Die vorliegende Arbeit hat die Kombination von Zwillingspolymerisation mit der Isocyanat- und Polyurethanchemie zum Inhalt. Dadurch wird das Verständnis der Zwillingspolymerisation erweitert und neue Ansätze zur Herstellung organisch-anorganischer Hybridmaterialien erhalten. Das Reaktionsverhalten von aminofunktionellen Zwillingsmonomeren gegenüber freien Isocyanaten wird untersucht. Durch Reaktion von 2-(3-Amino-n-propyl)-2-methyl-4H-1,3,2-benzodioxasilin mit unterschiedlichen Mono-, Diisocyanaten und isocyanatfunktionellen Prepolymeren sind Harnstoffderivate bzw. neuartige Prepolymere zugänglich, welche in der Lage sind zu polymerisieren. Die resultierenden Harnstoffe wurden charakterisiert und bezüglich ihrer Fähigkeit eine simultane Zwillingspolymerisation mit 2,2´-Spirobi[4H-1,3,2-benzodioxasilin] einzugehen untersucht. Ein Fokus lag auf der Untersuchung des Verhaltens der dargestellten Prepolymere. Diese wurden systematisch mit unterschiedlichen Polymerisationsparametern betrachtet. Eine Charakterisierung der Polymerisate erfolgte mittels Festkörper-NMR-Experimenten, Elektronenmikroskopie, TGA, sowie Extraktionsversuchen. Eine potenzielle Anwendungsmöglichkeit dieser Prepolymersysteme als Haftvermittler für Holz-Kunststoff-Verbundmaterialien wurde durch mechanische Zugscherversuche aufgezeigt. Neben der Betrachtung von 2-(3-Amino-n-propyl)-2-methyl-4H-1,3,2-benzodioxasilin-basierten Systemen wurde ein neuartiges aminofunktionelles Zwillingsmonomer, das Tris-furfuryloxy-3-aminopropylsilan erstmals dargestellt und charakterisiert. Eine Umsetzung mit Isocyanaten und isocyanatfunktionellen Prepolymer wurde analog zu den oben genannten Systemen durchgeführt. Mittels Röntgeneinkristallstrukturanalyse wurde die molekulare Struktur des entsprechenden Phenylisocyanat-Adduktes bestätigt. Die kationische Polymerisation der entsprechenden Harnstoffderivate führte zu neuartigen Hybridmaterialien, welche nach Extraktion mittels Festkörper-NMR-Experimenten charakterisiert wurden.:Inhalt 1. Einleitung und Zielsetzung 9 1.1 Einleitung und Motivation 9 1.2 Zielsetzung 10 2. Theoretische Grundlagen 12 2.1 Reaktionsverhalten der Isocyanate 12 2.1.1 Addition von H-aktiven Spezies 12 2.1.2 Allophanat- und Biuretbindungen 13 2.1.3 Dimerisierung und Trimerisierung 14 2.1.4 Thermische Stabilitäten, Reversibilität 15 2.1.5 Blockierung von Isocyanaten 17 2.2 Technisch relevante Vertreter für PU-Komponenten 19 2.2.1 Technisch verwendete Isocyanate 19 2.2.2 Alkohole 20 2.2.3 Prepolymere 21 2.2.4 Umriss einer Struktur- Eigenschaftsbeziehung von Polyurethanen 22 2.3. Modifizierung von Polyurethanen 23 2.3.1 PU Copolymere 23 2.4. Haftvermittler und Lacke auf PU-Basis 25 2.5.1. Mechanische Charakterisierung der Haftfestigkeit 26 2.5 Zwillingspolymerisation 27 2.5.1 Allgemein 27 2.5.2 Simultane Zwillingspolymerisation 28 3. Ergebnisse und Diskussion 30 3.1. Vorversuche zum Verhalten von Zwillingsmonomeren 30 3.1.1 Stabilität von Zwillingsmonomeren gegenüber freien Isocyanaten 30 3.1.2 Verhalten von Zwillingsmonomeren gegenüber substituierten Harnstoffen 33 3.1.3 Reaktion von aminofunktionellen Zwillingsmonomeren mit Monoisocyanat 34 3.1.4 Reaktion von 2-(3-Amino-n-propyl)-2-methyl-4H-1,3,2-benzodioxasilin (APSI) mit Diisocyanaten 41 3.1.5 Erkenntnisse der Voruntersuchungen mit niedermolekularen Isocyanaten 46 3.1.6 Reaktion von 2-(3-Amino-n-propyl)-2-methyl-4H-1,3,2-benzodioxasilin (APSI) mit isocyanathaltigen PU-Prepolymeren 47 3.2. Simultane Polymerisation von