This diploma thesis deals with chemical recyclation polylactide to lactide. In the theory is summarized actual state of knowledge about chemical recyclation of polylactides, their properties, preparations a possibilities of characterization. Experimental part of work verify ethanolysis of PLA withthe samples of granulate, waste filaments and textiles. In the experimental work is suggested an optimalization of alcoholysis to direct yield of oligomer suitable for depolymerization to lactide. This method was verified for 5 different samples of PLA, which 4 of them was made of waste PLA. The time needed for depolymerization was evaluated and the effect of catalysis. Lactide and PLA recyclates was further analyzed by NMR, FTIR, DSC and GPC.

This master thesis deals with the synthesis of lactide from lactic acid esters. The theoretical part focuses on the current understanding of technology of lactic acid, its alkyl esters and the cyclic lactic acid dimer - lactide, which is mainly used as a precursor for the synthesis of high moleculat weight biodegradable polylactide (PLA) and other copolymers. Experimental part is then focused on the synthesis of lactide from lactic acid alkyl esters, especially ethyl lactate. Examines the design of a suitable apparatus for this synthesis and the application of the most appropriate reaction conditions (temperature, pressure, catalysis) to optimize the preparation of the desired product. In the end, parameters of prepared lactide are characterized by using of various analytical techniques.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24643号 / 工博第5149号 / 新制||工||1983(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 河瀬 元明, 教授 大嶋 正裕, 教授 佐野 紀彰 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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L’objectif de cette thèse était la mise au point de nouvelles méthodes de synthèse innovantes permettant le recyclage de déchets carbonés ou l’utilisation de matières premières renouvelables, ceci afin d’améliorer la durabilité du secteur de la chimie industrielle et de réduire sa dépendance aux ressources fossiles. Dans cette optique, le travail a été réalisé en suivant trois axes de recherche principaux visant la mise au point de nouveaux procédés catalytiques pour la valorisation de l’acide oxalique, un dérivé du CO2, de déchets de matériaux polymères ainsi que de la biomasse. Afin d’atteindre les objectifs fixés, une stratégie basée sur le clivage réducteur des liaisons C–O et utilisant la réaction d’hydrosilylation catalysées par B(C6F5)3 a été adoptée. Cette stratégie a permis en premier lieu d’obtenir, à partir de l’acide oxalique, une large gamme de produits ayant différents degrés d’oxydation allant de l’acide glyoxylique trisilylé jusqu’à l’éthane. Il a été montré ensuite que le système B(C6F5)3-hydrosilane permet la dépolymérisation sélective de déchets plastiques (tels que PLA, PET et PC-BPA) ainsi que de polyesters bio-sourcés tels que l’acide tannique et la subérine, en une variété de molécules comprenant des alcools, des phénols et des alcanes. Enfin, l’efficacité de B(C6F5)3 comme catalyseur d’hydrosilylation sélectif a été démontrée pour le clivage réducteur des modèles de motifs α-O-4 et β-O-4, principales liaisons dans la lignine. Cette réaction a pu être extrapolée à la lignine issue du bois et une nouvelle démarche permettant l’obtention de produits aromatiques purs à partir de la lignine a été développée. / The objective of this thesis was the development of new innovative synthetic methods for recycling waste carbon compounds or renewable raw materials to improve the sustainability of the industrial chemical sector and reduce its dependence on fossil resources. In this context, the work has been performed following three main areas of research intended for the development of new catalytic processes for the valorization of oxalic acid, derived from CO2, waste polymer materials and biomass. To achieve these objectives, a strategy based on the reductive cleavage of C–O bonds using the hydrosilylation reactions catalyzed by B(C6F5)3 was selected. First, this strategy resulted in the generation of a wide range of products with different degrees of oxidation, from oxalic acid, ranging from trisilylated glyoxylic acid to ethane. Afterwards, the system B(C6F5)3-hydrosilane allowed the selective depolymerization of waste plastics (such as PLA, PET, PC-BPA) as well as bio-based polyesters such as tannic acid and suberin, to a variety of molecules including alcohols, phenols and alkanes. Finally, it has been shown that B(C6F5)3 is an efficient and selective hydrosilylation catalyst for the reductive cleavage of α-O-4 and β-O-4 models, the main linkages in lignin. This reaction was successfully transposed to lignin derived from wood and a new process for obtaining pure aromatic products from lignin has been developed.

