Este trabalho teve como objetivo estudar o processo de plasticização do amido via mistura física e por reação química para a produção de novos materiais. A plasticização via mistura física foi realizada empregando-se como agentes plasticização diferentes compostos hidroxilados. Os amidos termoplásticos (TPS) foram processadas em misturador intensivo a 150°C, a partir de misturas contendo de 15 a 40% de agente plasticizante. A plasticização via reação química foi realizada com isocianatos monofuncionais e difuncionais, os quais levaram a obtenção de produtos de enxertia e entrecruzamento, respectivamente. Os produtos obtidos foram caracterizados por difração de Raios X, Calorimetria Exploratória Diferencial (DSC), Termogravimetria (TG), Análise Dinâmico-Mecânica (DMA), Microscopia Eletrônica de Varredura (SEM) e Cromatografia de Permeação em Gel (HPSEC). O estudo dos diferentes plasticizantes propiciou a determinação das características que estas substâncias devem possuir para a preparação de amidos termoplásticos. O cisalhamento desenvolvido durante o processamento em misturador intensivo levou à perda da estrutura cristalina e à desestruturação dos grânulos de amido. O processamento do TPS em misturador intensivo não provoca mudanças significativas na massa molar do amido termoplasticizado. Os amidos termoplasticizados com sorbitol foram aqueles que apresentaram menores valores de absorção de água. Os valores de módulo de Young das amostras plasticizadas com propilenoglicol aumentaram com o aumento do conteúdo de plasticizante. Para as amostras plasticizadas com etilenoglicol o módulo aumenta até 30% de conteúdo de plasticizante, quando ocorre uma diminuição do valor do módulo. Os TPS plasticizados com propilenoglicol, 1, 4-butanodiol, sorbitol e dietilenoglicol apresentaram um aumento da temperatura de transição vítrea com o aumento do tero de plasticizante. Os diferentes TPS obtidos via mistura física apresentaram estabilidade térmica similares à exibida pelo amido in natura. As propriedades mecânicas destes materiais variaram de acordo com o tipo e a quantidade de plasticizante empregado. A análise dos produtos obtidos via reação química (amidos enxertados e entrecruzados) revelou que estas reações promoveram a desestruturação dos grânulos de amido e, independentemente do regente empregado, a modificação produziu derivados mais hidrofóbicos que o amido in natura. A reação do amido com o oligômero de poli-óxido de propileno tolueno di-isocianato permitiu a obtenção de um derivado com propriedades de material elastomérico e elevada capacidade de intumescimento. Os derivados enxertados ou entrecruzados apresentaram perda de cristalinidade, redução do caráter hidrofílico e estabilidades térmicas semelhantes à apresentada pelo amido in natura. / This main of this work was to study of the cornstarch granules plasticization by means of physical or chemical treatments in order to prepare new materials. The plasticization by physical processing was performed in an intensive mixer at 150°C using ditferent hydroxylated compounds as plasticizers. The production of thermoplastic starch (TPS) by chemical reaction was carried out using mono and di-isocyanates to obtain grafted and cross linked derivatives, respectively. All the products were characterized by X Ray Diffraction, Ditferential Scanning Calorimetry (DSC), Thermogravimetry (TG), Dynamical Mechanical Analysis (DMA), Scanning Electron Microscopy (SEM), High Pressure Size Exclusion Chromatography (HPSEC). The utilization of ditferent plasticizer permitted determining which characteristics the substances must present to be used in the TPS preparation. The shear developed in the processing step lead to the loss of crystalline pattern and disruption of the starch granules. The utilization of intensive mixer does not produce significant changes in the molar mass of the thermoplastic starch. TPS produced using sorbitol as plasticizer presented the lowest level of water uptake. The valous of Young modulus for TPS produced with propylene glycol increased with the content of plasticizer. To samples produced with ethylene glycol the values of Young modulus increased until 30% and after the modulus decrease. TPS prepared with propylene glycol, 1, 4-butanediol, sorbitol and diethyleneglycol showed an increase in the glass transition temperature with the increase in the plasticizer content. The ditferent TPS produced by physical mixture shoed thermal stabilities similar to the one exhibited by in natura starch. The mechanical properties of these materials were dependent of the type and amount of plasticizer. The analysis of the derivatives obtained by chemical reaction (grafted and cross linked) revealed the occurrence of disruption of the starch granules and, independent1y of isocyanate, the products presented higher hydrophobic character than that one presented by in natura starch. By reaction starch with propylene toluene polyoxide oligomer, it was obtained a derivative with elastomeric properties and high swelling capability. The grafted or cross linked derivatives showed loss of crystallinity, decrease in hydrophilic character, and thermal stability similar to the one exhibited by in natura starch.

Cette thèse porte sur la synthèse de polyuréthanes thermoplastiques plus durables à partir de dérivés des huiles végétales. La première voie étudiée est basée sur la réaction, largement utilisée, entre un diol et un diisocyanate. Aussi, pour s’affranchir de l’utilisation des diisocyanates toxiques, une approche via la polyaddition entre un bis carbonate cyclique et une diamine a également été étudiée. Pour ce faire des précurseurs bi-fonctionnels : diols, bis carbonates cycliques à 5 et 6 chainons et diamines ont été préparés à partir de dérivés de l’huile de tournesol (oléate de méthyle) et de l’huile de ricin (undécénoate de méthyle et acide sébacique). Les propriétés thermo-mécaniques des polyuréthanes et poly(hydroxyuréthane)s thermoplastiques obtenus ont pu être ajustées par le choix adapté de la structure chimique des précurseurs (gras) utilisés. Les travaux réalisés démontrent un effet de la taille du cycle du carbonate sur la réactivité. En effet, les (bis) carbonates cycliques à 6 chainons se sont avérés plus réactifs que leurs homologues à 5 chainons. De plus, la synthèse de diamines via un intermédiaire dinitrile semble très prometteuse pour le « design » d’une plateforme de diamines issues d’acides gras et de poly(hydroxyuréthane)s entièrement bio-sourcés. / This thesis aims to synthesize more sustainable thermoplastic polyurethanes from vegetable oil derivatives. The first route that has been investigated is based on the well-known reaction between a diol and a diisocyanate. Then to avoid the use of diisocyanates, the route via the polyaddition of a bis cyclic carbonate and a diamine have been studied as well. For this purpose, bifunctional precursors such as diols, bis 5- and 6-membered cyclic carbonates and diamines have been prepared from sunflower oil derivative (methyl oleate) and castor oil derivatives (methyl undecenoate and sebacic acid) The thermo-mechanical properties of the PUs have been modulated by designing and selecting the chemical structure of the (fatty acid-based) monomers. The performed model reaction kinetics revealed the higher reactivity of the 6-membered cyclic carbonates compare to the 5-membered ones. Finally, the developed route to fatty acid-based diamines via dinitriles synthesis in mild conditions was really efficient and this route is really promising to develop a fatty acid based-diamines platform and fully bio-based poly(hydroxyurethane)s.