Introducción y antecedentes El concepto de desarrollo sostenible surgió como idea principal tras la reunión de la comisión Brundtland en 1987. Esta reunión fue organizada por Naciones Unidas con el fin de tratar el deterioro del medio ambiente, originado por el desarrollo descontrolado de la humanidad. El desarrollo sostenible fue definido como un avance social y económico que asegure una vida sana y productiva al ser humano, pero que no comprometa las posibilidades de desarrollo de las generaciones venideras. Entre las conclusiones alcanzadas, se resaltó la necesitad de disponer de una mayor variedad de fuentes de energía. La filosofía de esta cumbre fue recogida en Agenda 21, un documento que pretendía servir como guía general de actuación para alcanzar un desarrollo sostenible a todos los niveles. Respecto a las ciencias, Agenda 21 subrayaba la necesidad de emplear todo el conocimiento científico en la consecución de los objetivos del desarrollo sostenible. En este sentido, la Environmental Protection Agency acuñó en 1998 un término, Green Chemistry, que reunía estas ideas y las aplicaba a la química a través de 12 principios que debían ser cumplidos en el camino hacia una química sostenible. Entre estos principios, el uso de fuentes renovables para la obtención de materias primas ha adquirido gran relevancia debido a las previsiones de agotamiento de una de las fuentes de energía y materias primas más importantes: el petróleo. Los aceites vegetales se incluyen entre estas fuentes renovables de materias primas, siendo actualmente una de las fuentes renovables más utilizadas por la industria química. Los aceites vegetales están básicamente compuestos por triglicéridos, que son moléculas formadas por glicerol y tres ácidos grasos. En general los ácidos grasos pueden ser completamente saturados o contener varios dobles enlaces que en algunos casos pueden encontrarse conjugados, pero también existen ácidos grasos que contienen grupos hidroxilo o epóxido. Cada aceite vegetal posee una distribución característica de ácidos grasos que determina sus propiedades físicas y químicas. En lo que respecta a la química de los polímeros, los aceites vegetales constituyen una atractiva materia prima debido a la amplia gama de transformaciones químicas que pueden llevarse a cabo para sintetizar monómeros de diversa naturaleza. La epoxidación de los dobles enlaces internos es la transformación más común, ya que permite, a través de la apertura del anillo oxiránico con diferentes reactivos, la introducción de una gran variedad de grupos funcionales. Los dobles enlaces internos pueden polimerizarse directamente en condiciones térmicas, con iniciadores de radicales o por polimerización catiónica. / Introducction The sustainable development concept came out of the United Nations Commision on Environment and Development in 1987 (Bruntland Commission) and it is defined as "the development that meets the needs of the present without compromising the ability of future generations to meet their own needs". From this point, both the society and the industry have considered what a sustainable development really means and the best ways to start to achieve it from their own standpoints. The principles of the United Nations Conference on environment and Development (UNCED) held in June 1992 in Rio de Janeiro, and Agenda 21, were formulated with the aim of preparing the world for the challenges of the 21st century. In this context, during the early 1990s the US Environmental Protection Agency (EPA) coined the phrase Green Chemistry "To promote innovative chemical technologies that reduce or eliminate the use of generation of hazardous substances in the design, manufacture and use of chemical products". The main challenges of Green Chemistry and Engineeiring can be summarized as: · utilizing renewable instead of scarce resources. · avoiding toxic/dangerous chemicals in safer processes to obtain safer products. · minimizing energy use. · minimizing waste and resource use, re-using products, recovering and recycling materials. So making processes globally more efficient. Plant oils are one of the most widely applied renewable raw materials in the chemical industry for non-fuel applications. Vegetable oils are triglycerides (tri-esters of glycerol with long-chain fatty acids) with varying composition of fatty acids depending on the plant they are extracted from. Depending on the composition of plant oils, their Chemicals and physical properties are different.Vegetable oils are very used in polymer chemistry. Triglycerides have different reactive points through which we can obtain polymers from plant oils.There are two main approaches:The first one is the chemical modification of the triglycerides obtaining a large number of polymerizable monomers like expoxides or alcohols. The second approach is the direct polymerization of the carbon-carbon doubles bonds of plant oils through a free radical or a cationic mechanism.The free radical polymerization of double bonds has received less attention than cationic mechanism which has been very studied by Larock's group.In both cases thermosetting polymers with comparable properties to those of industrial can be obtained. Because of increasing use of synthetic polymeric materials during the lasts decades and the large fraction of the fire load in homes, it is necessary the use of fire retardants to reduce combustibility of the polymers, and smoke or toxic fume production. To get these requirements, the development of effective flame retardant materials is a key factor. To reduce the flammability, flame retardants can act in the gas phase or in condensed phase. In the gas phase fire retardants act as scavengers of the highly reactive radical species that propagate the combustion. In the condensed-phase fire retardants interfere in the thermal degradation processes modifying the reaction pathways and promoting the formation of char instead of volatile degradation products. Finally some flame retardants can act in both phases. Objectives The main objective of this Thesis was to develop new fire retardant biobased thermosets from vegetable oils as renewable resources. To achieve this goal it was carried out the cationic copolymerization of soybean oil, styrene and divinylbenzene with different silicon-or boron-or phosphorus containing comonomers.