The oxidation of lignin model compounds was studied in conventional solvents in parallel with oxidations in ionic liquid solvents. Catalyst systems were investigated in ionic liquid solvents to determine how reaction rates and the selectivity for benzylic carbon oxidation were affected. Oxidation rates were often lower in ionic liquids than in conventional solvents ‒ as indicated by lower conversion in a standard reaction time ‒ likely due, at least in part, to the higher viscosity of ionic liquids. Mechano chemical treatment of Indulin AT kraft lignin by ball milling with KOH and toluene produced significant carbonyl functionality, among other changes. The chemical reactivity of the lignin was increased, resulting in greater lignin degradation from porphyrin oxidation followed by Baeyer-Villiger oxidation. The mechanochemical treatment produced a level of lignin oxidation that was similar to that produced by porphyrin-catalyzed oxidation. Combining mechanochemical treatment with porphyrin oxidation produced a synergistic positive effect on the depolymerization of lignin, as demonstrated by a significantly higher yield of monomers. The methyl ester of vanillic acid was obtained as the main monomeric product (after methylation), along with a small amount of methyl 5-carbomethoxyvanillate.

Actin is one of the most abundant and highly conserved proteins in eukaryotic cells. The globular protein assembles into long filaments, which form a variety of different networks within the cytoskeleton. The dynamic reorganization of these networks - which is pivotal for cell motility, cell adhesion, and cell division - is based on cycles of polymerization (assembly) and depolymerization (disassembly) of actin filaments. Actin binds ATP and within the filament, actin-bound ATP is hydrolyzed into ADP on a time scale of a few minutes. As ADP-actin dissociates faster from the filament ends than ATP-actin, the filament becomes less stable as it grows older. Recent single filament experiments, where abrupt dynamical changes during filament depolymerization have been observed, suggest the opposite behavior, however, namely that the actin filaments become increasingly stable with time. Several mechanisms for this stabilization have been proposed, ranging from structural transitions of the whole filament to surface attachment of the filament ends. The key issue of this thesis is to elucidate the unexpected interruptions of depolymerization by a combination of experimental and theoretical studies. In new depolymerization experiments on single filaments, we confirm that filaments cease to shrink in an abrupt manner and determine the time from the initiation of depolymerization until the occurrence of the first interruption. This duration differs from filament to filament and represents a stochastic variable. We consider various hypothetical mechanisms that may cause the observed interruptions. These mechanisms cannot be distinguished directly, but they give rise to distinct distributions of the time until the first interruption, which we compute by modeling the underlying stochastic processes. A comparison with the measured distribution reveals that the sudden truncation of the shrinkage process neither arises from blocking of the ends nor from a collective transition of the whole filament. Instead, we predict a local transition process occurring at random sites within the filament. The combination of additional experimental findings and our theoretical approach confirms the notion of a local transition mechanism and identifies the transition as the photo-induced formation of an actin dimer within the filaments. Unlabeled actin filaments do not exhibit pauses, which implies that, in vivo, older filaments become destabilized by ATP hydrolysis. This destabilization can be identified with an acceleration of the depolymerization prior to the interruption. In the final part of this thesis, we theoretically analyze this acceleration to infer the mechanism of ATP hydrolysis. We show that the rate of ATP hydrolysis is constant within the filament, corresponding to a random as opposed to a vectorial hydrolysis mechanism. / Aktin ist eines der am häufigsten vorkommenden und am stärksten konservierten Proteine in eukaryotischen Zellen. Dieses globuläre Protein bildet lange Filamente, die zu einer großen Vielfalt von Netzwerken innerhalb des Zellskeletts führen. Die dynamische Reorganisation dieser Netzwerke, die entscheidend für Zellbewegung, Zelladhäsion, und Zellteilung ist, basiert auf der Polymerisation (dem Aufbau) und der Depolymerisation (dem Abbau) von Aktinfilamenten. Aktin bindet ATP, welches innerhalb des Filaments auf einer Zeitskala von einigen Minuten in ADP hydrolysiert wird. Da ADP-Aktin schneller vom Filamentende dissoziiert als ATP-Aktin, sollte ein Filament mit der Zeit