L’ingénierie des biomatériaux a connu un essor prodigieux ces dernières décennies passant de matériaux simples à des structures plus complexes, particulièrement dans le domaine cardiovasculaire. Cette évolution découle de la nécessité des biomatériaux de permettre la synergie de différentes propriétés, dépendantes de leurs fonctions, qui ne sont pas forcément toutes compatibles. Historiquement, les premiers matériaux utilisés dans la conception de dispositifs médicaux étaient ceux présentant le meilleur compromis entre les propriétés physico-chimiques, mécaniques et biologiques que nécessitait leur application. Cependant, il se peut que le dispositif possède les bonnes propriétés physico-chimiques ou mécaniques, mais que sa biocompatibilité soit insuffisante induisant ainsi des complications cliniques. Afin d’améliorer ces propriétés biologiques tout en conservant les propriétés de volume du matériau, une solution est d’en modifier la surface. L’utilisation d’un revêtement permet alors de moduler la réponse biologique à l’interface biomatériau-hôte et de diminuer les effets indésirables. Ces revêtements sont optimisés selon deux critères principaux : la réponse biologique et la réponse mécanique. Pour la réponse biologique, les deux approches principales sont de mettre au point des revêtements proactifs qui engendrent l’adhérence, laprolifération ou la migration cellulaire, ou passifs, qui, principalement, sont inertes et empêchent l’adhérence de composés biologiques. Des revêtements plus complexes utilisent les deux approches permettant l’adhérence spécifique de certainescellules tout en empêchant l’adhérence d’autres composants biologiques. Cette pratique est très utile pour lutter contre la resténose, complication survenant après opération de l’athérosclérose qui obstrue les vaisseaux sanguins. Une pratique courante est la pose d’un stent qui permet d’ouvrir l’artère de nouveau et de rétablir le flux sanguin. Le phénomène de resténose obstrue de nouveau le vaisseau sanguin, majoritairement par la prolifération incontrôlée de cellules musculaires lisses. La recherche sur les revêtements contre la resténose vise à inhiber la prolifération de ces cellules tout en facilitant la ré-endothélialisation. Les revêtements permettraient alors, à la fois de favoriser l’adhérence et la prolifération de cellules endothéliales et de limiter celles des cellules musculaires lisses à la surface du stent ou en limitant toute adhérence non-spécifique. Il a été démontré lors d’études précédentes qu’un copolymère à base de dextrane et de poly(méthacrylate debutyle) (PBMA) répondait à ces critères biologiques et qu’il possédait en plus une bonne résistance à la déformation, paramètre important lié à la déformation induite lors de l’implantation d’un stent. L’approche de ce projet était d’utiliser ce copolymère comme revêtement de stent et d’en améliorer la stabilité à long terme en formant des liens covalents avec le substrat. Pour ce faire, cela nécessitait l’activation de la partie dextrane du copolymère afin de pouvoir le greffer au substrat. Il était important de vérifier pour chaque étape l’influence des modifications effectuées sur les propriétés biologiques et mécaniques des matériaux obtenus, mais aussi d’un point de vue de la chimie, l’influence que cette modification pouvait induire sur la réaction decopolymérisation.... / The last decades have witnessed the remarkable growth of biomaterial science and engineering field, especiallyfor cardiovascular applications, for which devices have evolved from simple material to complex structures.This development has stemmed from the necessity for biomaterials to exhibit different properties, related totheir function, which are not always inherently compatible. Historically, the first materials selected for medicaldevices conception were the ones exhibiting the best compromise between all the physicochemical, mechanicaland biological requirements. Nevertheless, while physicochemical and mechanical properties are often handilycombined, the development of materials which also possess suitable biological properties have proved to bemuch more challenging, leading to clinical complications.Surface