APSI-Isocyanat-Addukten mit Spiro 56 3.2.1. Simultane Polymerisation von APSI-p-fluoro-PI-Addukt mit Spiro 56 3.2.2 Polymerisation von APSI-IPDI-PolyTHF-Prepolymer 60 3.2.3 Simultane Polymerisation von APSI-Diisocyanat-Addukt mit Spiro 61 3.2.4 Polymerisation von Zwillingsprepolymeren 64 3.3 Aminofunktionelle Zwillingsmonomere zur Herstellung von neuartigen Polyfurfurylalkohol-Hybridmaterialien 85 3.3.1 Synthese von Tris-furfuryloxy-3-aminopropylsilan (TFAPSI) 85 3.3.2 Polymerisation von Tris-furfuryloxy-3-aminopropylsilan 85 3.3.3 Umsetzungen von Tris-furfuryloxy-3-aminopropylsilan mit Isocyanaten 87 3.3.4 Zwillingspolymerisation der Isocyanat-Addukte von 3-Aminopropyl-tris-furfuryloxysilan 90 4. Zusammenfassung und Ausblick 95 5. Experimenteller Teil 99 5.1 Chemikalien 99 5.2 Geräte 99 5.3 Synthesen 101 5.4 Polymerisationen 109 5.4.1 Polymerisation von APSI-basierten Monomeren 109 5.4.2 Polymerisation von TFAPSI-basierten Monomeren 110 6 Anhang 111 7 Literaturverzeichnis 126 Danksagung 131 Selbstständigkeitserklärung 132 Lebenslauf 133 Publikationen und Posterbeiträge 134

Ces travaux de thèse concernent l’étude de matériaux supramoléculaires en vue de générer de nouveaux élastomères silicones auto-cicatrisants. Dans un premier temps, l’étude de la bibliographie a permis de recenser les différentes voies intégrant de la chimie supramoléculaire développées dans le domaine des silicones et basées sur les liaisons hydrogène. L’effet des groupements associatifs sur les propriétés rhéologiques et mécaniques des matériaux a été discuté, et les limitations de ces systèmes soulignées. La chimie développée par l’équipe du Dr. Leibler, adaptée par la suite aux silicones par le Pr. Zhang et son équipe, a particulièrement été analysée lors de notre étude de compréhension. Les relations structures/propriétés n’étaient pas clairement élucidées à l’issue de cette étude de la bibliographie. Des études modèles impliquant un PDMS téléchélique aminé ainsi que de l’urée ont donc été réalisées. La caractérisation précise des structures des produits de réaction a permis de mettre en exergue certaines corrélations entre structures (choix du groupement associant, masse molaire du copolymère, fonctionnalité) et propriétés (rhéologiques et mécaniques) qui n’avaient alors pas été démontrées pour ces systèmes. Il a aussi été montré que la force des groupements et les enchevêtrements jouent un rôle primordial. Une chimie différente, inspirée des travaux de Yilgör et al sur les copolymères segmentés, a par la suite été envisagée, en mettant en jeu cette fois la réaction d’aza-Michael. Cette synthèse se démarque du premier système par un meilleur contrôle de la structure macromoléculaire finale. Un silicone supramoléculaire élastomère et auto-cicatrisant a été obtenu en combinant une fonctionnalité importante et une masse molaire finale élevée. Les propriétés mécaniques de ce polymère ont été optimisées par l’ajout de charges plus ou moins renforçantes. L’impact d’un tel renfort sur les propriétés auto-cicatrisantes du système a été discuté. / This PhD thesis focused on the investigation of supramolecular materials in order to generate new self-healing supramolecular silicone elastomers. Firstly, a literature review on silicone materials was realized and we identified the different ways developed in the silicone domain that imply supramolecular chemistry and in particular hydrogen-bonds. The influence of associating groups on rheological and mechanical properties of these