In this study / ferrocenyl and naphthalenyl substituted quinoxaline derivatives / 5,8- bis (2,3- dihydrothieno [3,4-b] [1,4] dioxin-5-yl)-2- (naphthalen-2-yl)- 3- ferrocenyl- 4a,8a-dihydroquinoxaline / 5,8- bis (2,3-dihydrothieno [3,4-b] [1,4]dioxin-5-yl) -2- (phenyl) -3-ferrocenylquinoxaline / 5,8-bis (2,3-dihydrothieno [3,4-b] [1,4]dioxin-5-yl) -2,3- di(naphthalen-2-yl)quinoxaline and trihexylthiophene and thiophene coupled benzimidazole derivatives / 4-(tert-butyl)-4,7-bis(4-hexylthiophen-2-yl)spiro[benzo[d]imidazole-2,1-cyclohexane] and 4-(tert-butyl)-4, 7-bis(thiophenyl)spiro[benzo[d]imidazole-2,1-cyclohexane] were used as photosensitizers to broaden the active area of diaryliodonium salts. Both quinoxaline and benzimidazole derivatives are expected to be efficient in cationic photopolymerization with a variety of vinyl and oxide monomers at room temperature upon long wavelength UV irradiation. Photopolymerization will be initiated by diphenyliodonium salts and monitored with Optical Pyrometry. Characterization will be completed with optical absorption, flourescence studies and photopolymerization under solar irradiation.

Benzimidazole and benzotriazole derivatives, 4-(2,3-Dihydrothieno[3,4-b][1,4] dioxin-5-yl)-7-(2,3-dihydrothieno[3,4b][1,4]dioxin-7-yl)-2-benzyl-1H-benzo[d] imidazole (BIm-Ed), 2-benzyl-4,7-di(thiophen-2-yl)-2H-benzo[d] [1,2,3] triazole (BBTS), and 2-benzyl-4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2Hbenzo[ d] [1,2,3] triazole (BBTES) were employed as photosensitizers for diaryliodonium salt photoinitiators in cationic photopolymerization of various epoxide and vinyl ether monomers. Diphenyliodonium hexafluorophosphate (Ph2I+PF6&macr / ) salt was used as the photoinitiator in this study. Extended conjugation and electron-rich moieties of the photosensitizers enabled the use of long wavelength UV and visible light emitting light sources in cationic photopolymerizations. Polymerizations were achieved at room temperature and monitored by optical pyrometry. Photopolymerization of a diepoxide monomer with ambient solar irradiation was examined.

L’objectif de cette étude est de synthétiser de nouveaux polymères aux propriétés spécifiques, en utilisant pour la première fois comme monomère un aldocétène : l’éthylcétène. La synthèse de l’éthylcétène a été entreprise en utilisant deux procédés distincts :d’une part la méthode de McCarney, qui a permis de le préparer dans un solvant par entraînement à la vapeur, et d’autre part le craquage de l’anhydride butyrique à 575°C sous 40mbar.La polymérisation ionique de l’éthylcétène a ensuite été réalisée, dans différentes conditions de solvant, de température et avec plusieurs amorceurs. La polymérisation anionique a abouti uniquement à la formation d’un polyester amorphe, tandis que la polymérisation cationique a conduit exclusivement à un polymère de structure polycétone,d’une grande stéréorégularité avec une cristallinité moyenne de 0,34. Une caractérisation fine de ces polymères a été effectuée par IRTF-ATR, RMN, TGA, DSC, GPC et diffraction desRX. / The aim of this study is to synthesize new polymers with specific properties, using for the first time an aldoketene as monomer, namely ethylketene.The synthesis of ethylketene was carried out by using two distinct processes: on the one hand the method of McCarney, which led to its synthesis in a solvent by co-distillation, and on the other hand the pyrolysis of butyric anhydride at 575°C under 40 mbar.The ionic polymerization of ethylketene was then carried out, using different solvents, temperatures and initiators. The anionic polymerization gave only amorphous polyesters,while the cationic polymerization led exclusively to a polyketonic polymer, highly stereoregular with an average cristallinity of 0.34. A precise characterization of thesepolymers was undertaken by FTIR-ATR, NMR, TGA, DSC, GPC and X-ray diffraction.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20403号 / 工博第4340号 / 新制||工||1673(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 澤本 光男, 教授 中條 善樹, 教授 赤木 和夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 新制・論文博士 / 博士(工学) / 乙第13542号 / 論工博第4205号 / 新制||工||1984(附属図書館) / (主査)教授 杉野目 道紀, 教授 大江 浩一, 教授 松原 誠二郎 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