modification represents a valid solution to improve the biological performances of medical deviceswhile maintaining the bulk properties of the material. Biomaterial coatings may modulate the biologicalresponse at the biomaterial-host interface and decreases the undesirable effects. Coatings have been optimizedin regards to two main aspects: the biological response and the mechanical response. For the biologicalresponse, the two main approaches consist in 1) inducing cell adhesion, proliferation or migration with proactivecoatings and 2) using inert material, mostly, and avoiding the adhesion of any biological componentswith passive coatings.More complex coatings include the two approaches, allowing the adhesion of a specific type of cell whilerepelling other biological components adhesion. This method has been very useful against the restenosisphenomenon which obstructs blood vessels. A common practice is vessel stenting, a procedure that enables thereopening of the vessel and the restoration of the blood flow. Restenosis causes the new narrowing of the vessel,mostly due to uncontrolled smooth muscle cell proliferation. Researchers looked for coatings capable oflimiting the restenosis occurrence by inhibiting this cell proliferation along with facilitating the reendothelialization.Thus, the coatings would be able to improve endothelial cells adhesion and proliferation andto inhibit smooth muscle cells ones as well as avoiding non-specific adhesion.Previous studies showed that a copolymer made of dextran and poly(butyl methacrylate) (PBMA) demonstratedsuch biological properties and a good resistance to deformation, which is an important parameter related to thedeformation implied in a stent implantation. In this work, the approach was to use this copolymer as a stentcoating and to increase its long-term stability by providing covalent bonds with the substrate. To do so, thedextran part of the copolymer firstly needed to be activated in order to be grafted to the surface. Thus, it wasimportant to ascertain the influence of the multiple modifications on the biological and mechanical propertiesof the resulting materials at each step, but also towards a chemical point of view, the influence that thesemodifications may have on the subsequent copolymerization.

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This thesis describes the synthesis and characterisation of novel mono and dinuclear homogenous [Zn(II)] and [In(III)] metal complexes. Their applications as catalysts for CO₂/epoxide or epoxide/anhydride ring opening copolymerisation and lactide ring opening polymerisation to generate polycarbonates and polyesters, respectively, are also reported. Chapter 3 reports the first indium phosphasalen catalysts for CO₂/cyclohexene oxide ring opening copolymerization. The catalysts are active at 1 bar pressure of CO₂ and are most effective without any co-catalyst. It is also possible to use the complexes to isolate and characterise the key intermediates in the catalytic cycle. Kinetic and spectroscopic analyses show that polymerisation proceeds via a rare cis-mononuclear coordination- insertion mechanism. Chapter 4 describes a series of mono and dinuclear zinc macrocycle catalysts with very high activities for the racemic lactide ring opening polymerisation. In most cases, the dinuclear zinc catalysts significantly out-perform the mono-zinc homologue. In addition, kinetic and spectroscopic investigations suggest a role for the ligand conformation in mediating rate. The catalysts perform very well under immortal conditions and operate at low catalyst loading, whilst conserving high activities. Chapter 5 presents four dinuclear zinc acetate salen catalysts for the ring opening copolymerisation of CO₂/cyclohexene oxide and phthalic anhydride/cyclohexene oxide. The catalysts show moderate activities for CO₂/epoxide copolymerisation but are highly active for epoxide/anhydride copolymerisation. Structure/activity relationship studies reveal that the more flexible and electron donating ligand displays the highest activity. Poly(ester-b-carbonate)s are also afforded using the most active catalyst in terpolymerisations of anhydride/epoxide/CO₂.

