Grâce aux développements des méthodes de synthèse et de caractérisation, les nanomatériaux constituent un champ d'investigation de plus en plus actif et attractif. Cette thèse s'attache à étudier un procédé de synthèse de nanoparticules d’oxyde de zinc par voie polyol. Ce procédé a l’avantage de fournir une large variété morphologique de particules présentant une bonne qualité cristalline. Dans cette thèse, nous montrons qu’en variant les paramètres de synthèse nous pouvons moduler la taille, la distribution de taille et la morphologie des nanoparticules pour les obtenir en forme de nanosphères aussi fines que 6 nm ou des nanofils aussi longs que600 nm. Notre étude systémique a porté sur un ensemble de paramètres qui contrôlent la réaction d’hydrolyse forcée incluant la stoechiométrie, la température, la nature du polyol mais également l’agitation, l’injection des réactifs et l’activation par ultra sons du milieu. Nous montrons que la forme des nanoparticules est déterminée par la compétition entre les réactions de croissance de différentes faces du cristal d’oxyde de zinc. Notre étude a permis aussi de comparer différents dispositifs de mélange comme le réacteur du laboratoire, le T de mélange et les jets libres. Par ailleurs, pour produire en masse ces nano objets nous avons développé une stratégie originale pour comprendre l’effet du mélange sur la taille des nanoparticules. Notre approche s’appuie sur la résolution numérique des équations de Navier-Stokes et la corrélation entre les profils d’énergie turbulente dissipée et la taille des nanoparticules mesurée expérimentalement. L’application au cas spécifique de l’oxyde de zinc nous a permis de produire jusqu’à ~50 g de nanoparticules par Batch. Ces nanoparticules ont par la suite été incorporées comme matériau semi conducteur dans des cellules photovoltaïques à colorant préparées à l’École Nationale Supérieure de Chimie de Paris. En effet, la richesse morphologique de ZnO obtenu par voie polyol laisse présager une bonne adsorption du colorant à sa surface. Nos résultats montrent que les rendements de photoconversion dépendent aussi bien de la morphologie que de la taille. Les meilleures cellules élaborées dans cette thèse ont un rendement qui avoisine 5.3 %. / Thanks to developments in synthesis methods and characterization techniques, nanomaterials research field is increasingly active and attractive. This thesis aims to investigate the polyol process for zinc oxide nanoparticles synthesis. Indeed, this method has the advantage of providing a wide variety of particle morphology with a good crystalline quality. In this thesis, we show that by varying the synthesis conditions we can adjust the size, the size distribution and the morphology of nanoparticles to obtain either shaped nanospheres as small as 6 nm or nanowires as long as 600 nm. Our systemic study focused on a set of parameters that control the forced hydrolysis reaction including stoichiometry, temperature, nature of the polyol but also mixing, injection of reagents and ultrasound activation. We show that the shape of the nanoparticles is determined by the competition between growth rates of different zinc oxide crystal facets. Our study also compared different mixing devices such as laboratory reactor, T- mixer and impinging jets. More over, to mass produce zinc oxide nanoparticles, we developed an original strategy to understand the effect of mixing on nanoparticle size. In our approach, we correlate the turbulent energy dissipated as obtained from Computation Fluid Dynamics with theme asured nanoparticle size. The application to the specific case of zinc oxide has allowed us to produce sample aliquots of ~50 g per Batch. These nanoparticles were subsequently incorporated into dye-sensitized solar cells as semi conducting material at the École Nationale Supérieure de Chimie de Paris. Indeed, the morphological richness of the zinc oxide produced via polyol process suggests good adsorption of the dye on their surfaces. Our results show that the photoconversion efficiencies depend both on the morphology and the size. Our best photoconversion efficiency approaches 5.3%.

