Neste estudo foi investigada a alcoólise enzimática do óleo de soja com etanol, utilizando t-butanol como solvente e enzimas imobilizadas Lipozyme TL IM, Lipozyme RM IM e Novozym 435 como catalisadores. As reações foram realizadas em um reator batelada fechado acoplado a um condensador e com constante agitação. Foram avaliadas a influência do t-butanol, do tipo de enzima utilizada, da razão molar álcool/óleo e da temperatura no rendimento em biodiesel. A etanólise do óleo de soja por sucessivas adições de álcool foi investigada e as melhores condições foram obtidas em presença de t-butanol, razão molar etanol/óleo igual a 3, temperatura de 50C e 5% (m/m) de Novozym 435. Nas reações conduzidas em presença de t-butanol não foram observadas diferenças significativas entre a adição direta e a escalonada do álcool. Os efeitos da adição de álcool só foram observados na ausência de t-butanol. O rendimento máximo em ésteres etílicos atingido foi cerca de 66% após 4h de reação com Novozym 435 na presença de solvente. / In this research, the enzymatic alcoholysis of soybean oil was investigated by using commercial immobilized lipases: Lipozyme TL IM, Lipozyme RM IM and Novozym 435 as catalysts. The reactions were carried out in a closed batch reactor with constant stirring and coupled with condenser. The influence of t-butanol, type of enzyme, molar ratio (alcohol/soybean oil) and temperature on biodiesel yield were evaluated. The ethanolysis of soybean oil by stepwise additions of ethanol was also investigated. The best conditions were obtained in t-butanol presence with ethanol/oil molar ratio of 3, temperature of 50oC and 5 wt.% Novozym 435. For the reactions carried out with t-butanol, the effects of stepwise alcohol addition were not observed, but it was realized in t-butanol absence. The maximum biodiesel yield achieved was 66% after 4h of reaction with Novozym 435 in t-butanol system.

Neste trabalho, foi investigada a alcoólise do óleo de soja com álcool utilizando uma lipase comercial imobilizada (Lipozyme RM IM). As reações foram realizadas em um reator batelada fechado acoplado a um condensador e com constante agitação. Foi determinada a influência do álcool (metanol ou etanol), quantidade de enzima, razão molar álcool/óleo de soja, solvente e temperatura na produção de biodiesel. A etanólise do óleo de soja por sucessivas adições de álcool foi investigada. As melhores condições foram obtidas em um sistema livre de solvente com razão molar etanol/óleo igual a 3,0, temperatura de 50C e concentração de enzima de 7% em massa. A etanólise em batelada com 3 adições sucessivas foi a mais eficiente para a produção de biodiesel. Nessas condições, o rendimento em ésteres etílicos foi cerca de 55% após 2h de reação. A alcoólise de óleo de soja com metanol e etanol também foi estudada com KOH. O efeito do álcool (metanol ou etanol), concentração do catalisador e razão molar entre álcool e óleo de soja foi determinada. O maior rendimento (92%) na alcoólise do óleo de soja com KOH foi obtido com metanol / In this work, enzymatic alcoholysis of soybean oil with alcohol was investigated using a commercial immobilized lipase (Lipozyme RM IM). Reactions were carried out in a closed batch reactor with constant stirring and coupled with condenser. The influence of alcohol (methanol or ethanol), enzyme amount, molar ratio of alcohol to soybean oil, solvent (n-hexane) and temperature on biodiesel production was determined. The ethanolysis of soybean oil by successive additions of ethanol was also investigated. The best conditions were obtained in a solvent-free system with ethanol/oil molar ratio of 3.0, temperature of 50oC and enzyme concentration of 7.0% (w/w). Three-step batch ethanolysis was most effective for the production of biodiesel. In these conditions, ethyl esters yield was about 55% after 2 hours of reaction. Alcoholysis of soybean oil with methanol and ethanol were also investigated using KOH. The effects of alcohol (methanol or ethanol), catalyst concentration and molar ratio of alcohol to soybean oil was determined. The highest yield (92%) in the alcoholysis of soybean oil using KOH was obtained with methanol