Nesta Dissertação, foram realizadas reações de copolimerização de 1,3-butadieno com diferentes alfa-olefinas (1-hexeno, 1-octeno e 1-dodeceno) utilizando-se um sistema catalítico do tipo Ziegler-Natta ternário constituído por versatato de neodímio, hidreto de diisobutilalumínio e cloreto de t-butila. O sistema catalítico também foi avaliado em reações de homopolimerização com cada alfa-olefina. As condições reacionais, tanto da síntese do catalisador como das reações de polimerização, foram mantidas constantes. Foi estudada a influência de diferentes teores de cada alfa-olefina (1, 3, 5, 10, 20 e 30 % em relação ao 1,3-butadieno) sobre a conversão da polimerização, a microestrutura, a massa molar, as propriedades viscosimétricas e a estabilidade térmica dos polímeros obtidos. Foi avaliada, ainda, a influência do tamanho da cadeia da alfa-olefina sobre as características da polimerização. Os polímeros foram caracterizados por espectroscopia na região do infravermelho (FTIR), cromatografia por exclusão de tamanho (SEC), viscosimetria capilar e termogravimetria (TG). A microestrutura dos polímeros, praticamente, não variou com a adição das alfa-olefinas. A massa molar numérica média (Mn) não sofreu alterações significativas, enquanto que a massa molar ponderal média (Mw) apresentou tendência ao aumento, quanto maior foi a incorporação de comonômero. A viscosidade intrínseca não apresentou uma tendência com a adição da alfa-olefina na reação, permanecendo na faixa de 2,015 a 3,557 dL/g. A estabilidade térmica do copolímero mostrou uma tendência a aumentar com a incorporação das alfa-olefinas / In this work, were performed copolymerization reactions of 1,3-butadiene with different alpha-olefins (1-hexene, 1-octene and 1-dodecene), using a ternary catalytic system of Ziegler-Natta, constituted by neodymium versatate, diisobutylaluminum hydride and t-butyl chloride. The catalytic system was also evaluated in homopolymerization reactions with the alpha-olefins. The reaction conditions, both the catalyst synthesis as the polymerization reactions, were kept constant. The influence of different content of each alpha-olefin (1, 3, 5, 10, 20 and 30% compared to 1,3-butadiene) on the polymerization conversion, the microstructure, molar mass, viscometric properties and thermal stability of polymers was studied. The influence of alpha-olefin chain size on polymerization characteristics was also evaluated. The polymers were characterized by infrared spectroscopy (FTIR), size exclusion chromatography (SEC), capillary viscometry and thermogravimetry (TG). The polymer microstructure, practically, did not change with the addition of alpha-olefins. The number average molecular mass (Mn) has not changed; while the weight average molecular mass (Mw) trended to increase. The intrinsic viscosity did not show a trend with the alpha-olefin addition, remaining in the range from 2.015 to 3.557 dL/g. The copolymer thermal stability showed a tendency to increase with the incorporation of alpha-olefins

Orientador: Rubens Maciel Filho / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-17T11:36:13Z (GMT). No. of bitstreams: 1 Lima_NadsonMuriloNascimento_D.pdf: 3180060 bytes, checksum: f741044cb982f1d0e9d33a4f7aba7597 (MD5) Previous issue date: 2010 / Resumo: A síntese de controladores representa uma importante vertente dos desenvolvimentos atuais no campo da pesquisa acadêmica e industrial. Um controlador bem projetado pode significar sucesso no que se refere aos objetivos de produção, sendo gerados materiais com as especificações desejadas e proporcionando que o sistema opere sob certas restrições, levando em consideração aspectos relativos à operabilidade, segurança e minimização de resíduos. Para tanto, sabe-se que as etapas de modelagem são fundamentais para a delineação de estratégias de controle. Contudo, a obtenção de representações matemáticas precisas e, ao mesmo tempo, aplicáveis para o controle da maioria dos processos de interesse da engenharia química é uma tarefa árdua, devido à presença de comportamentos dinâmicos não lineares e variantes ao longo do tempo e, por vezes, do espaço. Deste modo, busca-se a obtenção de modelos mais simples, porém dotados da imprescindível representatividade inerente aos sistemas de produção, a fim de serem projetadas estruturas de controle adequadas para cada necessidade específica. Esta tese enfoca o desenvolvimento de quatro controladores avançados híbridos preditivos não lineares multivariáveis, baseados em modelos nebulosos (fuzzy) funcionais não lineares multivariáveis, para processos de polimerização. Tais sistemas apresentam dinâmicas altamente complexas e de difícil modelagem matemática, dificultando, assim, a aplicação, com sucesso, de metodologias clássicas de controle ou avançadas baseadas em modelos convencionais. Foram considerados dois casos de estudo para a análise de desempenho das configurações de controle propostas: o processo de copolimerização em solução do metacrilato de metila com o acetato de vinila, e a copolimerização industrial do eteno/1-buteno com catalisador Ziegler-Natta solúvel. Os modelos fenomenológicos de ambos os processos já se encontram descritos na literatura, sendo considerados como plantas virtuais para a geração de dados dinâmicos e implementação dos desenvolvimentos sugeridos. A partir de simulações computacionais, os modelos nebulosos dinâmicos funcionais não lineares multivariáveis foram construídos ¿ os quais demonstraram excelentes capacidades para a predição das saídas dos processos como uma função dos dados dinâmicos de entrada ¿ sendo, posteriormente, acoplados à estrutura de controle preditivo MPC (Model-based Predictive Control). A escolha da metodologia MPC como base para o desenvolvimento das estratégias propostas deve-se ao fato de sua notória aplicabilidade industrial a processos químicos multivariáveis, além de possibilitar a incorporação de restrições operacionais nas variáveis controladas e manipuladas. Por fim, foram comparados os desempenhos entre os controladores híbridos delineados e duas estratégias de controle preditivo bastante difundidas na literatura. Os problemas regulatório e servo foram analisados, observando-se resultados satisfatórios em ambas as condições. Isto demonstra o alto potencial dos algoritmos propostos para o controle multivariável de sistemas não lineares. / Abstract: Controllers design has currently a great importance in the field of açademic and industrial research. A well-projected controller may mean the success regarding the aims of production, and it also provides the production of materials with desirable specifications and it allows that the system operates under specific restrictions, considering aspects related to operability, safety and minimization of residue. Then, it is known that modeling stages are fundamental for delineation of controller strategies. However, the obtaining of precise and applicable mathematical representations to the control of most of relevant process in chemical engineering is a challenging task, because of the presence of nonlinear dynamic behaviors and space-time mutable. Therefore, an effort is done to obtain the simpler models, but provided with the essential representativity inherent to production systems. Thus, suitable control structures could be designed for each specific necessity. This work focus on the development of four multivariable nonlinear predictive hybrid advanced controllers, based on multivariable nonlinear functional fuzzy models, to polymerization processes. Such systems present high complex dynamic and hard mathematical modeling, making difficult to apply classic controllers or advanced control methodologies based on conventional models. Two study cases for the performance analysis of the proposed controllers were considered: the copolymerization process of methyl methacrylate and vinyl acetate, and industrial copolymerization of ethene/1 butene with Ziegler-Natta catalysis. The phenomenologic models of the two processes already are described in relevant literature, and they are considered as virtual plants to create dynamic data and to implement the suggested developments. Based on computational simulations, multivariable nonlinear functional dynamic fuzzy models were made - they demonstrated excellent capacity for outputs prediction from input dynamic data - and they were, subsequently, inserted in the MPC (Model-based Predicitve Control) control structure. The choice of MPC methodology to develop the proposal structures is because of its wellknown industry applicability to multivariable chemical processes, beyond it makes possible the incorporation of restrictions in controlled and manipulated variables. Finally, the performance among outlined hybrid controllers and two predictive control strategies fairly widespread in the literature were compared. The regulatory and servo problems were analyzed and satisfactory results were observed in both conditions. This demonstrates the high potential of proposed algorithms to control multivariable nonlinear systems. / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Um modelo matemático da reação de copolimerização em emulsão de acrilato de butila e estireno em reator batelada e semi-batelada isotérmico foi desenvolvido e apresentou bons resultados quando comparado a experimentos disponíveis em literatura científica. O modelo contemplou a solução do balanço populacional, tanto para a distribuição de tamanho de partículas quando para a distribuição média de radicais por partícula. Contemplou-se também a solução do balanço de momentos, para obtenção da massa molar média numérica e mássica. O problema descrito foi resolvido através da solução numérica de um conjunto de equações algébricodiferenciais e o balanço populacional foi resolvido pelo método dos pivots fixos. Foi possível validar com boa aderência a conversão dos monômeros, o diâmetro médio de partículas, número de partículas por litro de emulsão, número médio de radicais por partícula, a distribuição de tamanho de partículas e a massa molar média numérica e mássica ao longo do tempo para um conjunto de experimentos. / A mathematical model of emulsion copolymerization reaction of styrene and butyl acrylate for batch and semi-batch isothermal reactor was developed and presented good results when compared to experiments available in the scientific literature. The model included the solution of the population balance for both particle size distribution and average number of radicals per particle. The balances of moments of the molecular weight distribution are solved to obtain the weight- and numberaveraged molecular weight of the polymer. The problem described was solved by numerical solution of a set of algebraic-differential equations and the population balance was solved by the method of fixed pivots. The model prediction were validated with a set of experiments with respect to the changes of monomer conversion, average particle diameter, number of particles per liter of emulsion, average number of radicals per particle, particle size distribution, number- and weight-average molecular weight during process time.

