Modificações químicas foram aplicadas às fibras celulósicas e ao amido com o objetivo de obter produtos com uma camada termoplástica externa, preservando a parte interna desses substratos (não modificada). O produto final deveria se comportar como um material compósito onde a parte interna não modificada é o agente de reforço e a camada termoplástica a matriz. As modificações foram realizadas através da inserção de pequenas cadeias de óxido propileno a cadeia carbônica do polissacarídeo (celulose e amido). As cadeias de poli(oxido propileno) enxertadas proporcionará uma camada termoplástica em torno da porção de polissacarídeo não modificada. A obtenção destes materiais pode dispensar as etapas de mistura e permitir o processamento térmico sem a necessidade de utilização de um segundo componente (matriz), uma vez que a própria capa polimérica desempenharia este papel. A construção da capa polimérica envolvente foi conduzida através da reação da celulose ou amido pré-ativados com o óxido de propileno. A etapa de ativação foi realizada com o tratamento dos substratos com KOH ou DABCO e a reação de enxertia foi realizada em sistema heterogêneo. Os materiais obtidos utilizando esses tratamentos foram caracterizados por diferentes técnicas (FTIR, Raios-X, MEV, TG, DSC, Ângulo de contato e ensaios de Resistência à Tração). Os resultados obtidos demonstraram que é possível de produzir materiais com características termoplásticas reforçadas através da reação em uma única etapa, sem a necessidade de laboriosos procedimentos sintéticos. / Chemical modifications were applied to cellulosic materials and starch with the objective to obtain products with an external thermoplastic layer while preserving the inner part of these substrates. The final products should behave as composite materials where the unmodified inner part is the reinforcement agent and the thermoplastic layer the matrix. The modifications were performed by grafting polypropylene oxide short chains to the polysaccharide backbone (cellulose and starch). The grafted polypropylene oxide chains will render a thermoplastic layer around the unmodified polysaccharide portions. The attainment of these materials can excuse the stages of mixture and allow the thermal processing without the necessity of use the second component (matriz), a time that the proper polymeric layer would play this role. The construction of the involving polymeric layer was conducted by reacting pre-activated cellulose (or starch) and propylene oxide (PO). The activation step was performed with KOH (or DABCO) treatment and the grafting reaction was carried through in heterogeneous system. The materials obtained following these treatments were characterized by different techniques (FTIR, X-Ray, MEV, TG, DSC, Contact Angle and Mechanical Analyses). The results had demonstrated that it is possible to produce materials with strengthened thermoplastic characteristics through the reaction in an only stage, without the necessity of laborious synthetic procedures.

Dans ce travail, la lignine extraite de la liqueur noire a été d'abord caractérisée et ensuite valorisé selon deux approches différentes: (i) une utilisation après une modification chimique pour la synthèse des mousses de polyuréthane et (ii) une pyrolyse simple pour fabriquer le charbon. En effet, une étude comparative concernant la caractérisation des fonctions hydroxyl a été réalisée en utilisant plusieurs méthodes et techniques, notamment, la titration et la spectroscopie RMN du 13C. Dans la première approche, la lignine a été convertie en polyols liquides grâce à une réaction d'extension de chaîne avec l'oxyde de propylène (oxypropylation). Les formulations des polyols ont été optimisées, en inspectant l'effet de différents paramètres : lignine/oxyde de propylène, le taux de catalyseur, la masse moléculaire, l'indice d'hydroxyle, la viscosité et la température de transition vitreuse. Les indices d'hydroxyles et la viscosité des polyols produits ont été caractérisés. Les mousses rigides de polyuréthane ont été évaluées en termes de densité, de morphologie et de propriétés mécaniques. La lignine a ensuite été utilisée comme précurseur de charbon sans aucun traitement d'activation et a été comparée avec le charbon commercial. Une étude cinétique d'adsorption a été réalisée et montré que l'équilibre d'adsorption est atteint au bout de 50 min, en suivant un modèle de pseudo-premier ordre. L'étude des isothermes d'adsorption a révélé que le CL retient efficacement les ions métalliques, et présente une capacité d'adsorption maximale entre 200 et 400 µmol/g pour des concentrations très inférieure à 20ppm. Le charbon obtenu après saturation en ions métalliques, a été régénéré efficacement par lavage avec une solution d'EDTA ou une solution d'acide nitrique.De plus, les deux approches d'utilisation de la lignine extraite de la liqueur noire d'alfa ont donnée des matériaux avec des propriétés prometteuses. Dans la majorité des cas, des matériaux avec des propriétés similaires à celles des matériaux conventionnels, ce qui présente une option viable d'une valorisation rationnelle de déchet industriel abondant