm), o que corresponde a uma remoção de 98-99,4% do Ru inicial. Em adição, o uso do ATC permitiu a realização de experimentos de reciclagem em meio bifásico para a ROMP de NBE, onde 3a e 5a foram ativos por vários ciclos. Apesar de menos ativo, 3a foi mais estável, por manter a atividade por maior número de ciclos. Foi observada baixa contaminação de Ru nos polímeros após cada ciclo (8-75 ppm), o que representa uma remoção de 98-99,9%. <br /> Como uma segunda parte do trabalho, os novos complexos [RuCl2(PPh3)2(4-CH2R-pip)], com R = H (1), Ph (2) e OH (3), foram sintetizados e aplicados como iniciadores para a ROMP de norborneno (NBE) e norbornadieno (NBD) sob diferentes tempos de reação, temperaturas e concentrações de monômero. Houve uma clara diferença nos rendimentos de homopolímero na ordem 1 > 2 > 3 na razão molar [monômero]/[Ru] = 5000 a 25 &deg;C de 5-60 min. A diferença nos rendimentos tende a desaparecer a 50 &deg;C, com rendimentos quantitativos para 15-30 min usando qualquer iniciador. Os resultados dos copolímeros obtidos a TA por 60 min a partir de soluções contendo quantidades fixas de NBE e quatro quantidades diferentes de NBD sugerem que o tipo de iniciador também afeta as reações, com maior inserção de NBD com 1. A ocorrência de ligações cruzadas aumentou com o aumento da carga de NBD, evidenciado pelo decréscimo nos valores de Mc e aumento valores de Tg. <br /> Em outra parte do doutorado, o novo complexo de RuIII [RuCl3(PCy3)2] foi sintetizado e caracterizado, se mostrando estável ao ar. O complexo foi aplicado como iniciador para ROMP em ar e apresentou significante diferença na reatividade para norborneno (NBE) e norbornadieno (NBD). Rendimentos quantitativos de poliNBD foram obtidos instantaneamente a 25 &deg;C, enquanto 40 % de poliNBE foi produzido em 5 min a 25 &deg;C e 95% em 60 min a 50 &deg;C. A copolimerização de NBE e NBD com diferentes razões molares iniciais [NBD]/[Ru] a 25 &deg;C resultaram em materiais com uma grande quantidade de NBD. Os valores de Tg mudaram de 37 (poliNBE) para 90 &deg;C (poli[NBE-co-NBD]) com o aumento da carga de NBD. A caracterização morfológica mostrou que os copolímeros apresentam uma tendência a serem mais organizados com a diminuição da carga de NBD, com um padrão bem definido do tipo favo de mel para a amostra contendo a menor quantidade de NBD. / A novel Grubbs-Hoveyda (GH) nitro-substituted ionic metathesis initiator [Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-5-NO2-C6H3)][OTf-]2 (3b) has been prepared. Bond lengths and chemical shifts were comparable to 3a ([Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-C6H3)][OTf-]2), although the NO2 substituent in the benzilidene moiety affords shorter Ru-O bond. Comparison between GH and 5-NO2-GH initiators indicates that the replacement of chlorides by pseudo-halides result in higher polarization of Ru=C bond and stronger Ru-O bond. 3b and the parent GH initiators [Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-]2 (3a) and [RuCl(1-CH3-4-CO2-Py+)(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-] (5a) were used for ROMP reactions under homogeneous and biphasic liquid/liquid conditions using the ionic liquid [BDMIM+][BF4-] and toluene. The catalysts were active for ROMP of norbornene(NBE)-based monomers, cis-cicloocteno (COE) and dicyclopentadiene (DCPD) under homogeneous conditions providing good yields. The monoionic catalyst 5a was more active than the dicationic 3a and 3b. ROMP under biphasic conditions allowed for preparing polymers with lower PDIs (1.2-2.4) and higher yields. The use of a chain transfer agent (CTA) allowed for polymers with low metal content (range between 10 and 80 ppm), which corresponds to a Ru-removal of 98-99.4%. In addition, the use of a CTA allowed for recycling experiments under biphasic conditions for ROMP of NBE, were 3a and 5a were active for several cycles. Besides less active, 