Dans cette étude, plusieurs voies ont été explorées dans l’objectif d’utiliser des polyesters aliphatiques issus de ressources oléagineuses comme additifs pour le renfort au choc du poly(L-lactide) (PLLA). Dans un premier temps, des poly(ester-amide)s (PEAs) ont été synthétisés à partir de dérivés de l’huile de ricin. La relation structure-propriétés des PEAs obtenus a été clairement établie. La dispersion des PEAs (à différents taux) par extrusion à l’état fondu dans une matrice de PLLA a ensuite été effectuée, démontrant un accroissement de la résilience de ces mélanges en comparaison au PLLA seul. Une étude systématique reliant la structure d’une large gamme de polyesters aux propriétés des mélanges polyesters/PLLA, a ensuite été réalisée. Une forte dépendance de la résilience des mélanges polyesters/PLLA avec la cristallinité de l’additif polyester a été observée et quantifiée.Une amélioration des propriétés mécaniques du PLLA a également été obtenue par polymérisation par ouverture de cycle du lactide amorcée par un poly(acide ricinoléique) di-hydroxy téléchélique. Les copolymères triblocs ainsi formés ont été caractérisés d’un point de vue morphologique et mécanique.Enfin, un travail exploratoire utilisant l’ADMET comme méthode de polymérisation a été conduit, permettant la synthèse de nouveaux polymères prometteurs pour le renfort au choc du PLLA. Notamment, la copolymérisation de α,ω-diènes bio-sourcés a permis de mimer le polyéthylène basse densité linéaire, couramment employé pour le renfort au choc du PLLA. / The objective of this thesis work, is to promote the use of fatty acid-based aliphatic polyesters as impact modifiers for poly(L-lactide) (PLLA).Firstly, poly(ester-amide)s (PEAs) have been synthesized from castor oil derivatives. The structure-properties relationship of the PEAs so-formed was clearly established. The PEAs were then melt-blended with PLLA by extrusion, yielding blends with improved impact strength compared to neat PLLA.A series of polyesters covering a wide range of thermo-mechanical properties was then employed to evaluate the influence of the polyester morphology on the properties of the blends with PLLA. A strong dependence of the impact strength of the blends was noticed with the crystallinity degree of the polyester additive.An improvement of the mechanical properties of PLLA was also obtained by ring-opening polymerization of lactide initiated by a di-hydroxy telechelic poly(ricinoleic acid). The so-formed triblock copolymers were fully characterized in terms of morphology and mechanical properties.Finally, an exploratory investigation related to the synthesis of PLLA impact modifiers by ADMET was carried out. Particularly, the copolymerization of two bio-based α,ω-dienes yielded a series of “LLDPE like” polyesters, LLDPE being a commonly used impact modifier for PLLA.

