An experimental and modeling investigation of nitroxide-mediated radical polymerization (NMRP) of styrene using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as controller is presented. The objective was to examine the effect of temperature, controller to initiator molar ratio, and initiation mode on conversion, molecular weight and polydispersity development, and also to generate a source of reliable experimental data for parameter estimation and further model validation purposes. Polymerizations with a bimolecular initiator (Benzoyl Peroxide; BPO) were carried out at 120 and 130°C, with TEMPO/BPO molar ratios of 0.9 to 1.5. The effects of temperature and TEMPO/BPO ratio on polydispersity, molecular weight averages and conversion (rate) were studied. Results indicate that increasing temperature increases the rate of polymerization while the decrease in molecular weights is only slight. It was also observed that increasing the ratio of TEMPO/BPO decreased both the rate of polymerization and molecular weights. To investigate the contribution of thermal self-initiation in NMRP of styrene, thermal NMRP of styrene with TEMPO in the absence of initiator was carried out at 120 and 130°C. The results were compared with regular thermal polymerization of styrene and NMRP of styrene in the presence of BPO. It was observed that although the thermal polymerization of styrene can be controlled to some extent in the presence of TEMPO to provide lower polydispersity polystyrene, the polymerization was never as controlled as that obtained by a BPO initiated NMRP. Additional experiments were conducted with a unimolecular initiator and compared to the corresponding bimolecular system with the same level of nitroxide at 120°C, to gain additional insight on the advantages and disadvantages of each system. In addition, the importance of diffusion-controlled (DC) effects on the bimolecular NMRP of styrene was assessed experimentally by creating conditions where DC effects may be present from the outset. The results were corroborated by mathematical modeling and it was concluded that DC-effects are weak in the NMRP of styrene, even in the presence of “worst case scenario” conditions created. Finally, a mathematical (mechanistic) model based on a detailed reaction mechanism for bimolecular NMRP of styrene was presented and the predicted profiles of monomer conversion, molecular weight averages and polydispersity were compared with experimental data. Comparisons suggest that the present understanding of the reaction system is still inconclusive, either because of inaccuracy in values of kinetic rate constants used or because of some possible side reactions taking place in the polymerization system that are not included in the model. This was somewhat surprising, given that papers on controlled radical polymerization, and NMRP in particular, have clearly dominated the scientific polymer literature in the last fifteen years or so.

An experimental and modeling investigation of nitroxide-mediated radical polymerization (NMRP) of styrene using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as controller is presented. The objective was to examine the effect of temperature, controller to initiator molar ratio, and initiation mode on conversion, molecular weight and polydispersity development, and also to generate a source of reliable experimental data for parameter estimation and further model validation purposes. Polymerizations with a bimolecular initiator (Benzoyl Peroxide; BPO) were carried out at 120 and 130°C, with TEMPO/BPO molar ratios of 0.9 to 1.5. The effects of temperature and TEMPO/BPO ratio on polydispersity, molecular weight averages and conversion (rate) were studied. Results indicate that increasing temperature increases the rate of polymerization while the decrease in molecular weights is only slight. It was also observed that increasing the ratio of TEMPO/BPO decreased both the rate of polymerization and molecular weights. To investigate the contribution of thermal self-initiation in NMRP of styrene, thermal NMRP of styrene with TEMPO in the absence of initiator was carried out at 120 and 130°C. The results were compared with regular thermal polymerization of styrene and NMRP of styrene in the presence of BPO. It was observed that although the thermal polymerization of styrene can be controlled to some extent in the presence of TEMPO to provide lower polydispersity polystyrene, the polymerization was never as controlled as that obtained by a BPO initiated NMRP. Additional experiments were conducted with a unimolecular initiator and compared to the corresponding bimolecular system with the same level of nitroxide at 120°C, to gain additional insight on the advantages and disadvantages of each system. In addition, the importance of diffusion-controlled (DC) effects on the bimolecular NMRP of styrene was assessed experimentally by creating conditions where DC effects may be present from the outset. The results were corroborated by mathematical modeling and it was concluded that DC-effects are weak in the NMRP of styrene, even in the presence of “worst case scenario” conditions created. Finally, a mathematical (mechanistic) model based on a detailed reaction mechanism for bimolecular NMRP of styrene was presented and the predicted profiles of monomer conversion, molecular weight averages and polydispersity were compared with experimental data. Comparisons suggest that the present understanding of the reaction system is still inconclusive, either because of inaccuracy in values of kinetic rate constants used or because of some possible side reactions taking place in the polymerization system that are not included in the model. This was somewhat surprising, given that papers on controlled radical polymerization, and NMRP in particular, have clearly dominated the scientific polymer literature in the last fifteen years or so.