instabiler werden. Neuere Experimente, in denen abrupte dynamische Änderungen während der Filamentdepolymerisation beobachtet wurden, deuten jedoch auf ein gegenteiliges Verhalten hin: Die Aktinfilamente werden mit der Zeit zunehmend stabiler. Mehrere Mechanismen für diese Stabilisierung wurden bereits vorgeschlagen, von strukturellen Übergängen des gesamten Filaments bis zu Wechselwirkungen der Filamentenden mit dem experimentellen Aufbau. Das zentrale Thema der vorliegenden Dissertation ist die Aufklärung der unerwarteten Unterbrechungen der Depolymerisation. Dies geschieht durch eine Kombination von experimentellen und theoretischen Untersuchungen. Mit Hilfe neuer Depolymerisationexperimente mit einzelnen Filamenten bestätigen wir zunächst, dass die Filamente plötzlich aufhören zu schrumpfen und bestimmen die Zeit, die von der Einleitung der Depolymerisation bis zum Auftreten der ersten Unterbrechung vergeht. Diese Zeit unterscheidet sich von Filament zu Filament und stellt eine stochastische Größe dar. Wir untersuchen daraufhin verschiedene hypothetische Mechanismen, welche die beobachteten Unterbrechungen verursachen könnten. Die Mechanismen können experimentell nicht direkt unterschieden werden, haben jedoch verschiedene Verteilungen für die Zeit bis zur ersten Unterbrechung zur Folge. Wir berechnen die jeweiligen Verteilungen, indem wir die zugrundeliegenden stochastischen Prozesse modellieren. Ein Vergleich mit der gemessenen Verteilung zeigt, dass der plötzliche Abbruch des Depolymerisationsprozesses weder auf eine Blockade der Enden, noch auf einen kollektiven strukturellen Übergang des gesamten Filaments zurückzuführen ist. An Stelle dessen postulieren wir einen lokalen Übergangsprozess, der an zufälligen Stellen innerhalb des Filaments auftritt. Die Kombination von weiteren experimentellen Ergebnissen und unserem theoretischen Ansatz bestätigt die Vorstellung eines lokalen Übergangsmechanismus und identifiziert den Übergang als die photo-induzierte Bildung eines Aktindimers innerhalb des Filaments. Nicht fluoreszenzmarkierte Aktinfilamente zeigen keine Unterbrechungen, woraus folgt, dass ältere Filamente in vivo durch die ATP-Hydrolyse destabilisiert werden. Die Destabilisierung zeigt sich durch die Beschleunigung der Depolymerisation vor der Unterbrechung. Im letzten Teil der vorliegenden Arbeit untersuchen wir diese Beschleunigung mit theoretischen Methoden, um auf den Mechanismus der ATP-Hydrolyse zu schließen. Wir zeigen, dass die Hydrolyserate von ATP innerhalb des Filaments konstant ist, was dem sogenannten zufälligen Hydrolysemechanismus entspricht und im Gegensatz zum sogenannten vektoriellen Mechanismus steht.

Made available in DSpace on 2014-12-17T14:07:01Z (GMT). No. of bitstreams: 1 GenaroZC_partes_autorizadas_pelo_autor.pdf: 1229479 bytes, checksum: 5495990b3c8d250f3f3eb0d7bcc6bbd4 (MD5) Previous issue date: 2009-05-29 / In this work, mixed oxides were synthesized by two methods: polymeric precursor and gel-combustion. The oxides, Niquelate of Lanthanum, Cobaltate of Lanthanum and Cuprate of Lanthanum were synthesized by the polymeric precursor method, and treated at 300 ? C for 2 hours, calcined at 800 ? C for 6h in air atmosphere. In gel-combustion method were produced and oxides using urea and citric acid as fuel, forming for each fuel the following oxides Ferrate of Lanthanum, Cobaltato of Lanthanum and Ferrato of Cobalt and Lanthanum, which were submitted to the combustion process assisted by microwave power maximum of 10min. The samples were characterized by: thermogravimetric analysis, X-ray diffraction; fisisor??o of N2 (BET method) and scanning electron microscopy. The reactions catalytic of depolymerization of poly (methyl methacrylate), were performed in a reactor of silica, with catalytic and heating system equipped with a data acquisition system and the gas chromatograph. For the catalysts synthesized using the polymeric precursor method, the cuprate of lanthanum was best for the depolymerization of the recycled polymer, obtaining 100% conversion in less time 554 (min), and the pure polymer, was the Niquelate of Lanthanum, with 100% conversion in less time 314 (min). By gel-combustion method using urea as fuel which was the best result obtained Ferrate of Lanthanum for the pure polymer with 100% conversion in less time 657 (min), and the recycled polymer was Cobaltate of Lanthanum with 100 % conversion in less time 779 (min). And using citric acid to obtain the best result for the pure polymer, was Ferrate of Lanthanum with 100% conversion in less time 821 (min and) for the recycled polymer, was Ferrate of Lanthanum with 98.28% conversion in less time 635 (min) / Neste trabalho, foram sintetizados ?xidos mistos por dois m?todos: precursores polim?ricos e gel-combust?o. Os ?xidos, Niquelato de Lant?nio, Cobaltato de