M.Sc. / Lewis acids play an important role in catalysis; they are associated with mild conditions, high selectivities and unique reactivities. Traditional Lewis acids such as AlCb and BF3 successfully catalyse such well known reactions as the Friedel-Crafts acylation reaction, Aldol condensation reactions and many more. These catalysts, however, must be used in a stoichiometric amount and are destroyed during the aqueous workup procedures. Lately, there has been a lot of interest in the role of metal triflate as Lewis acid catalysts. They were found to be effective in a wide range of reactions when used in catalytic amounts. They were also found to be recyclable and reusable without the loss of activity. Most of this research has been centred around the lanthanide triflates as well as scandium, bismuth and yttrium triflates. Very little research has been done using aluminium triflate and this triflate forms the focus ofthis study. The work contained in this dissertation demonstrates that Al(OTf)3 is an efficient catalyst for the ring opening of a variety of epoxides by alcohols when present in only ppm amounts. These reactions provided products in very high yields and selectivities. Simple acyclic and cyclic epoxides readily underwent ring opening reactions with a range of alcohols, typically providing the monoglycol ethers as single compounds (from the cyclic epoxides) or as mixtures of the two possible glycol monoethers (from the acyclic epoxides). In the case of styrene oxide, essentially a single compound was isolated. In contrast, the glycidyl ethers required slightly higher catalyst loadings before similar rates and conversions to product were observed. Additionally, an interesting selectivity was observed in the orientation of the attack of the alcohol onto the epoxide, which appeared to be chelation controlled. Similarly, the Al(OTf)3 also catalysed the aminolysis of a variety of epoxides. These reactions proceeded smoothly with catalytic amounts of the triflate present, and served to nicely highlight the role that steric and electronic factors played in these reactions. A preliminary study was carried out into the efficacy of Al(OTf)3 as a catalyst for Friedel-Crafts acylation and aromatic nitration reactions. From these studies it is evident that the Al(OTf)3 is indeed an effective catalyst for these reactions when present in substoichiometric levels and further studies will be carried out in this area in the future.

This diploma thesis deals with chemical recyclation polylactide to lactide. In the theory is summarized actual state of knowledge about chemical recyclation of polylactides, their properties, preparations a possibilities of characterization. Experimental part of work verify ethanolysis of PLA withthe samples of granulate, waste filaments and textiles. In the experimental work is suggested an optimalization of alcoholysis to direct yield of oligomer suitable for depolymerization to lactide. This method was verified for 5 different samples of PLA, which 4 of them was made of waste PLA. The time needed for depolymerization was evaluated and the effect of catalysis. Lactide and PLA recyclates was further analyzed by NMR, FTIR, DSC and GPC.

Este estudo enfocou a mediação por íons metálicos divalentes da solvólise da ligação éster formada entre peptídeos e resinas, método desenvolvido por nós para a preparação de peptídeos C-modificados. Os objetivos foram: i) adaptá-lo para a estratégia Fmoc de síntese, ii) buscar resinas adequadas para tal propósito, iii) verificar qual íon metálico é mais eficiente para mediar tal reação; iv) investigar o possível mecanismo pelo qual os íons metálicos mediam as reações estudadas. Para isso, foram testadas as resinas derivadas do ácido p-hidroximetilbenzóico (HMBA-AM, HMBA-PEGA, HMBA-TG) e do álcool p-benziloxibenzílico (Wang), os mediadores metálicos Ca2+ e Zn2+, condições reacionais determinadas em estudos anteriores do nosso grupo de pesquisa (50% nucleófilo/ DMF) e os solventes nucleófilos metanol, etanol, propan-1-ol, propan-2-ol, butan-1-ol, álcool benzílico, butilamina e hexilamina. O desligamento de aminoácidos e peptídeos esterificados das resinas ocorreu com altos rendimentos (72 - 98%). A resina HMBA-AM e o íon Zn2+ demonstraram ser a combinação mais eficiente. Análises de espectroscopia de infravermelho na presença e ausência do íon metálico indicaram um mecanismo de reação no qual a coordenação do íon Zn2+ com o álcool facilita a formação do íon alcóxido, o qual é um nucleófilo melhor que o álcool e com capacidade de atacar o carbono da carbonila da ligação éster entre o peptídeo e a resina. / The present study was focused on divalent metal ions-mediated solvolysis of the ester linkage formed between peptides and resins, a method developed by us for the preparation of C-modified peptides. The aims were: i) to adapt it for the Fmoc synthesis strategy; ii) to search resins suitable for such purpose; iii) to determine which divalent metal ion is the most efficient reaction mediator; iv) to investigate the mechanism by which the metal ion mediates the solvolysis reactions studied. Therefore, we employed the resins p-hydroxymethylbenzoic acid (HMBA-AM, HMBA-PEGA, HMBA-TG) and p-benzyloxybenzyl (Wang) alcohol, the metal ions Ca2+ and Zn2+, the optimized solvolysis conditions found in our previous studies (50% nucleophile/DMF) and the nucleophilic solvents methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, benzyl alcohol, butylamine and cyclohexylamine. Detachment of esterified amino acids or peptides from resins gave high yields (72-98%). HMBA-AM resin and Zn2+ ion showed to be the most effective combination of resin and metal ion. Infrared spectroscopy analysis of the peptide-resins in absence and presence of such metal ion suggested a mechanism of reaction where the coordination of Zn2+ ion with the alcohol promotes its deprotonation to give the alkoxide ion, which is a better nucleophile and can attack the carbonyl carbon of the ester linkage formed between the amino acid and the resin.