Living radical polymerization has proved to be a powerful tool for the synthesis of polymers as it allows for a high degree of control over the polymer microstructure and the synthesis of tailored molecular architectures. Although it has great potential, its use on an industrial scale is limited due to environmental and economical aspects. Nitroxide mediated polymerization is explored to bring this technology closer to adoption in commercial applications. One of the obstacles encountered using nitroxide mediated polymerization in microemulsion systems is the difficulty in controlling both the particle size and target molecular weight. Due to the nature of the formulation, a decrease in the target molecular weight is coupled to an increase in the particle size. For many applications, it is important to be able to design polymer particles with both specifications independently. Strategies to decouple these two properties and processing conditions required for targeting a range of particle sizes and molecular weights for n butyl acrylate latexes are presented. Furthermore, in an attempt to reduce the large amounts of surfactant typically used in microemulsions, these methods were explored at low surfactant to monomer ratios (0.2 to 0.5 by wt.) in order to reduce the costs associated with excess surfactant and post processing steps for surfactant removal (high surfactant levels also give poor water-resistance in coatings). Stable nanolatexes with particle sizes <40 nm have been obtained by other groups using NMP in microemulsions with SG1 but have done so by using much higher surfactant to monomer ratios (~2.5 by wt.) and at much lower solids content (6 10 wt. %). In this work, molecular weights of 20,000 to 80,000 g∙mol-1 were targeted and stable, n-butyl acrylate microemulsions with particle sizes ranging from 20 120 nm were prepared at a solids content of 20 wt. % using much lower surfactant concentrations. Although numerous studies have shown the effects of process parameters on particle sizes and methods to control the molecular weight, the decoupling of the molecular weight and particle size effect in NMP microemulsions under these conditions has not been done to this extent. In copolymer systems, nitroxide mediated polymerization also provides an efficient method to synthesize well defined block copolymers. Random copolymers are widely used as protective colloids, but the use of block copolymers for these applications has not been well studied. It is unclear what effects do the importance of a narrow molecular weight distribution and purity of block copolymers have on their performance as protective colloids. In order to investigate this, a range of block copolymers with different properties would need to be synthesized for systematic analysis. The direct synthesis of polystyrene b poly(acrylic acid) copolymers of varying lengths and compositions was successful by use of nitroxide mediated polymerization in bulk and solution polymerization. The characterization of these amphiphilic block copolymers was explored by titration and nuclear magnetic resonance spectroscopy. / Thesis (Master, Chemical Engineering) -- Queen's University, 2012-09-28 15:43:00.513

