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281	熱可塑性エポキシ樹脂を母材とするCFRTPの静的および疲労特性の改善と実用に関する研究 / ネツカソセイエポキシジュシオボザイトスル CFRTP ノセイテキオヨビヒロウトクセイノカイゼントジツヨウニカンスルケンキュウ西田裕紀, Hironori Nishida 22 March 2018 (has links) 熱可塑性エポキシ樹脂を母材とするCFRTPの母材を高分子量化することにより静的および疲労特性の改善を行えることを示し，重量平均分子量の違いによりそれらの特性が大きく変化する変曲点が存在することを明らかにした．さらに，CFRTPの実用化のためにミシンステッチを利用したCFRTPテープ積層法を提案し，その試作機を作成することで，CFRTPテープ自動積層装置の実用性を明らかにした． / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University 熱可塑性エポキシ複合材料重量平均分子量機械的特性疲労寿命自動テープ積層装置テープ積層 Thermoplastic epoxy CFRTP Composites Weight-average molecular weight Mechanical properties Fatigue life Automated tape placement Tape lay-up
282	Effet de la stérilisation par électrons accélérés sur les COC et sur l'impact des interactions avec des molécules actives / Effect of electron beam radio-sterilization on cyclo olefin copolymers and its impact on the interactions with active molecules Barakat, Hala 24 January 2013 (has links) L’objectif de ce travail de thèse était d’étudier l’effet de la stérilisation par électrons accélérés sur les copolymères d’oléfines cycliques (COC), utilisés comme conditionnement de produits pharmaceutiques, ainsi que son impact sur les interactions avec des formulations pharmaceutiques. Grâce à la méthodologie analytique adoptée qui a fait appel à différentes techniques de caractérisation, telles que la chromatographie d’exclusion stérique, la chromatographie liquide haute performance à polarité de phases inversée, la spectroscopie infra rouge à transformée de Fourier, la microscopie à force atomique et les mesures d’angles de contact, nous avons pu mettre en évidence différents types de modifications dans le volume et sur la surface du matériau après stérilisation ainsi qu’après vieillissement. La modification principale du dans la masse du matériau, observée à la dose réglementaire de stérilisation (25 kGy), est la scission des chaînes du polymère, qui s’accompagne de la création de composés de faible masse molaire, donc de migrants potentiels risquant d’influencer la sécurité d’emploi des COC. En effet, certains de ces composés ont été retrouvés avec une concentration relativement importante dans les solutions de mise en contact avec les COC stérilisés, et notamment en solution aqueuse. Toutefois, l’étude préliminaire de toxicité a montré l’absence de cytotoxicité des extractibles obtenus à la dose de la stérilisation.Les modifications relatives à la surface des COC radio-stérilisés sont, quant à elles, de deux natures : physique avec une augmentation de la rugosité de surface et chimique avec la formation de produits d’oxydation polaires ; ces deux types de modifications conduisent à l’augmentation de la mouillabilité de surface. Cependant dans certains cas, notamment après vieillissement, ces modifications sont relativement faibles, même à des doses supérieures à celle préconisée pour la stérilisation, ce qui peut être corrélé à l’absence de l’effet de l’irradiation sur le comportement des COC vis-à-vis des solutions médicamenteuses. En effet, aucune variation de la sorption des principes actifs choisis n’a été montrée entre les COC irradiés et non irradiés vieillis. / The aim of this work was to study the effect of electron beam radio-sterilization on cyclo olefins copolymers (COC) used as pharmaceutical storage materials, as well as to investigate its impact on the interaction with pharmaceuticals formulations. Due to the analytical methodology used which dealt with different techniques of characterization such as size exclusion chromatography, reversed phase high performance liquid chromatography, Fourier transformed infrared spectroscopy, atomic force microscopy and contact angle measurements, we have been able to put into evidence different kinds of modifications both in the bulk and on the surface of the sterilized material and also after ageing.The principal modification of material’s bulk, observed at the recommended dose for sterilization (25 kGy), was polymer chains scissions, accompanied with creation of low molecular weight compounds, that are potentials migrants that risk to affect the safe use of COC. Indeed, some of these compounds have been found with a relatively important concentration in the solutions where sterilized COC was stored, especially in aqueous solutions. However, the preliminary study of toxicity has shown the absence of cytotoxicity of the extractables obtained at the sterilization dose.Surface modifications of radio-sterilized COC are of two types: a physical one, with an increase of the surface’s roughness and a chemical one with the formation of polar oxidation products; these two modifications result in an increase of surface’s wettability that may be important. However, in some cases such as for aged samples, these modifications are relatively weak even at doses higher than the one recommended for sterilization, which can explain the absence of the effect of radiation on the behavior of COC towards drug solutions. Indeed, no variation of drug sorption has been observed between aged COC irradiated and none irradiated. Stérilisation Électrons accélérés Scission Oxydation Chromatographie d’exclusion stérique Rugosité de surface Mouillabilité Composés de faible masse molaire Vieillissement Compatibilité Interactions Sorption Migration Toxicité Cyclo olefins copolymers (COC) Sterilization Electrons beam Scission Oxydation Size exclusion chromatography Surface roughness Wettability Low molecular weight compounds Ageing Compatibility Interactions Sorption Migration Toxicity