Lant?nio e Cuprato de Lant?nio, foram sintetizados pelo m?todo dos precursores polim?ricos, sendo tratados termicamente a 300 ?C por 2h, calcinados a 800 ?C por 6h, em atmosfera de ar. No m?todo gel-combust?o foram produzidos os ?xidos utilizando como combust?vel Ur?ia e ?cido C?trico, formando para cada combust?vel os seguintes ?xidos Ferrato de Lant?nio, Cobaltato de Lant?nio e Ferrato de Cobalto e Lant?nio, que foram submetidos ao processo de combust?o assistida por microondas ? pot?ncia m?xima por 10min. As amostras foram caracterizadas por: an?lise termogravim?trica; difra??o de raio-X; fisisor??o de N2 (m?todo de B.E.T.) e microscopia eletr?nica de varredura. As rea??es catal?ticas de despolimeriza??o do Poli (metacrilato de metila), foram realizadas em um reator de s?lica, com sistema catal?tico e aquecimento munido de um sistema de aquisi??o de dados e o cromat?grafo a g?s. Para os catalisadores sintetizados utilizando o m?todo dos precursores polim?ricos, o Cuprato de Lant?nio, foi melhor para a despolimeriza??o do pol?mero reciclado, obtendo 100 % de convers?o em menor tempo 554 (min), e para o pol?mero puro, foi o Niquelato de Lant?nio, com 100 % de convers?o em menor tempo 314 (min). Pelo m?todo de gel-combust?o utilizando Ur?ia como combust?vel o que obteve melhor resultado foi o Ferrato de Lant?nio, para o pol?mero puro com 100 % de convers?o em menor tempo 657 (min), e para o pol?mero reciclado foi o Cobaltato de Lant?nio com 100 % de convers?o em menor tempo 779 (min). E utilizando ?cido C?trico o que obteve melhor resultado para o pol?mero puro, foi o Ferrato de Lant?nio com 100 % de convers?o em menor tempo 821 (min) e para o pol?mero reciclado, foi o Ferrato de Lant?nio com 98,28 % de convers?o em menor tempo 635 (min)

La substitution des composés carbonés d'origine fossile par des matières premières renouvelables représente un enjeu majeur et stratégique pour l'environnement, l'économie, et la santé publique. Nous nous sommes particulièrement intéressés au cas des dérivés du phénol, largement utilisés dans le domaine des matériaux synthétiques (résines, plastiques). Des travaux antérieurs ont démontré le potentiel des monomères de flavanols, sous-unités constitutives des chaines polymériques des tanins condensés comme substituts aux phénols issus de la pétrochimie, tels que le bisphénol A, l'objectif du présent travail a été de contribuer au développement d'une voie industrielle d'accès à de tels composés par dépolymérisation des tanins condensés (proanthocyanidines), une ressource végétale abondante mais actuellement peu exploitée pour ce type d'applications. Cette dépolymérisation peut être obtenue par rupture de la liaison interflavanique en milieu acide et piégeage des carbocations formés par un réactif nucléophile. Différentes stratégies et conditions ont été étudiées pour mieux comprendre le rôle de l'acide, du nucléophile, du solvant et l'impact de la température sur la réaction de dépolymérisation. Les stratégies sélectionnées, menées sur un dimère B2 pur servant de modèle et sur un extrait industriel de tanins de pépins de raisins blancs issus de marcs à l'échelle du gramme, ont été comparées en termes de rendement, de cinétique, de stabilité des produits, et de facilité de mise en œuvre et de traitement dans la perspective d'une production à plus grande échelle respectant au mieux les objectifs du développement durable et les contraintes de l'industrialisation. / The substitution of fossil carbon by renewable raw materials is a major strategic challenge for the environment, economy and public health. Our thesis focuses on the utilisation of phenol derivatives, which are widely used in the field of synthetic materials (resins, plastics). Previous studies have demonstrated the potential of plant flavanol monomers as substitutes for petrochemical phenols such as bisphenol A. The objective of this work was to contribute to the development of an industrial access to such compounds by depolymerization of condensed tannins (proanthocyanidins), an abundant plant resource currently untapped for such applications. Depolymerization can be performed by breaking the interflavan bonds in acidic medium and scavenging the released carbocations by a nucleophilic reagent. Various strategies and conditions were studied and compared to better understand the role of the acid, the nucleophile and the solvent and temperature in the depolymerisation reaction. The selected strategies, applied on a pure B2 dimer used as a model and an industrial seed tannins extract from white grape pomace at the gram scale, were compared in terms of performance, kinetics, product stability, ease of implementation and work-up in the context of a larger scale production complying with the objectives of sustainable development and the constraints of industrialization.