3a was more stable, once it was active for more cycles. Low Ru contamination was observed for the polymers after each cycle (8-75 ppm), a Ru-removal of 98-99.8%. <br /> As a second part of the work, the novel [RuCl2(PPh3)2(4-CH2R-pip)] complexes, with R = H (1), Ph (2) or OH (3), were synthesized and applied as initiators for ROMP of norbornene (NBE) and norbornadiene (NBD) under different reaction times, temperatures and monomer concentrations. There was clear difference in the homopolymer yields in the order 1 > 2 > 3 at [monomer]/[Ru] molar ratio of 5000, at 25 &deg;C for 5-60 min. Difference in the yields tend to disappear at 50 &deg;C, with quantitative yields for 15-30 min with any type of initiator. Results from copolymers obtained at RT for 60 min from fixed amounts of NBE with four different amounts of NBD suggest that the type of initiator also affects the reactions, with more insertion of NBD with 1. The occurrence of cross-linking enhanced as the NBD loading increased, evidenced by decrease in the Mc and increase in the Tg values. <br /> In other part of PhD, the novel RuIII complex [RuCl3(PCy3)2] was synthesized and characterized, being stable in air. The complex was applied as initiator for ROMP in air and presented significant difference in reactivity for ROMP of norbornene (NBE) and norbornadiene (NBD). Quantitative yields of polyNBD were obtained instantaneously at 25 &deg;C, whereas 40 % of polyNBE resulted for 5 min at 25 &deg;C or 95% for 60 min at 50 &deg;C. Copolymerization of NBE and NBD with different starting [NBD]/[Ru] molar rations at 25 &deg;C resulted in materials with large amount of NBD. Tg values changed from 37 (polyNBE) to 90 &deg;C (poly[NBE-co-NBD]) as the NBD loading increased. Morphological characterization showed that the copolymers present a tendency to be more organized as the NBD loading decreases, with a well-defined honeycomb-like pattern for the copolymer isolated from the run with the lowest NBD load.

Um novo iniciador para metátese do tipo GH nitro-substituído [Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-5-NO2-C6H3)][OTf-]2 (3b) foi preparado. Os comprimentos de ligação e deslocamentos químicos foram comparáveis aos do iniciador 3a ([Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-C6H3)][OTf-]2), embora o substituinte NO2 na porção benzilideno resulte numa ligação Ru-O mais curta. A comparação entre os iniciadores do tipo GH e 5-NO2-GH indica que a substituição dos cloretos por pseudo-haletos resulta em maior polarização da ligação Ru=C e uma ligação Ru-O mais forte. O iniciador 3b e os iniciadores análogos do tipo GH [Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-]2 (3a) e [RuCl(1-CH3-4-CO2-Py+)(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-] (5a) foram usados para reações de ROMP em meio homogêneo e em meio bifásico líquido/líquido usando o líquido iônico [BDMIM+][BF4-] e tolueno. Os catalisadores foram ativos para a ROMP de monômeros a base de norborneno (NBE), cis-cicloocteno (COE) e diciclopentadieno (DCPD) em meio homogêneo com bons rendimentos. O catalisador mono-iônico 5a foi mais ativo que os catalisadores 3a e 3b. As reações de ROMP em meio bifásico permitiram a síntese de polímeros com baixos valores de IPD (1,2-2,4) e altos rendimentos. O uso de um agente de transferência de cadeia (ATC) gerou polímeros com baixo teor de metal (entre 10 e 80 ppm), o que corresponde a uma remoção de 98-99,4% do Ru inicial. Em adição, o uso do ATC permitiu a realização de experimentos de reciclagem em meio bifásico para a ROMP de NBE, onde 3a e 5a foram ativos por vários ciclos. Apesar de menos ativo, 3a foi mais estável, por manter a atividade por maior número de ciclos. Foi observada baixa contaminação de Ru nos polímeros após cada ciclo (8-75 ppm), o que representa uma remoção de 98-99,9%. <br /> Como uma segunda parte do trabalho, os novos complexos [RuCl2(PPh3)2(4-CH2R-pip)], com R = H (1), Ph (2) e OH (3), foram sintetizados e aplicados como iniciadores para a ROMP de norborneno (NBE) e norbornadieno (NBD) sob diferentes tempos de reação, temperaturas e concentrações de monômero. Houve uma clara diferença nos rendimentos de homopolímero na ordem 1 > 2 > 3 na razão molar [monômero]/[Ru] = 5000 a 25 &deg;C de 5-60 min. A diferença nos rendimentos tende a desaparecer a 50 &deg;C, com rendimentos quantitativos para 15-30 min usando qualquer iniciador. Os resultados dos copolímeros obtidos a TA por 60 min a partir de soluções contendo quantidades fixas de NBE e quatro quantidades diferentes de NBD sugerem que o tipo de iniciador também afeta as reações, com maior inserção de NBD com 1. A ocorrência de ligações cruzadas aumentou com o aumento da carga de NBD, evidenciado pelo decréscimo nos valores de Mc e aumento valores de Tg. <br /> Em outra parte do doutorado, o novo complexo de RuIII [RuCl3(PCy3)2] foi sintetizado e caracterizado, se mostrando estável ao ar. O complexo foi aplicado como iniciador para ROMP em ar e apresentou significante diferença na reatividade para norborneno (NBE) e norbornadieno (NBD). Rendimentos quantitativos de poliNBD foram obtidos instantaneamente a 25 &deg;C, enquanto 40 % de poliNBE foi produzido em 5 min a 25 &deg;C e 95% em 60 min a 50 &deg;C. A copolimerização de NBE e NBD com diferentes razões molares iniciais [NBD]/[Ru] a 25 &deg;C resultaram em materiais com uma grande quantidade de NBD. Os valores de Tg mudaram de 37 (poliNBE) para 90 &deg;C (poli[NBE-co-NBD]) com o aumento da carga de NBD. A caracterização morfológica mostrou que os copolímeros apresentam uma tendência a serem mais organizados com a diminuição da carga de NBD, com um padrão bem definido do tipo favo de mel para a amostra contendo a menor quantidade de NBD. / A novel Grubbs-Hoveyda (GH) nitro-substituted ionic metathesis initiator [Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-5-NO2-C6H3)][OTf-]2 (3b) has been prepared. Bond lengths and chemical shifts were comparable to 3a ([Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-C6H3)][OTf-]2), although the NO2 substituent in the benzilidene moiety affords shorter Ru-O bond. Comparison between GH and 5-NO2-GH initiators indicates that the replacement of chlorides by pseudo-halides result in higher polarization of Ru=C bond and stronger Ru-O bond. 3b and the parent GH initiators [Ru(1-CH3-4-CO2-Py+)2(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-]2 (3a) and [RuCl(1-CH3-4-CO2-Py+)(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-] (5a) were used for ROMP reactions under homogeneous and biphasic liquid/liquid conditions using the ionic liquid [BDMIM+][BF4-] and toluene. The catalysts were active for ROMP of norbornene(NBE)-based monomers, cis-cicloocteno (COE) and dicyclopentadiene (DCPD) under homogeneous conditions providing good yields. The monoionic catalyst 5a was more active than the dicationic 3a and 3b. ROMP under biphasic conditions allowed for preparing polymers with lower PDIs (1.2-2.4) and higher yields. The use of a chain transfer agent (CTA) allowed for polymers with low metal content (range between 10 and 80 ppm), which corresponds to a Ru-removal of 98-99.4%. In addition, the use of a CTA allowed for recycling experiments under biphasic conditions for ROMP of NBE, were 3a and 5a were active for several cycles. Besides less active, 3a was more stable, once it was active for more cycles. Low Ru contamination was observed for the polymers after each cycle (8-75 ppm), a Ru-removal of 98-99.8%. <br /> As a second part of the work, the novel [RuCl2(PPh3)2(4-CH2R-pip)] complexes, with R = H (1), Ph (2) or OH (3), were synthesized and applied as initiators for ROMP of norbornene (NBE) and norbornadiene (NBD) under different reaction times, temperatures and monomer concentrations. There was clear difference in the homopolymer