The use of biodiesel as a fuel has showed a high potential all over the world. In spite of the possible environmental benefits of the vegetable oil use to conversion into biodiesel as a substitute for the diesel, barrels in the economic and ethic points of view, as soil and water use in competition with food cultures and to other technical purposes, motivated the search of alternative raw material for biodiesel production. Among the studied alternatives, the reutilization of residual animal and vegetable oils and fats from food frying processes has shown to be attractive, because the consumption of fried and pre fried food has increased in the last years, causing rise in production of OGRF´s ( Fried Residual Fats and Oils). In this work transesterification reactions of vegetables oils and fats used in frying processes was studied for biodiesel production with immobilized lipases. The samples of OGRF´s were collected in commercial establishments in Maceió city. These samples were characterized concerning its acidity index, iodine index, cinematic viscosity, specific mass, fat acid composition. A study on temperature in which the lipase (Novozym 435) presents better enzymatic activity, in the range between 40-60ºC, was carried out. The alcoholysis reaction was catalyzed by immobilized commercial lipase Novozym 435, the experiments were done according to an factorial experimental design 24-1 where the variables study were: temperature (40-60°C), reaction time (24-72h), enzyme concentration (5-10%) and oil-ethanol rate (1:3-1:9). The determination of yield in ethyl esters (biodiesel) was accomplished by gas chromatography. Among these results, the higher yield was obtained in higher conditions of temperature, enzyme concentration, reaction time and oil: ethanol rate. / A utilização de biodiesel como combustível tem apresentado um potencial promissor no mundo inteiro. Apesar dos possíveis benefícios ambientais no emprego de óleos vegetais para conversão em biodiesel como substituto ao diesel, barreiras do ponto de vista econômico e ético, como concorrência do uso do solo e água com culturas alimentares e para outros fins técnicos, motivaram a busca de matérias-primas alternativas para produção deste biocombustível. Dentre as alternativas estudadas, a reutilização de óleos e gorduras vegetais e animais residuais de processos de fritura de alimentos tem se mostrado atraente, pois o consumo de alimentos fritos e pré-fritos tem aumentado nos últimos anos, provocando um aumento na produção de OGRF’s (Óleos e Gorduras Residuais de Fritura). Neste trabalho estudaram-se reações de alcoólise de óleos e gorduras comestíveis usados em frituras para produção de biodiesel catalisada por lipase imobilizada. As amostras de OGRF’s foram coletadas em estabelecimentos comerciais da cidade de Maceió. Estas amostras foram então caracterizadas quanto aos índices de acidez e de iodo, viscosidade cinemática, massa específica e composições em ácidos graxos. Um estudo para se determinar a temperatura em que a enzima (Novozym 435) apresenta melhor atividade, na faixa compreendida entre 40-60°C, foi realizado. A reação de alcoólise foi catalisada pela lipase comercial imobilizada Novozym 435. Os experimentos foram realizados de acordo com um planejamento experimental fatorial fracionário 24-1 onde as variáveis estudadas foram temperatura (40-60°C), tempo de reação (24-72h), concentração de enzimas (5-10%) e razão óleo:etanol (1:3-1:9). A determinação do rendimento em ésteres etílicos (biodiesel) foi realizada por cromatografia gasosa. Dentre os resultados, o maior rendimento (87,3%) foi obtido nas condições de maiores temperatura, concentração enzimas, tempo reacional e razão óleo:etanol.