Ce travail concerne l'étude de la polymérisation de l'éthylène allant de l'homopolymérisation purement radicalaire jusqu'à la copolymérisation utilisant un mécanisme hybride radicalaire/catalytique. Ce travail montre que le polyéthylène peut être synthétisé par voie radicalaire dans des conditions expérimentales beaucoup plus douces que celles utilisées industriellement (P>1000 bar et T>100°C). L'éthylène a été polymérisé à partir de 10°C et 5 bar de pression d'éthylène. Un important effet activateur du solvant a été mis en évidence. De plus la polymérisation en milieu dispersé aqueux de l'éthylène a aussi été étudiée. Des latex stables de PE avec des taux de solide de 40% ont pu être obtenus. Deux morphologies de nanoparticules, cylindre ou sphère, ont été observées. La copolymérisation radicalaire avec des monomères vinyliques polaires a été également étudiée en solution ou en émulsion. Des insertions d'éthylène jusqu'à 50% ont été obtenues. De plus l'influence du comonomère et du solvant organique utilisé sur la polymérisation radicalaire de l'éthylène a été quantifiée. Une nouvelle technique de polymérisation hybride radicalaire/catalytique a été développée pour pouvoir obtenir toute la gamme de compositions possibles de copolymères éthylène/monomère polaire à partir d'un complexe de nickel qui amorce la polymérisation radicalaire et catalyse également la polymérisation de l'éthylène. Ce complexe subit une rupture homolytique réversible de la liaison nickel carbone et permet la synthèse de copolymères multiblocs. Des insertions d'éthylène de 1% à 99% ont été obtenues en faisant varier la pression d'éthylène et la concentration en comonomères polaires / This work aims to study ethylene polymerization from the free radical polymerization process to the copolymerization by a hybrid radical/catalytic mechanism. PE is synthesized by free radical polymerization under milder experimental conditions than industrial ones (P>1000 bar and T>100°C). Indeed free radical polymerization of ethylene is efficient even down to pressure of 5 bar and temperature of 10°C. Several unexpected behaviors are observed such as a high solvent activation effect. Beside the slurry process in organic solvent, polymerization in aqueous dispersed media is also performed. Stable PE latexes are obtained with solid contents up to 40%. Two different PE particles morphologies are observed cylinder-like and sphere-like. Then free radical copolymerization is studied using a broad range of polar vinyl monomers in organic solvent and emulsion. Insertions up to 50% of ethylene are obtained under mild conditions. The ambivalent role of comonomer as monomer and activator of the polymerization is highlighted. In order to obtain a wide range of composition of polar/non-polar copolymers a new technique of polymerization has been developed. A nickel complex is used to initiate the free radical polymerization and to catalyse the coordination/insertion ethylene polymerization. This nickel complex is capable of a reversible homolytic cleavage of its nickel-carbon bond. Finally, this hybrid process is used to copolymerize efficiently ethylene with various polar vinyl monomers. Multiblock copolymers with ethylene content from 1% to 99% are obtained by simply varying the monomer feeds

Plusieurs complexes de salphen à base de métaux transition (Cr, Co, Fe) ont été synthétisés et utilisés comme catalyseurs pour la copolymérisation d’époxydes avec du monoxyde de carbone (CO), des anhydrides ou du dioxyde de carbone (CO2). De nouveaux complexes à base de Zn, Al, Mg ont également été testés pour la copolymérisation d’époxydes avec CO2.La partie première s’intéresse principalement à la copolymérisation d’oxyde de propylène avec du monoxyde de carbone. Le complexe salphen de chrome et Co2(CO)8 ont été utilisées comme catalyseurs. Quel que soit le complexe utilisé, il a été observé une faible activité et les produits de carbonylation attendus (polyester et lactone) ont été obtenus en faible quantité. En