materials was discussed, and the restrictions of such systems were highlighted. The chemistry developed by Dr. Leibler and co-workers, later adapted to silicones by Pr Zhang and his team, was deeply investigated during our comprehension study. Relationships between structure and properties were nonetheless not fully elucidated in these studies. Model reactions involving telechelic amino-PDMS and urea were then carried out. The thorough characterization of the final structure of the reaction products highlighted few correlations between structural parameters (choice of the type of associating group, molecular weight of copolymer, functionality) and properties (rheological and mechanical) that had not been demonstrated yet for these systems. We showed that, among others, the strength of the associating groups as well as the entanglements play a fundamental role. A different chemistry, inspired by Yilgör and co-workers’ studies on segmented copolymers, was later considered by carrying out an aza-Michael reaction. This synthesis differs from the previous one by its better control of the final macromolecular structure. A supramolecular silicone elastomer with self-healing abilities was obtained by combining a large functionality together with a high final molecular weight. Mechanical properties of this material were further enhanced through the addition of more or less reinforcing fillers. The influence of such reinforcement on self-healing capacity of this system was discussed.

Materiais dielétricos flexíveis e filmogênicos são essências para a produção de diversos dispositivos tecnológicos, tais como Organic Light Emiting Diodes (OLED), Transistores de Efeito de Campo (FET do Inglês Field Emission Transistor) ou fotovoltaicos orgânicos (OPV do Inglês Organic Photovoltaics). Dentro deste contexto, é importante salientar o esforço de desenvolver rotas sintéticas mais sustentáveis baseadas em matérias-primas e processos mais amigáveis ao meio ambiente. No Grupo de Química de Materiais Híbridos e Inorgânicos (GQMATHI) há mais de dez anos se pesquisa rotas sintéticas de preparação de oligômeros e polímeros de uretanas usando CO2 como matéria-prima. Assim, são sintetizados os materiais classificados como polihidroxi-uretânicos, que são obtidos a partir do monômero bis-ciclocarbonato de polidimetilsiloxano (CCPDMS) mediante a reação de polimerização por abertura de anel (ROP - do inglês Ring Oppening Polymerization). O monômero é obtido pela reação de cicloadição de CO2 no seu respectivo epóxido: poli(dimetil-siloxano) diglicidil éter (PDMS). Neste projeto os materiais hidroxi-uretânicos foram sintetizados, utilizando tanto o CCPDMS como monômero precursor da reação, como o ciclocarbonato de bisfenol A diglicidil éter (CCDGEBA). O oligômero formado foi ensaiado em diferentes proporções destes dois ciclocarbonatos na reação frente à uma diamina (5-Amino-1,3,3-trimetilciclohexanometilamina ,IFDA). Utilizou-se como grupo terminador de cadeia o 3-aminopropiltrietóxissilano (APTS). Os ciclocarbonatos foram caracterizados por espectroscopia vibracional (FTIR) e de ressonância magnética nuclear (RMN) de 13C e 1H. Na espectroscopia vibracional a formação do grupamento ciclocarbonato foi obtida pela presença da banda de carbonila em 1790 cm-1 , enquanto na RMN os sinais do duplo dubleto próximo de 4,5 ppm (1H) e o pico em 154 ppm (13C) foram interpretados como sinais carcaterísticos do grupo ciclocarbonato. O material oligomérico sintetizado a partir dos