yields in the order 1 > 2 > 3 at [monomer]/[Ru] molar ratio of 5000, at 25 &deg;C for 5-60 min. Difference in the yields tend to disappear at 50 &deg;C, with quantitative yields for 15-30 min with any type of initiator. Results from copolymers obtained at RT for 60 min from fixed amounts of NBE with four different amounts of NBD suggest that the type of initiator also affects the reactions, with more insertion of NBD with 1. The occurrence of cross-linking enhanced as the NBD loading increased, evidenced by decrease in the Mc and increase in the Tg values. <br /> In other part of PhD, the novel RuIII complex [RuCl3(PCy3)2] was synthesized and characterized, being stable in air. The complex was applied as initiator for ROMP in air and presented significant difference in reactivity for ROMP of norbornene (NBE) and norbornadiene (NBD). Quantitative yields of polyNBD were obtained instantaneously at 25 &deg;C, whereas 40 % of polyNBE resulted for 5 min at 25 &deg;C or 95% for 60 min at 50 &deg;C. Copolymerization of NBE and NBD with different starting [NBD]/[Ru] molar rations at 25 &deg;C resulted in materials with large amount of NBD. Tg values changed from 37 (polyNBE) to 90 &deg;C (poly[NBE-co-NBD]) as the NBD loading increased. Morphological characterization showed that the copolymers present a tendency to be more organized as the NBD loading decreases, with a well-defined honeycomb-like pattern for the copolymer isolated from the run with the lowest NBD load.

Romantic relationship dissolution has been implicated in the onset of mood disorders (Monroe et al.,1999; Overbeek et al., 2003). It is therefore imperative that researchers and mental health professionals have an understanding of the factors that contribute to dysfunctional responses so as to assist vulnerable individuals with developing healthy strategies for coping with relationship dissolution. Prior research on the relationship between initiator status (i.e., who ended the relationship) and subsequent emotional distress has been mixed, with multiple researchers finding that a person's level of distress was unrelated to whether he or she ended the relationship. I hypothesized that the effect of initiator status on post-break-up distress would vary as a function of trait self-esteem such that individuals with low self-esteem would experience more distress after being rejected by their partners, whereas individuals with high self-esteem would be no more distressed after a rejection than after acting as the rejecter. I tested this hypothesis using two designs. First, I used a prospective, naturalistic design in which university students were assessed for emotional responses following the dissolution of their romantic relationships. Those who had self-reported lower trait self esteem at the outset of the study experienced higher levels of break-up-specific distress. On the other hand, those who had reported higher trait self-esteem did not exhibit differing distress levels as a function of who ended the relationship. This pattern was replicated in a laboratory design in which university students imagined breaking up with their partners. Participants with low trait self-esteem experienced more negative mood, reported lower state self-esteem, and evaluated themselves more negatively after a scenario in which they were rejected as compared to a scenario in which they rejected their partners. Participants with high self-esteem did not differ on any of these variables as a function of rejection condition. Results are discussed in terms of the theoretical implications for understanding self-esteem processes and the effects of romantic rejection. Implications for interventions for individuals with low self-esteem who are coping with romantic rejection are also explored. / Thesis (Ph.D, Psychology) -- Queen's University, 2007-07-12 12:36:26.478

Techn. Universiẗat, Diss., 2006--München.