Parmi les bio-polymères issus des ressources renouvelables, les polysaccharides fournissent une alternative intéressante aux polymères de synthèse. Dans ce contexte, l’objectif de ce travail de thèse est basé sur la conception des copolymères amphiphiles pour la préparation de nouveaux biomatériaux. Ainsi, l’hydroxypropylméthylcellulose (HPMC) a été étudiée en raison de ses propriétés remarquables, dont la biocompatibilité, la biodégradabilité, la rétention d'eau et la gélification thermoréversible. Ces propriétés sont utiles pour de nombreuses applications telles que le relargage de médicament, la préparation des membranes et la formation de biomatériaux. L'hydrolyse enzymatique avec des endo cellulases issues de Trichoderma reesei a été étudiée pour produire des fragments d'HPMC ayant une masse molaire (Mw) entre 6000 et 30000 g mol-1. Les paramètres de l’activité enzymatique ont été étudiés en fonction de : la nature de substrat, le temps de réaction et la concentration de l'enzyme. Les polymères obtenus ont été comparés à ceux produits par hydrolyse acide. Il a été constaté que la structure des polymères issus d’un procédé d’hydrolyse, varie en termes de degré de substitution pour un même Mw. Cet effet donne lieu à différentes propriétés de gélification thermoréversible. Des copolymères amphiphiles tels que HPMC-b-poly (propylène glycol) et HPMC-b-PLA ont été préparés par amination réductrice et par couplage click thiol-ene, respectivement. Les propriétés d’agrégation ont été caractérisées par la diffusion de la lumière (DLS), le microscope électronique en transmission (TEM) et par la séparation de phase obtenue par la mesure du point de trouble. / Following the concept of bio-refinery, we propose to produce small fragments of biopolymers that can be used further as building blocks to prepare novel polymeric architectures. In the case of polysaccharides, enzymatic hydrolysis enables to form reducing end groups after each cleavage on the polymer chain. Reaction by reductive amination affords the possibility to introduce polysaccharides fragments in a large variety of materials going from amphiphilic copolymers to more sophisticated devices. Hydroxypropyl methylcellulose (HPMC) was used in this work because of its remarkable properties including biocompatibility, biodegradability, water retention and thermoreversible gelation beneficial for many applications such as drug delivery, film and biomaterial formation. Enzymatic hydrolysis using endo cellulases from Trichoderma reesei was investigated to produce a library of HPMC fragments with molecular weight (Mw) from 6000 to 30000 g mol-1. Mw control was carried out by varying the procedure conditions including the nature of starting HPMC, reaction time and enzyme concentration. The obtained polymers were compared to those produced by acidic hydrolysis.According to the preparation conditions, the structure of short chain polymers regarding substitution degrees varied for the same Mw giving rise to different clouding temperature and thermoreversible gelation properties. Amphiphilic block copolymers HPMC-b-poly(propylene glycol) and HPMC-b-PLA were prepared by reductive amination and by the thiol-ene click reaction, respectively. Self-assembly properties of these novel block copolymer were characterized by dynamic light scattering (DLS), transmission electron microscope (TEM), and clouding point temperature.