ciclocarbonatos foi caracterizado por análise termogravimétrica (TGA), calorimetria diferencial de varredura (DSC), análise dinâmico-mecânica (DMA) bem como filmes dos mesmos foram preparados via spin coating. Os filmes foram caracterizados eletricamente por medidas de espectroscopia de impedância, visando avaliar a possibilidade do material ser utilizado como camada dielétrica em transístores orgânicos do tipo FET. Visando um melhor desempenho do material hidroxi-uretânico nesta aplicação o dióxido de titânio (constante dielétrica (ε) ≈ 100) foi introduzido na matriz polimérica. Assim sendo, a introdução desta cerâmica classificará o material formado como um material compósito do tipo híbrido inorgânico-orgânico. Este híbrido também foi caracterizado por espectroscopia de impedância revelando um aumento da constante dielétrica, porém um aumento da perda dielétrica também foi observada para o híbrido. / Flexible and film-forming dielectric materials are essential for the production of various technological devices, such as Organic Light Emitting Diodes (OLED), Field Effect Transistors (FETs) or organic photovoltaics (OPVs). Within this context, it is important to highlight the effort to develop more sustainable synthetic routes based on raw materials and more environmentally friendly processes. In the Group of Chemistry of Hybrid and Inorganic Materials (GQMATHI) more than ten years ago, synthetic routes for preparation of oligomers and polymers of urethanes using CO2 as raw material have been investigated. Thus, materials classified as polyhydroxy urethanes, which are obtained from the bis-cyclocarbonate monomer of polydimethylsiloxane (CCPDMS) are synthesized by the Ring Oppening Polymerization (ROP) reaction. The monomer is obtained by the cycloaddition reaction of CO2 in its respective epoxide: poly (dimethylsiloxane) diglycidyl ether (PDMS). In this project the hydroxy urethane materials were synthesized, using two different types of precursor monomer : the CCPDMS and bisphenol A diglycidyl ether cyclocarbonate (CCDGEBA). The oligomer formed was tested in different ratios of these two cyclocarbonates in the reaction against a diamine (5-Amino-1,3,3-trimethylcyclohexanemethylamine (IFDA)). The aminopropyltriethoxysilane (APTS) was used as the chain terminator group. After the synthesis of the cyclocarbonates, characterizations were made by vibrational spectroscopy (IR) and nuclear magnetic resonance (NMR) of 13C and 1H. The successful formation of the cyclocarbonate was confirmed by the 1790 cm-1 peak in the vibrational spectroscum as well as by the dublet near 4.5 ppm (1H NMR) and the singlet at 154 ppm (13 C NMR). The oligomeric hydroxyurethane synthesized from the cyclocarbonates reaction with IFDA and APTS was characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic-mechanical analysis (DMA) and films were prepared by spin coating. The electrical characterization of the films was made by impedance spectroscopy, aiming to evaluate its application on organic FET´s as adielectric layer . In order to improve the performance of the hydroxy urethane material for this application, titanium dioxide (dielectric constant (ε) ≈ 100) was incorporated into the oligomer matrix, thus an hybrid nanocomposite material was formed. The impedance chacacterization of the hybrid was performed showing higher dielectric constant for this new material, although observed a higher dielectric loss, 9 vs 0,2 ,respectively for the hydroxyurethane and the hybrid.