<p> The polymerization of styrene to polystyrene was studied using gamma radiation from a Co^60 source as the free radical initiator. Conversions up to 50% were obtained and the molecular weight distribution, intrinsic viscosity, bulk viscosity, and osmotic pressure of several samples were measured. A theoretical kinetic model was developed using a slightly modified conventional kinetic scheme and employing a viscosity correction for the termination rate constant. The model predicts conversion over the range studied and molecular weight distributions are in agreement within the limitations of the experimental equipment to measure this parameter.</p> / Thesis / Master of Engineering (MEngr)

Phenolic resins are important components of the composite industry because of their excellent flame retardance and cost effectiveness. However, the common procedure for curing phenolic novolac resins uses hexamethylenetetramine (HMTA) and releases volatiles during the cure, which produce networks with numerous voids. This results in materials that lack the toughness necessary for structural applications. An alternative to curing with HMTA is to crosslink the pendant phenolic groups in the novolac resin with epoxy reagents. This reaction proceeds by nucleophilic addition without the release of any volatiles, thereby creating a void-free network. Flame retardance can be achieved by using an excess of the phenolic component. Network densities can also be controlled to maximize both toughness and stiffness by tailoring the stoichiometry of the reagents. Structure-property relationships of phenolic/epoxy networks have been investigated. Glass transitions decreased, and toughness increased, as the phenolic content in the network was increased. Both results could be correlated to the decrease in network densities along this series, which was investigated by measuring the rubbery moduli well above T_g. Fracture toughness of phenolic/epoxy networks measured by K_1c reached 1.03 MPa-m^1/2, compared with an epoxy control with K^1c = 0.62 MPa-m^1/2 and phenolic control with K_1c = 0.16 MPa-m^1/2. In addition, an increase in novolac content improves flame retardance rather dramatically. The peak heat release rate (PHRR) dropped from 1230 kW/m²⁺ for the epoxy control to 260 kW/m²⁺ for the phenolic/epoxy networks, which approached that of a phenolic resol (PHRR = 116 kW/m²⁺). Phenolic/epoxy composite flame retardance also showed significant improvement when compared to epoxy composites. Melt processability of phenolic/epoxy composites has been achieved through the use of latent nucleophilic initiators. Kinetics of the phenolic/epoxy cure reactions with latent initiators demonstrated that monomeric phosphine initiators yielded faster cure reactions as compared to polymeric initiators. These latent initiators allow composite melt processing, such as prepregging or pultrusion, without premature curing. In addition, cure cycles can be reduced from 4 hours to less than 30 minutes. Composites prepared using these latent initiators had toughness exceeding that of epoxy composites and fatigue limits significantly higher than those of vinyl ester composites. <i>Vita removed, June 10, 2013, per author's request. GMc</i> / Ph. D.

"In situ polymerizing hydrogel systems play an important role in many tissue engineering applications. They have proven to be useful in biomedical applications that require conversion of liquid macromer solution to tissue compliant hydrogel under physiological conditions. A series of poly(ethylene glycol)-co-poly(lactate) diacrylate macromers were synthesized with variable PEG molecular weight and lactate content. The macromer compositions were confirmed by NMR spectroscopy and ion chromatography. These macromers were polymerized to form hydrogels by free radical polymerization using either redox or photochemical initiators. The current study focused on the optimization of polymerization conditions. Compressive modulus and residual acrylate analysis were used to evaluate polymerization efficiency. To characterize the network structure, the swelling ratio values were converted to the average molecular weight between crosslinks ( ) and mesh sizes (ξ) using Flory-Rehner theory. Current study suggested hydrophobic modification is desired to achieve high polymerization efficiency. Electrospinning is a developing technique to produce ultra fine fibrous structures from polymer solutions. Current research efforts have focused on understanding the effects of principal parameters such as molecular weight distribution (MWD) and polymer surfactant interactions on the morphology of the electrospun patterns. Fundamental understanding of the dilute solution rheology of the polydisperse polymer/solvent and polymer/solvent/surfactant systems was first established. Using viscometry, the on-set of entanglement concentrations could be obtained for various systems. Electrospinning was then carried out to evaluate the effects of polymer molecular weight, molecular weight distribution (MWD) and the polymer-surfactant interaction on the fiber formation and morphological features. The importance of increased chain entanglements due to high molecular weight component within the polydisperse system and the expansion of the coil dimension by binding the surfactant micelles have been recognized. The critical concentrations for incipient as well as stable fiber formation were determined. "

Universiẗat, Diss., 2001--Göttingen.

Universiẗat, Diss., 2004--Bremen.