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O poliuretano (PU) representa um dos grupos mais importantes de polímeros, com uma grande variedade de tipos e alta versatilidade de aplicações. É uma classe de polímeros na qual as unidades formadoras da cadeia polimérica são interligadas por ligações uretânicas, -O(CO)(NH)- . As macromoléculas são formadas pela reação de pré-polímeros contendo grupos terminais hidroxila com di-isocianatos. Quando excesso de diisocianato é empregado, a macromolécula resultante terá, em suas extremidades, grupos isocianato que podem então reagir com diferentes dióis poliméricos para extender adicionalmente as cadeias, ou com trióis para formar ligações cruzadas (Allcock et al., 2003). Devido a alta versatilidade do poliuretano e por ser o principal componente de produtos de alto consumo como colchões e geladeiras, o volume de resíduo de PU gerado é cada vez maior e por se tratar de um termo-fixo sua reciclagem não é um processo simples. O objetivo do presente trabalho é analisar os efeitos do uso de um poliol reciclado através de um processo de glicólise especifico nas propriedades mecânicas de uma espuma rígida de poliuretano. Diversos métodos de glicólise foram analisados da literatura e com base nas informações encontradas uma rota ótima foi proposta/escolhida. O produto gerado foi então caracterizado e utilizado em diferentes proporções em substituição ao poliol base em formulações padrão de espumas rígidas de poliuretano, de forma que os efeitos da adição do mesmo sobre as características finais relevantes da espuma pudessem ser observadas. O processo de reciclagem apresentado no presente estudo mostrou-se um processo efetivo no tratamento de resíduos industriais de espuma de poliuretano rígido, uma vez que o processo é rápido, de custo relativamente baixo e produz um produto final de qualidade comparável ao dos produtos virgens existentes no mercado. A funcionalidade e número de OH superiores do poliol recuperado trazem inclusive melhorias na estrutura mecânica da espuma final obtida a partir do uso do mesmo. A presença de impurezas advindas de reações secundárias mostraram sua influência na alteração da reatividade da reação de formação da espuma de poliuretano, porém este fato pôde ser ajustado através de alterações no nível de catalisadores adicionados a formulação. / The polyurethane (PU) represents one of the most important groups of polymers, with very versatile types and applications. It is a class of polymers in which the polymeric chain components are linked by uretanic linkages, -O(CO)(NH)-. The macromolecules are formed by the reaction of pre-polymers containg hydroxyl end groups with di- isocyanates. When excess of Isocyanate is used, the resulting macromolecule will have, in its edges, isocyanate groups that can react with different polymeric diols to extent additionally the chains, or with triols to form cross-linked polymers. (Allcock et al., 2003) The unlimited nature of the components A and B plus the several applications makes the PU one of the most versatile plastics. Due to its high versatility and for being the main component in mass consumption products like refrigerators and mattresses, the volume of PU residues generated is each time higher and once it is a thermoset its recycling methods are not easy. The objective of the present work is analyzing the effects of the use of a recycled polyol obtained through a specific glycolysis process in the mechanical properties of rigid PU foam. Different glycolysis methods were analyzed from previous art and an ideal route was established. The recycled polyol was characterized and used in different proportions in substitution of the conventional polyol in standard formulations for rigid foam production, thus the effects of this substitution could be observed. The proposed recycling process showed to be very effective in the recovering of polyols from PU rigid foam residues, once the process is fast, relatively low cost and produces a final product with equivalent quality of a conventional polyol. The higher functionality and OH number of the recovered polyol brings to the final foam superior mechanical properties. The presence of secondary products like primary amines generated in the process could be noticed by the increase in the reactivity of the formulations using the recycled polyol, although this fact was proved to be manageable through adjustments in the aminic catalyst add to the formulations.