revanche, la combinaison in-situ de ces deux catalyseurs a montré une activité supérieure. Cela a conduit à la formation de la lactone cyclique (β-butyrolactone) et de poly(ester-co-éther) de faible masse molaire, ce qui marque une faible compatibilité de ces complexes.La partie suivante traite de la copolymérisation d’époxydes avec des anhydrides catalysée par des complexes de salphen à base de chrome et fer ou d’une base organique simple. Les complexes utilisés sans co-catalyseur ont été inactifs, mais la combinaison avec la base organique (PPNCl) comme co-catalyseur a conduit à la copolymérisation alternée des deux monomères, produisant des polyesters avec des masses molaires jusqu’ à 10 kg.mol-1 et une faible dispersité. PPNCl s’est révélée être la base la plus efficace pour la copolymérisation alternée des époxydes et des anhydrides. Les bases organiques simples utilisées seules ont aussi permis l’obtention de polyesters, mais avec des temps de polymérisation cinq fois plus longs.Enfin, la troisième partie présente la copolymérisation des époxydes avec CO2 en présence de complexes salphen de Cr ou de Co. Les complexes salphen cobalt ont été significativement plus efficaces pour la copolymérisation de l’oxyde de propylène (PO) ou de l’oxyde de cyclohexène (CHO) avec CO2 que leurs homologues à base de chrome. Les polycarbonates obtenus avec les complexes de cobalt ont plus de 99% d’unités carbonate, des masses molaires allant de 10 à 35 kg.mol-1 et une faible dispersité. Les études cinétiques ont permis de montrer que la polymérisation est contrôlée. Des analyses par spectrométrie de masse MALDI-TOF ont permis de vérifier la microstructure et le mécanisme d’activation. Toutefois, pour la copolymérisation de PO avec CO2, les complexes salphen cobalt ont une activité plus faible (100-450 h-1) ainsi qu’une sélectivité en polycarbonate moindre (40-90%) que les complexes salen cobalt. Une sélectivité de 100% vers la synthèse de polycarbonate a néanmoins pu être obtenue lors de la copolymérisation de CHO avec CO2. Enfin, les complexes β-diminate, ketiminate et aminidate d’Al, Zn et Mg utilisés pour la copolymérisation d’époxydes avec CO2 se sont révélés décevants car présentant une activité très faible et seuls des homopolyéthers ont été obtenus. / A series of salphen complexes based on Cr, Co and Fe was synthesized and used as catalysts in ring-opening copolymerization of different substrates: (i) epoxides with carbon monoxide (CO), (ii) epoxides with anhydrides and (iii) epoxides with carbon dioxide (CO2). Additionally, a screening of catalytic activity for the last substrate was performed with novel Zn, Al and Mg non-salen based complexes.The first part of the Thesis deals with the copolymerization of propylene oxide with carbon monoxide using asymmetric salphen chromium complex and Co2(CO)8 in order to prepare a synthetic equivalent of polyhydroxybutyrate (PHB) otherwise accessible by fermentation of various substrates. Very poor catalytic performances towards carbonylated products (PHB or β-butyrolactone (BBL)) were observed with any of the two complexes. The combination of both salphen chromium and Co2(CO)8 complexes led to increased formation of BBL. Low molar mass poly(ester-co-ether) was only prepared, suggesting a poor compatibility of selected complexes.The second part of the work is focused on the copolymerization of epoxides with anhydrides catalyzed by salphen chromium or iron complexes combined with simple organic bases as cocatalysts. Salphen complexes alone were almost inactive, while in the presence of bis(triphenylphosphineiminium)chloride (PPNCl) they afforded highly alternating polyesters with molar mass up to 10 kg.mol-1 and low dispersity. Surprisingly, organic bases alone afforded similar, highly alternating polyesters at five-time lower polymerization rate. PPNCl was found to be an effective catalyst for the highly alternating copolymerization of various epoxides and anhydrides.The last part of our investigations refers to the