Ces travaux de thèse ont pour but de développer des procédés de polymérisation efficaces catalysés par des complexes organométalliques à base d'or. Dans une première partie, nous avons développé un nouveau procédé de polymérisation par polyaddition faisant intervenir des carbènes d'or formés par réaction de cycloisomérisation d'esters propargyliques catalysée par un complexe d'or carbophile. Des structures polymères originales et inédites composées d'un motif de répétition phényle vinylcyclopropane ont été proposées. Cette méthodologie a été appliquée à une variété d'esters propargyliques, tout en portant une attention particulière à l'augmentation de la solubilité et du degré de polymérisation des polymères. Une post-fonctionnalisation par l'hydrolyse de l'ester palmitate a été décrite et a permis d'accéder à une nouvelle architecture de polycétones. Des travaux préliminaires de conduction électrique ont montré que ces polycyclopropanes conjugués se comportaient comme des semi-conducteurs. Dans une seconde partie, une combinaison de deux processus de polymérisation associant, une polymérisation cationique vivante et une polymérisation radicalaire photo-induite pour la préparation de copolymères à blocs a été étudiée. Le complexe dinucléaire d'or(I) [Au2( μdppm)2]Cl2 a prouvé toute son efficacité pour catalyser la polymérisation par photo-ATRP d'acrylates en solution et en laminé, contrôlée par la lumière visible ou UVA. Finalement, des résultats préliminaires ont montré qu'il est possible de combiner une polymérisation cationique par RAFT catalysée par un acide de Lewis avec une polymérisation radicalaire photo-induite par RAFT sans utilisation de catalyseur photorédox. / The aim of this PhD work was to develop highly effective polymerization processes using gold complexes and the synthesis of original polymers. On the first research topic we have developed the first polymerization process through a gold carbenoic intermediate, leading to an original polymer composed by a phenyl vinylcyclopropyl monomer unit. This methodology was utilized to the polymerization of a variety of propargylic esters. Special attention has been paid to increase the solubility and the polymerization degree of the polymers. Post-functionnalization by hydrolysing the ester group leads to a new polyketone architecture. Preliminary electric studies showed that this conjugated polycyclopropane acts as a semi-conductor. The aim of the second research topic was to control efficiently the formation of block copolymers by combining living cationic and photo-induced radical polymerizations catalyzed in a one-pot procedure. A dinuclear gold(I) complex based photocatalyst [Au2(μ-dppm)2]Cl2 catalyzed efficiently polymerization of acrylates in solution and in laminate through an atom transfer radical polymerization process controlled by light exposure (visible or UV-A light). Finally, preliminary results showed it is possible to combine cationic reversible addition-fragmentation chain transfer polymerization catalyzed by a Lewis acid with radical reversible addition-fragmentation chain transfer polymerization without photoredox catalyst or radical initiator but only with an external stimuli, the light.

This study is focused on the use of visible light in photoinitiated cationic polymerization. Photoinitiated polymerization of oxiranes, vinyl ethers, and other vinyl monomers was achieved. In doing so, (2-(2,3 dihydrobenzo [b][1,4]dioxin-6-yl)-3-(2,3-dihydrobenzo[b]-[1,4]dioxin-7-yl)-5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-8-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7yl) quinoxaline) (DBQEd) and poly(2,3,5,8-tetra(thiophen-2-yl)quinoxaline) (TTQ), two dibenzo[a,c]phenazine derivatives / 10,13-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)dibenzo[a,c] phenazine (PHED) and 10,13-bis(4-hexylthiophen-2-yl)dibenzo[a,c]phenazine (PHEHT) were utilized as the photosensitizers for diaryliodonium salt photoinitiators. Novel dyes based on the dibenzo[a,c]phenazine and quinoxaline skeleton were shown to be efficient in carrying out the cationic photopolymerizations of a wide variety of epoxide, oxetane, and vinyl monomers at room temperature upon irradiation with long-wavelength UV and visible light. The polymerizations were initiated at room temperature in the presence of diphenyliodonium hexafluorophosphate (Ph2I+PF-6) and monitored by optical pyrometry (OP). The photopolymerization of an epoxide monomer via solar irradiation was also demonstrated.

Kyoto University (京都大学) / 0048 / 新制・論文博士 / 博士(工学) / 乙第12199号 / 論工博第3988号 / 新制||工||1438(附属図書館) / 26271 / UT51-2008-C969 / (主査)教授 堀井 文敬, 教授 渡辺 宏, 教授 金谷 利治 / 学位規則第4条第2項該当