O poliuretano (PU) representa um dos grupos mais importantes de polímeros, com uma grande variedade de tipos e alta versatilidade de aplicações. É uma classe de polímeros na qual as unidades formadoras da cadeia polimérica são interligadas por ligações uretânicas, -O(CO)(NH)- . As macromoléculas são formadas pela reação de pré-polímeros contendo grupos terminais hidroxila com di-isocianatos. Quando excesso de diisocianato é empregado, a macromolécula resultante terá, em suas extremidades, grupos isocianato que podem então reagir com diferentes dióis poliméricos para extender adicionalmente as cadeias, ou com trióis para formar ligações cruzadas (Allcock et al., 2003). Devido a alta versatilidade do poliuretano e por ser o principal componente de produtos de alto consumo como colchões e geladeiras, o volume de resíduo de PU gerado é cada vez maior e por se tratar de um termo-fixo sua reciclagem não é um processo simples. O objetivo do presente trabalho é analisar os efeitos do uso de um poliol reciclado através de um processo de glicólise especifico nas propriedades mecânicas de uma espuma rígida de poliuretano. Diversos métodos de glicólise foram analisados da literatura e com base nas informações encontradas uma rota ótima foi proposta/escolhida. O produto gerado foi então caracterizado e utilizado em diferentes proporções em substituição ao poliol base em formulações padrão de espumas rígidas de poliuretano, de forma que os efeitos da adição do mesmo sobre as características finais relevantes da espuma pudessem ser observadas. O processo de reciclagem apresentado no presente estudo mostrou-se um processo efetivo no tratamento de resíduos industriais de espuma de poliuretano rígido, uma vez que o processo é rápido, de custo relativamente baixo e produz um produto final de qualidade comparável ao dos produtos virgens existentes no mercado. A funcionalidade e número de OH superiores do poliol recuperado trazem inclusive melhorias na estrutura mecânica da espuma final obtida a partir do uso do mesmo. A presença de impurezas advindas de reações secundárias mostraram sua influência na alteração da reatividade da reação de formação da espuma de poliuretano, porém este fato pôde ser ajustado através de alterações no nível de catalisadores adicionados a formulação. / The polyurethane (PU) represents one of the most important groups of polymers, with very versatile types and applications. It is a class of polymers in which the polymeric chain components are linked by uretanic linkages, -O(CO)(NH)-. The macromolecules are formed by the reaction of pre-polymers containg hydroxyl end groups with di- isocyanates. When excess of Isocyanate is used, the resulting macromolecule will have, in its edges, isocyanate groups that can react with different polymeric diols to extent additionally the chains, or with triols to form cross-linked polymers. (Allcock et al., 2003) The unlimited nature of the components A and B plus the several applications makes the PU one of the most versatile plastics. Due to its high versatility and for being the main component in mass consumption products like refrigerators and mattresses, the volume of PU residues generated is each time higher and once it is a thermoset its recycling methods are not easy. The objective of the present work is analyzing the effects of the use of a recycled polyol obtained through a specific glycolysis process in the mechanical properties of rigid PU foam. Different glycolysis methods were analyzed from previous art and an ideal route was established. The recycled polyol was characterized and used in different proportions in substitution of the conventional polyol in standard formulations for rigid foam production, thus the effects of this substitution could be observed. The proposed recycling process showed to be very effective in the recovering of polyols from PU rigid foam residues, once the process is fast, relatively low cost and produces a final product with equivalent quality of a conventional polyol. The higher functionality and OH number of the recovered polyol brings to the final foam superior mechanical properties. The presence of secondary products like primary amines generated in the process could be noticed by the increase in the reactivity of the formulations using the recycled polyol, although this fact was proved to be manageable through adjustments in the aminic catalyst add to the formulations.

Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-06-28T19:58:26Z No. of bitstreams: 1 FICHA_CATALOGR?FICA_EMBUTIDA_Disserta??o Cristiano_Jaeger Stradolini_Processo Poliol.pdf: 3080490 bytes, checksum: 6539be3aad396dd1f8b30cd3389b1469 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-07-06T13:07:04Z (GMT) No. of bitstreams: 1 FICHA_CATALOGR?FICA_EMBUTIDA_Disserta??o Cristiano_Jaeger Stradolini_Processo Poliol.pdf: 3080490 bytes, checksum: 6539be3aad396dd1f8b30cd3389b1469 (MD5) / Made available in DSpace on 2018-07-06T13:12:44Z (GMT). No. of bitstreams: 1 FICHA_CATALOGR?FICA_EMBUTIDA_Disserta??o Cristiano_Jaeger Stradolini_Processo Poliol.pdf: 3080490 bytes, checksum: 6539be3aad396dd1f8b30cd3389b1469 (MD5) Previous issue date: 2018-03-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / During the past few years, nanosized noble metals have attracted much attention due to their unique electrical and physical properties. Among them, silver has been the subject of several studies, by having the highest electrical and thermal conductivity between all metals. For that reason, its one-dimensional nanometric structure (nanowires) has been receiving a lot of attention, due to its potential in the manufacture of devices that offer good electrical conduction and optical transparency. There are several methods of synthesis for the production of these silver nanowires, however the most widely used is the polyol process, due to its simplicity and low cost. Several studies show the influence of different parameters of the polyol process (reaction time, temperature and etc.) on the final morphology of the nanowires. Thus, a well-defined protocol of good practice for obtaining long and thin silver nanowires is required. The main objective of this work is the development of a low cost protocol capable of generating nanowires with great lengths by modifying the polyol process parameters. Variations were also performed in the method of addition of the main synthesis reagent, silver nitrate, and its influence on the final morphology of the silver nanowires was studied. In this work, by using the polyol process, nanowires up to 40 ?m in length were reported, demonstrating the effectiveness of the developed technique and conclusions about the final results were presented. / Ao decorrer dos ?ltimos anos, metais nobres na escala nanom?trica t?m atra?do muita aten??o, devido as suas propriedades el?tricas e f?sicas ?nicas. Dentre eles, a prata vem sendo alvo de diversos estudos, por possuir a maior condutividade el?trica e t?rmica entre todos os metais. Por conta disto, sua estrutura nanom?trica unidimensional (nanofios) vem recebendo muita aten??o, pelo seu potencial na fabrica??o de dispositivos que exijam alta condutividade el?trica e transpar?ncia ?ptica. Atualmente, existem diversos m?todos de s?nteses para a produ??o destes nanofios de prata, por?m o mais utilizado ? o processo poliol, por ser simples e de baixo custo. Diversos estudos demonstram a influ?ncia de diferentes par?metros do processo poliol (tempo de rea??o, temperatura e etc.) sobre a morfologia final dos nanofios. Assim, se faz necess?rio um protocolo bem definido de boas pr?ticas para a obten??o de fios longos e finos. O principal objetivo deste trabalho ? o desenvolvimento de um protocolo de baixo custo capaz de gerar nanofios com grandes comprimentos, atrav?s de altera??es nas vari?veis do processo poliol, como, por exemplo, varia??es no m?todo de adi??o do principal reagente da s?ntese, o nitrato de prata. Foi estudada a sua influ?ncia na morfologia final dos nanofios. Neste trabalho, os resultados finais apresentaram que nanofios de at? 40 ?m de comprimento foram produzidos pelo processo poliol, demonstrando a efic?cia da t?cnica desenvolvida e foram apresentadas as conclus?es acerca dos resultados atingidos.