copolymerization of epoxides with CO2 using salphen chromium and especially salphen cobalt complexes. Cobalt catalysts were significantly more active in propylene oxide (PO)/CO2 and cyclohexene oxide (CHO)/CO2 copolymerization compared to their chromium analogues. Highly alternating polycarbonates (> 99%) with low dispersity and molar mass 10-35 kg.mol-1 were prepared by salphen cobalt complexes. Kinetic studies showed that these polymerizations are controlled and MALDI-TOF MS analysis was used for initiation mechanism clarification. Compared to widely investigated salen Co catalysts, salphen Co complexes exhibit lower activity (100-450 h-1) and selectivity to polymer (40-90%) in propylene oxide/CO2 copolymerization, while 100% selectivity to polycarbonate was achieved in the copolymerization of CHO and CO2. Alternatively, new Al, Zn and Mg-based catalysts were tested for CO2 activation, however, they usually led only to epoxide homopolymerization. / V této práci byla připravena řada salfenových komplexů na bázi chromu, kobaltu a železa. Tyto komplexy byly použity jako katalyzátory pro kopolymerizace epoxidů s různými substráty: (i) s oxidem uhelnatým (CO), (ii) s anhydridy a (iii) s oxidem uhličitým (CO2). U nových komplexů na bázi zinku, hliníku a hořčíku byla dále testována možnost jejich použití jako katalyzátorů pro kopolymerizace epoxidů s CO2.První část práce se zabývá kopolymerizací epoxidů s oxidem uhelnatým s využitím asymetrického salfenového komplexu na bázi chromu a Co2(CO)8 s cílem připravit kopolymer na bázi přírodního polyhydroxybutyrátu (PHB). Salfenový komplex chromu i Co2(CO)8 vykazovaly velmi nízké aktivity při karbonylaci propylenoxidu a poskytovaly pouze nepatrné množství produktů (cyklického β-butyrolaktonu a PHB). Kombinace obou katalytických komplexů vedla k výraznému zvýšení aktivity ve prospěch cyklického produktu (β-butyrolaktonu) i polymeru. Kopolymerizací PO s CO byl získán pouze nízkomolekulární poly(ester-co-ether), což naznačuje špatnou vzájemnou kompatibilitu těchto komplexů.Druhá část je zaměřena na kopolymerizace epoxidů s anhydridy katalyzované salfenovými komplexy chromu a železa v kombinaci s jednoduchými organickými bázemi. Samotné salfenové komplexy chromu a železa nevedly ke vzniku polymeru. V kombinaci s nukleofilním kokatalyzátorem bis(trifenylfosfin)iminium chloridem (PPNCl) ovšem tyto komplexy poskytly alternující kopolymery epoxidu a anhydridu (polyestery) s molárními hmotnostmi do 10 kg.mol-1 a nízkou dispersitou. Dále bylo zjištěno, že samotné organické báze poskytují podobně jako salfenové komplexy vysoce alternující kopolymery se srovnatelnou molární hmotností i úzkou dispersitou, i když je zapotřebí 5x delších polymerizačních časů. Nejvyšší účinnost ze všech testovaných bází měl PPNCl. Tato báze byla dále efektivně použita pro kopolymerizace řady epoxidů a anhydridů za vzniku vysoce alternujících kopolymerů. Třetí část pojednává o kopolymerizacích epoxidů s CO2 s využitím salfenových komplexů chromu a kobaltu. Bylo zjištěno, že kobaltové komplexy jsou oproti chromovým mnohem efektivnější katalyzátory jak při kopolymerizacích propylenoxidu (PO) s CO2 tak i cyklohexenoxidu (CHO) s CO2. Salfenové komplexy kobaltu poskytly polykarbonáty s vysokým obsahem karbonátových jednotek v kopolymeru (> 99%), úzkou dispersitou a s molárními hmotnostmi 10-35 kg.mol-1. Studie kinetiky odhalila kontrolovaný průběh kopolymerizace. Dále byla provedena MALDI-TOF analýza výsledných polykarbonátů s cílem objasnit mechanismus iniciace kopolymerizace. Ve srovnání se salenovými komplexy kobaltu vykazují salfenové komplexy při kopolymerizacích PO s CO2 nižší aktivitu (100-450 h-1) i selektivitu na polykarbonát (40-90%). Při kopolymerizacích CHO s CO2 byla ovšem selektivita 100%. Nové komplexy na bázi Al, Mg a Zn byly také testovány jako katalyzátory pro kopolymerizace epoxidů s CO2, nicméně jejich aktivita byla nízká a výsledkem těchto reakcí byly pouze polykarbonáty s nízkým podílem karbonátových jednotek nebo polyethery.