Le jihadisme comporte toujours une dimension apocalyptique. La Fin des Temps ouvrant à la conquête définitive du monde par l'extension du Dar al-islam, passe par la venue d'un Messie politique qui vaincra l'Antéchrist incarné par un juif, dont tous les disciples sont aussi des juifs.Le jihadisme est inséparable d'un montage mental et psychique qui suscite un noyau archaïque de Violence et de Mort. Les paradis offerts par la Mort en Guerrier dans le nom de Dieu sont ceux de la Jouissance absolue.Le judaïsme talmudique, celui auquel s'oppose le Coran médinois, semble être l'antithèse absolu du montage des jouissances jihadistes.Les textes originels ont été interprétés par un des deux courants de l'islam dans une version d'héroïsation, de légitimation et de sacralisation de ce noyau originaire de destructivité. Dès leur origine, la figure du Juif représente donc le point critique qu'il s'agit d'éradiquer aussi bien métaphysiquement que dans sa réalité.Les processus d'adhésion ne conduisent pas nécessairement à une addiction à la jouissance archaïque absolue. De nombreux radicalisés en France sont plutôt des infra-jihadistes pris dans la recherche d'une vindicte restaurant leur narcissisme blessé. Leur engagement dans la restauration de la Gloire de Dieu leur fait espérer une plénitude identitaire rétablissant un sentiment de musulmanité glorieuse.A ce niveau, la Haine-du-Juif inhérente à la lecture radicale du Coran et des Hadiths se trouve potentialisée par les discours complotistes-antisémites, véhiculées par les réseaux sociaux et certaines prêches.Notre recherche se poursuivra autour d'une analyse des processus narratifs inhérents aux textes eux-mêmes. / Jihadism always has an apocalyptic dimension. The End of Time opening to the final conquest of the world by the extension of the Dar al-islam, through the advent of a political Messiah who will defeat the Antichrist, incarnated by a Jew, of which all followers are also Jewish.Jihadism is inseparable from a mental and psychic assembly that creates an archaic nucleus of Violence and Death. Paradise offered by the Warrior of Death in the name of God is that of absolute pleasure.Judaism under Rabbinic and Talmudic expressions, the one the Koran of Medina is violently opposed to, seems to be the absolute antithesis of the jihadist idea of enjoyment.The original texts have been interpreted in one of the two branches of islam in a heroic, legitimate and sacred version in this original nucleus of destructiveness. Ever since the beginning of time, the figure of the Jew represents the critical point and it is to be eradicated both physically and mentally.The accession process do not necessarily lead to an addiction to archaic absolute enjoyment. Many radicalized in France are rather infra-jihadists caught in the search of restoring vindictiveness narcissism, even though they are hurt. Their commitment on the path to restoring the glory of God is their hope for a true identity restoring a sense of fulness in the Muslim religion.At this level, the feeling of Hate-the-Jew inherent in radical interpretation of the Koran and the Hadith is potentiated by the many complotistes and anti-Semitic speeches, carried on by social networks and sermons.Our research will continue to have a grip on the analysis narrative processes in texts themselves.

This research explores the role that radical-molecule complexes play in the chemistry of Earth's atmosphere. The formation of such complexes can have direct and pronounced effects on the reaction and product outcome of atmospheric chemical reactions. Some attention is also given to the formation of radial-radical pre-reactive complexes in the HO + ClO system. Peroxy radicals (RO2) can form stable complexes with polar compounds such as H2O, NH3, and CH3OH. For the simplest RO2 radical, HO2, complex formation (e.g., HO2-H2O, HO2-NH3, and HO2-722;CH3OH) gives rise to a significant increase in the HO2 self-reaction rate constant. Although this phenomenon has been observed since the mid-1970s, no satisfactory explanation has been put forward to explain this effect. Herein a rationale for the enhancement of the HO2 self-reaction is given based on extensive geometric, mechanistic and natural bond orbital (NBO) analyses. The apparent lack of a rate enhancement for the methyl peroxy (CH3O2) self-reaction is also presented. The combined insights gained from these two systems are then extended to predict if a water enhancement is expected for the 2-hydroxyethyl peroxy (HOCH2CH2O2) self-reaction kinetics. The computational results of this study are then compared to experimental work and conclusions are drawn towards a general procedure to predict the presence/absence of water initiated rate enhancements in RO2 systems as a whole. Original work regarding the formation of a series of organic RO2-H2O complexes is presented. This work established the effects of different functional groups on the stability of organic peroxy radicals and makes estimates of the associated atmospheric lifetimes and equilibrium constants. This work is further extended to the family of peroxy radicals that form from the atmospheric oxidation of isoprene (the most abundant non-methane biologically emitted hydrocarbon). For the first time, complexes of isoprene peroxy radicals with water are presented along with atmospheric lifetime estimates. Conclusions are made as to the effect of water on the product branching ratio of the isoprene peroxy radical + NO2. The oxidation of hexanal to form hexanal peroxy radicals is discussed within the context of the formation of hexanal peroxy water complexes.Aerosol formation is also perturbed as a result of complexation. Aerosol formation under atmospheric conditions is hypothesized to be initiated by radical-molecule complex formation. For example, in the absence of ammonia, the nucleation of H2SO4 in water vapor to form sulfuric acid aerosols is slow. However, as the concentration of NH3 rises, a marked increase in the rate of sulfuric acid aerosol formation is observed. This work explores the effects of the photolysis products of NH3 (NH2 and NH) on the rate of aerosol formation in systems involving H2SO4, HNO3, HC(O)OH, and CH3C(O)OH. With the exception of H2SO4-NH3 and HNO3-NH3 (geometries already published in the literature), minimum energy structures are presented here for the first time for each of the acid-NHx complexes. Thermochemical data and lifetime estimates are provided for each complex. Conclusions about the relevance of acid-NH2 and acid-NH in the formation of atmospheric aerosols are set forth. Finally, mechanistic insights into the reaction of the hydroxyl radical (OH) and Cl2O are obtained via analysis of the two potential energy surfaces that both involve the formation of HO-Cl2O pre-reactive complexes.