O grafeno, material com duas dimensões (2D), formado por átomos de carbono hibridizados em sp2, tem atraído muita atenção da comunidade científica devido às propriedades elétricas, térmicas e mecânicas excepcionais que este material apresenta. Nanopartículas (NPs) de metais e de óxidos metálicos têm sido incorporadas sobre a estrutura do grafeno com o objetivo de obter materiais compósitos. Este trabalho teve por objetivo principal desenvolver uma nova rota para a preparação de compósitos de grafeno/NPs metálicas e de óxidos metálicos pelo método do poliol modificado, em etapa única. O óxido de grafeno (GO) foi sintetizado pelo método Hummers modificado e reduzido e esfoliado pelo processo pioliol modificado para obtenção do grafeno. Ajustou-se a metodologia proposta para que o GO obtido pudesse ser utilizado diretamente no meio reacional do processo poliol sem a necessidade de secagem e redispersão. Foram testadas diversas condições de síntese do grafeno variando-se a presença e tipo de surfactante, o solvente e diferentes condições de aquecimento. As variações de síntese permitiram observar que a presença do surfactante oleilamina aumenta a capacidade redutora do sistema e inibe a formação de outras estruturas de carbono além do grafeno e taxas de aquecimento menores favorecem a formação de grafeno em detrimento destas outras estruturas, enquanto patamares de temperatura intermediários levam à formação dessas estruturas secundárias de carbono. As sínteses foram também adaptadas para a obtenção de compósitos de grafeno/NPs de FePt e Fe3O4. Estas sínteses foram realizadas de duas maneiras: com os precursores metálicos e o GO presentes no balão desde o início da síntese e com os precursores metálicos presentes no balão desde o início da síntese e hot injection do GO. Para os compósitos, as sínteses realizadas em benzil éter (BE) favoreceram a formação de partículas. Para os compósitos de grafeno/NPs de Fe3O4, observou-se que a quantidade de precursor de Fe é crucial para a formação das NPs. Os resultados indicaram que a metodologia empregada foi muito eficiente para produção de grafeno e de compósitos de grafeno/NPs em etapa única e o processo poliol se mostrou muito versátil, de maneira que os resultados obtidos indicam que é possível obter compósitos de grafeno com qualquer sistema de NPs que venham a ser sintetizadas pelo processo poliol, apenas pelo ajuste das condições de síntese, em etapa única. / Graphene, a two dimensional material, composed only by sp2 hybridized carbon atoms, have attracted much attention of the scientific comunity due to the exceptional electrical, thermal and mechanical properties this material presents. Metallic and metal oxide nanoparticles (NPs) have been incorporated over graphene structure in order to obtain composite materials. The main goal of this work was to develop a new synthetic route to obtain graphene and metallic and metal oxide NPs composites, in one step. Graphene oxide (GO) was sinthesized by the modified Hummers method and exfoliated and reduced by the modified polyol process to obtain graphene. The proposed methodology was adjusted for the obtained GO to be used directly in the polyol process reactional means, not being necessary to dry and to redisperse the material. Several synthesis conditions were tested to obtain graphene, varying the presence of the surfactant and its type, solvent and heating rates. The synthesis diversity let us observe that the presence of oleylamine improved the reducing capacity of the system and it inhibited other carbon structures formation besides graphene. Also, smaller heating rates favor graphene formation to the detriment of these other structures, whereas intermediate temperature plateaus lead to the formation of carbon secondary structures. The synthesis were also adapted in order to obtain graphene/NPs of FePt and Fe3O4 composites. These synthesis were performed in two ways: both metallic precursors and GO present in the flask since the begining of the synthesys and only methalic precursors present in the flask since the begining of the synthsys, with a GO hot injection. Regarding the composites, synthesis performed in benzyl ether (BE) favor the particles formation. And specifically on the graphene/NPs of Fe3O4 composites, it was observed that Fe precursor quantity is decisive on the NPs formation. The results indicated that the employed methodology was very efficient to produce graphene and graphene/NPs composites in one step. And the polyol process proved to be very versatile, thereby the obtained results indicate it\'s possible to obtain graphene/NPs composites, in one step, with any NPs system that can be synthesized by the polyol process, only by adjusting the synthesis condition.