Materiais dielétricos flexíveis e filmogênicos são essências para a produção de diversos dispositivos tecnológicos, tais como Organic Light Emiting Diodes (OLED), Transistores de Efeito de Campo (FET do Inglês Field Emission Transistor) ou fotovoltaicos orgânicos (OPV do Inglês Organic Photovoltaics). Dentro deste contexto, é importante salientar o esforço de desenvolver rotas sintéticas mais sustentáveis baseadas em matérias-primas e processos mais amigáveis ao meio ambiente. No Grupo de Química de Materiais Híbridos e Inorgânicos (GQMATHI) há mais de dez anos se pesquisa rotas sintéticas de preparação de oligômeros e polímeros de uretanas usando CO2 como matéria-prima. Assim, são sintetizados os materiais classificados como polihidroxi-uretânicos, que são obtidos a partir do monômero bis-ciclocarbonato de polidimetilsiloxano (CCPDMS) mediante a reação de polimerização por abertura de anel (ROP - do inglês Ring Oppening Polymerization). O monômero é obtido pela reação de cicloadição de CO2 no seu respectivo epóxido: poli(dimetil-siloxano) diglicidil éter (PDMS). Neste projeto os materiais hidroxi-uretânicos foram sintetizados, utilizando tanto o CCPDMS como monômero precursor da reação, como o ciclocarbonato de bisfenol A diglicidil éter (CCDGEBA). O oligômero formado foi ensaiado em diferentes proporções destes dois ciclocarbonatos na reação frente à uma diamina (5-Amino-1,3,3-trimetilciclohexanometilamina ,IFDA). Utilizou-se como grupo terminador de cadeia o 3-aminopropiltrietóxissilano (APTS). Os ciclocarbonatos foram caracterizados por espectroscopia vibracional (FTIR) e de ressonância magnética nuclear (RMN) de 13C e 1H. Na espectroscopia vibracional a formação do grupamento ciclocarbonato foi obtida pela presença da banda de carbonila em 1790 cm-1 , enquanto na RMN os sinais do duplo dubleto próximo de 4,5 ppm (1H) e o pico em 154 ppm (13C) foram interpretados como sinais carcaterísticos do grupo ciclocarbonato. O material oligomérico sintetizado a partir dos ciclocarbonatos foi caracterizado por análise termogravimétrica (TGA), calorimetria diferencial de varredura (DSC), análise dinâmico-mecânica (DMA) bem como filmes dos mesmos foram preparados via spin coating. Os filmes foram caracterizados eletricamente por medidas de espectroscopia de impedância, visando avaliar a possibilidade do material ser utilizado como camada dielétrica em transístores orgânicos do tipo FET. Visando um melhor desempenho do material hidroxi-uretânico nesta aplicação o dióxido de titânio (constante dielétrica (ε) ≈ 100) foi introduzido na matriz polimérica. Assim sendo, a introdução desta cerâmica classificará o material formado como um material compósito do tipo híbrido inorgânico-orgânico. Este híbrido também foi caracterizado por espectroscopia de impedância revelando um aumento da constante dielétrica, porém um aumento da perda dielétrica também foi observada para o híbrido. / Flexible and film-forming dielectric materials are essential for the production of various technological devices, such as Organic Light Emitting Diodes (OLED), Field Effect Transistors (FETs) or organic photovoltaics (OPVs). Within this context, it is important to highlight the effort to develop more sustainable synthetic routes based on raw materials and more environmentally friendly processes. In the Group of Chemistry of Hybrid and Inorganic Materials (GQMATHI) more than ten years ago, synthetic routes for preparation of oligomers and polymers of urethanes using CO2 as raw material have been investigated. Thus, materials classified as polyhydroxy urethanes, which are obtained from the bis-cyclocarbonate monomer of polydimethylsiloxane (CCPDMS) are synthesized by the Ring Oppening Polymerization (ROP) reaction. The monomer is obtained by the cycloaddition reaction of CO2 in its respective epoxide: poly (dimethylsiloxane) diglycidyl ether (PDMS). In this project the hydroxy urethane materials were synthesized, using two different types of precursor monomer : the CCPDMS and bisphenol A diglycidyl ether cyclocarbonate (CCDGEBA). The oligomer formed was tested in different ratios of these two cyclocarbonates in the reaction against a diamine (5-Amino-1,3,3-trimethylcyclohexanemethylamine (IFDA)). The aminopropyltriethoxysilane (APTS) was used as the chain terminator group. After the synthesis of the cyclocarbonates, characterizations were made by vibrational spectroscopy (IR) and nuclear magnetic resonance (NMR) of 13C and 1H. The successful formation of the cyclocarbonate was confirmed by the 1790 cm-1 peak in the vibrational spectroscum as well as by the dublet near 4.5 ppm (1H NMR) and the singlet at 154 ppm (13 C NMR). The oligomeric hydroxyurethane synthesized from the cyclocarbonates reaction with IFDA and APTS was characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic-mechanical analysis (DMA) and films were prepared by spin coating. The electrical characterization of the films was made by impedance spectroscopy, aiming to evaluate its application on organic FET´s as adielectric layer . In order to improve the performance of the hydroxy urethane material for this application, titanium dioxide (dielectric constant (ε) ≈ 100) was incorporated into the oligomer matrix, thus an hybrid nanocomposite material was formed. The impedance chacacterization of the hybrid was performed showing higher dielectric constant for this new material, although observed a higher dielectric loss, 9 vs 0,2 ,respectively for the hydroxyurethane and the hybrid.