No description available.

t-Butoxyl radical has been used as a chemical model for hydrogen abstractions in many enzymatic and biological systems. However, the question has arisen as to how well this reactive intermediate mimics these systems. In addressing this concern, absolute rate constants and Arrhenius parameters for hydrogen abstraction by t-butoxyl radical were measured for a broad class of substrates including amines, hydrocarbons, and alcohols using laser flash photolysis. Initially, no obvious reactivity relationship between rate constant and substrate structure was observed for these homolytic reactions. However, by closely examining the Arrhenius parameters for hydrogen abstraction, a pattern was revealed. For substrates with C-H bond dissociation energy (BDE) > 92 kcal/mole, activation energy increases with increasing BDE (as expected). However, for substrates with a lower BDE, the activation energy levels out at approximately 2 kcal/mole, essentially independent of structure. Viscosity studies with various solvents were conducted, ruling out the possibility of diffusion-controlled reactions. Entropy rather than enthalpy appears to be the dominating factor at 25°C, contributing to the free energy barrier for these reactions. Laser flash photolysis was also used to study radical anions. Using an indirect photoexcitation method, the properties of radical anions, generated from aryl ketones, were investigated. These radical anions, such as t-butyl phenyl ketone and cyclopropyl phenyl ketone, measured to have decay rate constants of 1.0 x 106 s-1, although they are known to be persistent when studied electrochemically. They also had measured activation energies around 6.0 kcal/mole and log A values close to 9.5. By extending the molecules's conjugation, the decay rate constants increased to greater than 107 s-1, decreased their activation energy by half, and lowered the log A values to 8.0. This trend was observed in aryl ketones such as trans-1-benzoyl-3-phenyl cyclopropane. It is believed that the generation of a benzyl radical during the decay that facilitates the enhancement of the unimolecular decays. These unimolecular decays were also observed with the previously studied hypersensitive SET probes, 5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one and 1,1,-dimethyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one. The decay rate constants for these radical anions were measured to be greater than 108 s-1, driven by the formation of an aromatic ring. / Ph. D.

The dissociative electron transfer reactions of a series of α-epoxyketones and tetra-n-butylammonium acetate have been examined by electrochemical and computational techniques. Results for both the direct electrochemical (linear sweep voltammetry and convolution voltammetry) and indirect electrochemical (homogeneous redox catalysis) reductions of the epoxyketones are presented. In cases where the ring-closed radical anion generated by reduction of the epoxyketones is resonance stabilized (aromatic epoxyketones) the mechanism proceeds in a stepwise fashion, where the electron transfer and bond breaking reactions occur in sequential, discrete steps. On the other hand, where there is no additional resonance stabilization afforded to the ring-closed epoxide radical anion (aliphatic epoxyketones) the reaction proceeds in a concerted fashion, where electron transfer and ring cleavage occur simultaneously. The presence (or absence) of resonance stabilization in the ring-opened distonic radical anion plays little role in the kinetics of these dissociative electron transfers. Computations with the Density Functional Theory (B3-LYP and BHandH-LYP) on α-epoxyketones are also presented, and are in good agreement with the electrochemical results. The oxidative dissociative electron transfers of the acetate anion in "dry" and "wet" (0.5 M H2O) acetonitrile were also characterized with direct and indirect electrochemical experiments, again utilizing linear sweep voltammetry, convolution voltammetry, and homogeneous redox catalysis. There is a significant change in the observed oxidation potential of the anion upon addition of water, as well as an apparent decrease in the intrinsic barrier to the electron transfer. The possible transition from a concerted to stepwise mechanism for the dissociative electron transfer of acetate upon addition of water is examined - the electrochemical data is compared to theoretical models for both the concerted and stepwise processes. It is determined that the indirect electrochemical experiments do not proceed through an outer sphere electron transfer. Additionally, it is shown that the difference between the direct oxidation of acetate in anhydrous and wet acetonitrile is unlikely to be the result of transition from a purely concerted mechanism to a purely stepwise mechanism based on thermodynamic considerations. / Ph. D.

No description available.

No description available.