283	Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes Boyd, Ramon Cornell 23 January 2007 Two distinct overall research objectives are in this Masters thesis. Very little relates the two chapters apart from the ligands. The first chapter addresses diastereoselective homogeneous copper catalyzed cyclopropanation reactions. Cyclopropanation of styrene and ethyl diazoacetate (EDA) is a standard test reaction for homogeneous catalysts. Sterically bulky salicylaldimine (SAL) ligands should select for the ethyl trans-2-phenylcyclopropanecarboxylate diastereomer. Steric bulk poorly influences trans:cis ratios. Salicylaldiminine ligands do not posses the correct symmetry to affect diastereoselectivity. The SAL ligand belongs to the Cs point group in the solid state. Other ligand motifs are more effective at altering the trans:cis ratios. The second chapter addresses the general route toward successful copper(II) ethylene polymerization catalysts. Catalytic activity of the copper(II) complexes is very low. Polymer chain growth from a copper catalyst is very unlikely. Copper-carbon bonds decompose by homolytic cleavage or C-H activation. Copper-alkyls and aryls readily decompose into brown colored oils and salts with different colors. Ligand transfer to trimethylaluminum (TMA) appears to explain low yield ethylene polymerization. bulky migratory insertion mechanism coordination/insertion methodology d-block metal late transition metal phenolic ring coordination number ketimine precatalysts ketimine nitrogen bis(salicylaldiminato)copper(II) ratio cyclopropane steric bulk salicylaldiminato TMA salt trimethylaluminum aryl oil alkyl copper-aryls copper-alkyls C-H activation homolytic homolytic cleavage copper(II) polymerization ethylene cis trans symmetry diastereomer salicylaldimine SAL EDA ethyl diazoacetate styrene cyclopropanation copper diastereoselective steric protection stable CH(SiMe3)2 intermediate catalytic activity associated TMA free TMA vacant coordination site hydrolysis Lewis acid halogen anionic anionic ligand donor ligand monodentate anionic ligand aluminum(III) monodentate polymer chain polymer chain aluminum-carbon bond bulky SAL ligand open coordination site first row transition metal PE paramagnetic high molecular weight polyethylene alkylate methylaluminoxane MAO anionic ligands arylate aluminum carbon aluminum carbon bond beta-hydrogen elimination beta hydrogen elimination Aufbau reaction Aufbau neutral dialkyl aluminum aluminum-alkyl aluminum alkyl copper(0)
284	Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes Boyd, Ramon Cornell 23 January 2007 (has links) Two distinct overall research objectives are in this Masters thesis. Very little relates the two chapters apart from the ligands. The first chapter addresses diastereoselective homogeneous copper catalyzed cyclopropanation reactions. Cyclopropanation of styrene and ethyl diazoacetate (EDA) is a standard test reaction for homogeneous catalysts. Sterically bulky salicylaldimine (SAL) ligands should select for the ethyl trans-2-phenylcyclopropanecarboxylate diastereomer. Steric bulk poorly influences trans:cis ratios. Salicylaldiminine ligands do not posses the correct symmetry to affect diastereoselectivity. The SAL ligand belongs to the Cs point group in the solid state. Other ligand motifs are more effective at altering the trans:cis ratios. The second chapter addresses the general route toward successful copper(II) ethylene polymerization catalysts. Catalytic activity of the copper(II) complexes is very low. Polymer chain growth from a copper catalyst is very unlikely. Copper-carbon bonds decompose by homolytic cleavage or C-H activation. Copper-alkyls and aryls readily decompose into brown colored oils and salts with different colors. Ligand transfer to trimethylaluminum (TMA) appears to explain low yield ethylene polymerization. bulky migratory insertion mechanism coordination/insertion methodology d-block metal late transition metal phenolic ring coordination number ketimine precatalysts ketimine nitrogen bis(salicylaldiminato)copper(II) ratio cyclopropane steric bulk salicylaldiminato TMA salt trimethylaluminum aryl oil alkyl copper-aryls copper-alkyls C-H activation homolytic homolytic cleavage copper(II) polymerization ethylene cis trans symmetry diastereomer salicylaldimine SAL EDA ethyl diazoacetate styrene cyclopropanation copper diastereoselective steric protection stable CH(SiMe3)2 intermediate catalytic activity associated TMA free TMA vacant coordination site hydrolysis Lewis acid halogen anionic anionic ligand donor ligand monodentate anionic ligand aluminum(III) monodentate polymer chain polymer chain aluminum-carbon bond bulky SAL ligand open coordination site first row transition metal PE paramagnetic high molecular weight polyethylene alkylate methylaluminoxane MAO anionic ligands arylate aluminum carbon aluminum carbon bond beta-hydrogen elimination beta hydrogen elimination Aufbau reaction Aufbau neutral dialkyl aluminum aluminum-alkyl aluminum alkyl copper(0)

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