Neste trabalho, foi estudada uma rota alternativa para síntese de poliuretanos sem a utilização de isocianatos (NIPU) por um processo de fabricação seguro e utilizando CO2 como insumo. A produção destes poliuretanos \"verdes\" ocorreu através da reação entre ciclocarbonatos e diaminas. A caracterização da estrutura química e a análise dos produtos da reação de formação dos poliuretanos foi possível com a utilização de espectroscopia de infravermelho com transformada de Fourier (FTIR) e espectroscopia de ressonância magnética nuclear (RMN). Foram sintetizados também os ciclocarbonatos pela reação de cicloadição de CO2 ao grupo oxirano de uma resina epóxi e o co-catalisador (resinato de zinco) utilizado na obtenção dos carbonatos cíclicos. Para otimização da formação dos ciclocarbonatos desenvolveu-se um reator de síntese, o qual permitiu a análise do rendimento da reação em função dos parâmetros de síntese controlados: pressão de CO2, temperatura do meio reacional, tempo de síntese, gaseificação da resina epóxi com CO2 (por agitação mecânica ou sistema de refluxo de CO2) e fonte de aquecimento (convencional ou utilizando radiação de microondas). A estrutura química do carbonato obtido, o rendimento e os possíveis subprodutos da reação de cicloadição também foram analisados por FTIR e RMN. / Seeking to optimize the formation of ciclocarbonates, it was developed a reactor in a closed system (no atmospheric emissions of CO2) in which the parameters of synthesis could be controlled: CO2 pressure, temperature of the reaction medium, distribution and concentration of CO2 gas bubbles in epoxy resin. The development of the ciclocarbonate synthesis\'s reactor included new systems to improve the gas-liquid contact between the reactants (aerator and CO2 reflux system) and also a heating system using microwave radiation. It were synthesized in this research, the co-catalyst (zinc resinate), the ciclocarbonate under different conditions of: pressure, temperature, synthesis time, heating source, aeration and catalyst, and \"green\" polyurethanes by an alternative route instead of the use of isocyanates, which have potential in specific applications (control of properties through chemical structure of the polymer). The result of the carbonates formation reaction was analyzed by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (RMN) to obtain the carbonates\'s chemical structure\'s, yield and the reaction\'s by-products. Non-isocyanate polyurethanes (NIPU) were obtained from a manufacturing process and secure using CO2 as an input. The characterization of the chemical structure and the yield and by-product\'s analysis of the polyurethanes formation reaction also happened by FTIR and RMN.

The aim of this research project was to study the possible synthesis of the morphine analog 3-oxo-5-phenylmorphan via the photochemical cyclization of the acyl azide of 1-phenylcyclohexaneacetic acid.