et provenant d'une source renouvelable. / Lignin precipitated from black liquor of alfa (Stipa tenacissima) soda cooking before being carefully characterized and valorized following two different approaches: (i) its utilization after chemical modification in view of preparing rigid polyurethane foams; and (ii) its simple pyrolysis simple, in order to prepare charcoal. In fact, a comparative study concerning the careful characterization of the hydroxyl functions was realized using several methods and techniques, namely: the conductimetric titration and 13C-NMR spectroscopy. In the first approach, the precipitated lignin was converted in liquid polyols thanks to a chain-extension reaction with propylene oxide. These formulations were optimized by inspecting the effect of different parameters: lignin/propylene oxide ratio, the amount of catalyst, the molecular weight of the prepared polyols, the hydroxyl index and the glass transition temperature. The hydroxyl indexes and the viscosity of the prepared polyols were determined. The rigid polyurethane foams were studied in terms of their density, morphology and mechanical properties. The lignin was then used as a precursor for the preparation of charcoal without any activation treatment and compared with commercial homologue. The kinetic of the adsorption was performed and showed that the adsorption equilibrium is reached at about 50 min, and followed a pseudo-first order kinetic model. The adsorption isotherms revealed that lignin-based charcoal retained efficiently the metallic ions and presented a maximum adsorption capacity varying from 200 to 400 µmol/g. This is true even for concentrations much lower than 20 ppm. Le saturated lignin-based charcoal was efficiently regenerated by washing with solutions of EDTA or a nitric acid.The two approaches of the valorization of lignin precipitated from black liquor gave materials with promising properties. Thus, in the majority of cases, materials with properties similar to conventional ones were obtained, which presents a viable option of rational valorization of this industrial abundant and renewable by-product.

Modificações químicas foram aplicadas às fibras celulósicas e ao amido com o objetivo de obter produtos com uma camada termoplástica externa, preservando a parte interna desses substratos (não modificada). O produto final deveria se comportar como um material compósito onde a parte interna não modificada é o agente de reforço e a camada termoplástica a matriz. As modificações foram realizadas através da inserção de pequenas cadeias de óxido propileno a cadeia carbônica do polissacarídeo (celulose e amido). As cadeias de poli(oxido propileno) enxertadas proporcionará uma camada termoplástica em torno da porção de polissacarídeo não modificada. A obtenção destes materiais pode dispensar as etapas de mistura e permitir o processamento térmico sem a necessidade de utilização de um segundo componente (matriz), uma vez que a própria capa polimérica desempenharia este papel. A construção da capa polimérica envolvente foi conduzida através da reação da celulose ou amido pré-ativados com o óxido de propileno. A etapa de ativação foi realizada com o tratamento dos substratos com KOH ou DABCO e a reação de enxertia foi realizada em sistema heterogêneo. Os materiais obtidos utilizando esses tratamentos foram caracterizados por diferentes técnicas (FTIR, Raios-X, MEV, TG, DSC, Ângulo de contato e ensaios de Resistência à Tração). Os resultados obtidos demonstraram que é possível de produzir materiais com características termoplásticas reforçadas através da reação em uma única etapa, sem a necessidade de laboriosos procedimentos sintéticos. / Chemical modifications were applied to cellulosic materials and starch with the objective to obtain products with an external thermoplastic layer while preserving the inner part of these substrates. The final products should behave as composite materials where the unmodified inner part is the reinforcement agent and the thermoplastic layer the matrix. The modifications were performed by grafting polypropylene oxide short chains to the polysaccharide backbone (cellulose and starch). The grafted polypropylene oxide chains will render a thermoplastic layer around the unmodified polysaccharide portions. The attainment of these materials can excuse the stages of mixture and allow the thermal processing without the necessity of use the second component (matriz), a time that the proper polymeric layer would play this role. The construction of the involving polymeric layer was conducted by reacting pre-activated cellulose (or starch) and propylene oxide (PO). The activation step was performed with KOH (or DABCO) treatment and the grafting reaction was carried through in heterogeneous system. The materials obtained following these treatments were characterized by different techniques (FTIR, X-Ray, MEV, TG, DSC, Contact Angle and Mechanical Analyses). The results had demonstrated that it is possible to produce materials with strengthened thermoplastic characteristics through the reaction in an only stage, without the necessity of laborious synthetic procedures.