High-protein nutrition (HPN) bars (≥ 30% protein) have limited shelf life and become excessively hard during storage. Various mechanisms have been proposed to explain the hardening. The objectives of this research were to investigate the chemistry of HPN bar hardening and propose solutions for slowing it and improving bar texture. In phase 1, HPN bars were made containing 34% whey protein isolate (WPI) or milk protein concentrate (MPC) powder, along with either sorbitol syrup or glycerol, and vegetable shortening or cocoa butter. Substituting MPC for WPI made the bars brittle and crumbly. Using glycerol initially made bars softer but accelerated hardening. Cocoa butter increased bar hardness because of its higher solid to liquid content. Most water (~99%) in HPN bars made using sorbitol syrup is present as bound water, with ~0.9% as intermediate water and ~0.1% as bulk water. During storage bound water increased ~0.02 g/100 g of solids while intermediate water decreased, suggesting changes in state of water taking place at protein surfaces. During storage, there were changes in protein conformation indicated by an increase (~4°C) in heat denaturation temperature of β-lactoglobulin and α-lactalbumin and a 15 to 40% decrease in denaturation enthalpy. In phase 2, various bar formulations were tested involving different proportions of proteins, lactose, glycerol, and sorbitol syrup, as well as type of lipid component, and disulfide bonds inhibition. Decreases in bar hardening occurred when MPC and WPI and sorbitol syrup and glycerol were used in combination. In phase 3, HPN bars made with 38% protein powder as a 50:50 combinations of WPI and MPC and with 20% of sorbitol syrup substituted with glycerol, had good texture and minimal hardening during storage. Bar hardening was not caused by phase separation of protein and sorbitol, Maillard browning, or formation of inter-molecular disulfide bonds. Minimizing bar hardening requires prevention of entropy-induced protein aggregation by masking hydrophobic regions on protein surfaces and preventing formation of extended protein networks. It is proposed that preferential exclusion of cosolvents causes glycerol to be oriented at protein surfaces such that its carbon backbone masks hydrophobic regions thus avoiding a decrease in entropy of water molecules. (229 pages)

There are many diverse classes of biologically active natural products containing chiral 1,5- or 1,5,7-polyol moieties, including the novel fibrinogen receptor antagonist tetrafibricin, a potential antiplatelet therapeutic drug to treat various arterial thrombotic diseases. There have been some elegant synthetic strategies developed to synthesize these challenging 1,5-diol motifs; however, many of them suffer from a variety of inherent limitations. To overcome many of these challenges, our group has developed an iterative configuration-encoded strategy to access 1,5-polyols with unambiguous stereocontrol by exploiting Julia–Kocienski couplings of enantiopure α-siloxy-γ-sulfononitrile building blocks with alcohol stereocenters previously established via asymmetric catalysis. Our method is a strategy level innovation that allows for the efficient and rapid access to all stereoisomers of a 1,5-polyol family from cheap and easily accessible reagents, without the need to determine the configuration of each alcohol stereocenter in the growing polyol chain. We were able to modify our configuration-encoded 1,5-polyol methodology to access the anti,syn-1,5,7-triol within the C15–C25 fragment of tetrafibricin with excellent selectivity by incorporating differentiable protection and merging this approach with the tactic of diastereoselective intramolecular conjugate addition via benzylidene acetal construction to access the syn-1,3-diol functionality. We also applied our iterative configuration-encoded strategy to the synthesis of the 1,5-polyol-containing C26–C40 fragment of tetrafibricin with excellent stereoselectivity by modifying our previous route to the C27–C40 segment. By overcoming the challenges associated with the reduction of α-siloxynitriles and extending the carbon chain to alter the subsequent Mukaiyama aldol coupling location, we were able to furnish the C26–C40 fragment with the correct protection and functionality for further coupling to the C15–C25 segment. With the C15–C25 and C26–C40 fragments in hand, we joined these segments via asymmetric BF3⋅OEt2-mediated Mukaiyama aldol construction with high 1,3-anti stereoinduction. We determined the preceding stereoselectivity by first using the simplified model C26–C40 fragment and found that replacing the TBDPS with TBS protection of the β-siloxy aldehyde increased the level of 1,3-anti induction. To complete the C15–C40 fragment of tetrafibricin, we performed an intramolecular hydroxyl-directed anti-reduction to furnish the desired anti,anti,anti-1,3,5,7-tetraol moiety. We were able to establish the configurations of these chiral alcohols using a battery of 2D NMR experiments. Finally, to complete the total synthesis of tetrafibricin, we have proposed a route to couple our C15–C40 fragment with the C8–C14 segment via a precedented asymmetric aldol reaction, followed by coupling to the known C1–C7 polyene fragment. With minor functional group transformations and a global deprotection, access to the natural product tetrafibricin should be achievable.