Furopyranones and furopyrrolones are furan-fused bicyclic heterocycles containing pyranone and pyrrolone framework respectively. Many natural products and pharmaceutical agents include these core structures. In this study, new synthetic methodologies were developed for the synthesis of furopyranone and furopyrrolone derivatives. In the first section of this thesis, methyl 2-(2-methoxy-2-oxoethyl)-3-furoate was hydrolyzed forming 2-(carboxymethyl)-3-furoic acid which underwent intramolecular cyclization reaction using two different methodologies forming furopyranone derivatives. In the second part of the study, 2-(carboxymethyl)-3-furoic acid was regioselectively converted to acyl azide, which was accomplished by utilizing the reactivity differences between the two acid functionalities within the molecule. This acyl azide was then transformed into urea derivative to perform cyclization reaction yielding a new furan-fused heterocycle, furopyrrolone. In both parts of this study, ring closure reactions were achieved benefiting from the reactivities of different carbonyl groups within the molecules.

Synthesizing nitrogen containing heterocyclic compounds is one of the leading research areas throughout the organic chemistry due to their significant activities on biological systems. Among the various biologically active molecules, indole derivatives are of prime importance on the grounds of their proven clinical roles. Objective of this study is to synthesize new indole derivatives those may contribute treatment of several diseases like their analogues via a recently developed synthetic methodology. Besides this, another objective is to observe and discuss effects of two different substituents on the homophtalic acid system through the synthetic route. Initially starting from homophtalic and 3-methoxybenzoic acid two different homophtalic acid derivatives were synthesized as starting materials. Then the corresponding acyl azide and isocyanate derivatives were generated which might further be used as a precursor to construct a variety of indole derivatives. After synthesizing urea derivatives, ring-closure under the basic conditions generated the heterocyclic units. Whole products were conscientiously purified and characterized.

Universiẗat, Diss., 2003--Freiburg (Breisgau).

Neste trabalho, foi estudada uma rota alternativa para síntese de poliuretanos sem a utilização de isocianatos (NIPU) por um processo de fabricação seguro e utilizando CO2 como insumo. A produção destes poliuretanos \"verdes\" ocorreu através da reação entre ciclocarbonatos e diaminas. A caracterização da estrutura química e a análise dos produtos da reação de formação dos poliuretanos foi possível com a utilização de espectroscopia de infravermelho com transformada de Fourier (FTIR) e espectroscopia de ressonância magnética nuclear (RMN). Foram sintetizados também os ciclocarbonatos pela reação de cicloadição de CO2 ao grupo oxirano de uma resina epóxi e o co-catalisador (resinato de zinco) utilizado na obtenção dos carbonatos cíclicos. Para otimização da formação dos ciclocarbonatos desenvolveu-se um reator de síntese, o qual permitiu a análise do rendimento da reação em função dos parâmetros de síntese controlados: pressão de CO2, temperatura do meio reacional, tempo de síntese, gaseificação da resina epóxi com CO2 (por agitação mecânica ou sistema de refluxo de CO2) e fonte de aquecimento (convencional ou utilizando radiação de microondas). A estrutura química do carbonato obtido, o rendimento e os possíveis subprodutos da reação de cicloadição também foram analisados por FTIR e RMN. / Seeking to optimize the formation of ciclocarbonates, it was developed a reactor in a closed system (no atmospheric emissions of CO2) in which the parameters of synthesis could be controlled: CO2 pressure, temperature of the reaction medium, distribution and concentration of CO2 gas bubbles in epoxy resin. The development of the ciclocarbonate synthesis\'s reactor included new systems to improve the gas-liquid contact between the reactants (aerator and CO2 reflux system) and also a heating system using microwave radiation. It were synthesized in this research, the co-catalyst (zinc resinate), the ciclocarbonate under different conditions of: pressure, temperature, synthesis time, heating source, aeration and catalyst, and \"green\" polyurethanes by an alternative route instead of the use of isocyanates, which have potential in specific applications (control of properties through chemical structure of the polymer). The result of the carbonates formation reaction was analyzed by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (RMN) to obtain the carbonates\'s chemical structure\'s, yield and the reaction\'s by-products. Non-isocyanate polyurethanes (NIPU) were obtained from a manufacturing process and secure using CO2 as an input. The characterization of the chemical structure and the yield and by-product\'s analysis of the polyurethanes formation reaction also happened by FTIR and RMN.