Este estudo enfocou a mediação por íons metálicos divalentes da solvólise da ligação éster formada entre peptídeos e resinas, método desenvolvido por nós para a preparação de peptídeos C-modificados. Os objetivos foram: i) adaptá-lo para a estratégia Fmoc de síntese, ii) buscar resinas adequadas para tal propósito, iii) verificar qual íon metálico é mais eficiente para mediar tal reação; iv) investigar o possível mecanismo pelo qual os íons metálicos mediam as reações estudadas. Para isso, foram testadas as resinas derivadas do ácido p-hidroximetilbenzóico (HMBA-AM, HMBA-PEGA, HMBA-TG) e do álcool p-benziloxibenzílico (Wang), os mediadores metálicos Ca2+ e Zn2+, condições reacionais determinadas em estudos anteriores do nosso grupo de pesquisa (50% nucleófilo/ DMF) e os solventes nucleófilos metanol, etanol, propan-1-ol, propan-2-ol, butan-1-ol, álcool benzílico, butilamina e hexilamina. O desligamento de aminoácidos e peptídeos esterificados das resinas ocorreu com altos rendimentos (72 - 98%). A resina HMBA-AM e o íon Zn2+ demonstraram ser a combinação mais eficiente. Análises de espectroscopia de infravermelho na presença e ausência do íon metálico indicaram um mecanismo de reação no qual a coordenação do íon Zn2+ com o álcool facilita a formação do íon alcóxido, o qual é um nucleófilo melhor que o álcool e com capacidade de atacar o carbono da carbonila da ligação éster entre o peptídeo e a resina. / The present study was focused on divalent metal ions-mediated solvolysis of the ester linkage formed between peptides and resins, a method developed by us for the preparation of C-modified peptides. The aims were: i) to adapt it for the Fmoc synthesis strategy; ii) to search resins suitable for such purpose; iii) to determine which divalent metal ion is the most efficient reaction mediator; iv) to investigate the mechanism by which the metal ion mediates the solvolysis reactions studied. Therefore, we employed the resins p-hydroxymethylbenzoic acid (HMBA-AM, HMBA-PEGA, HMBA-TG) and p-benzyloxybenzyl (Wang) alcohol, the metal ions Ca2+ and Zn2+, the optimized solvolysis conditions found in our previous studies (50% nucleophile/DMF) and the nucleophilic solvents methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, benzyl alcohol, butylamine and cyclohexylamine. Detachment of esterified amino acids or peptides from resins gave high yields (72-98%). HMBA-AM resin and Zn2+ ion showed to be the most effective combination of resin and metal ion. Infrared spectroscopy analysis of the peptide-resins in absence and presence of such metal ion suggested a mechanism of reaction where the coordination of Zn2+ ion with the alcohol promotes its deprotonation to give the alkoxide ion, which is a better nucleophile and can attack the carbonyl carbon of the ester linkage formed between the amino acid and the resin.

Cette étude porte sur l’élaboration de polymères greffés à base de poly(éthylène alcool vinylique) (EVOH) et de la polycaprolactone (PCL). La réaction de greffage a lieu par la réaction d’alcoolyse entre les groupements ester de la polycaprolactone et les groupements alcools le long des chaînes d’EVOH. L’étude catalytique et cinétique par des études GC/MS très détaillées, facilitées par l’utilisation de réactions modèles avec le 1-dodécyl benzoate et le 2-dodécanol, montre la possibilité de la synthèse par extrusion réactive. L’activité catalytique de 1.5.7-triazabicyclo[4.4.0]dec-5-ene pour la réaction d’alcoolyse sans solvant et pas extrusion réactive a été confirmé. Les conditions de l’extrusion permettant un taux de greffage optimal ont été déterminées et l’effet déterminant de la température a été confirmé. Le taux de greffage peut être obtenu par des analyses 1H-RMN. Ces résultats combinés à la microscopie électronique à balayage et en transmission ont permis de déterminer les caractéristiques optimales des polymères employés afin de former des mélanges nanostructurés. Les mêmes conditions de synthèse appliqués à d’autres matériaux comme le polyméthacrylate de méthyle, acide polylactique et poly(3-hydroxybutyrate-co-3-hydroxyvalérate) ont permis l’élaboration des copolymères greffés pour des applications biomédicales / This study focuses on the development of graft polymers based on poly (ethylene vinyl alcohol) (EVOH) and polycaprolactone (PCL). The grafting reaction takes place by the alcoholysis reaction between ester groups of the polycaprolactone and alcohol groups along the chains of EVOH. The catalytic and kinetic studies by GC / MS highly detailed, facilitated by the use of model reactions with 1-dodecyl benzoate and 2-dodecanol, shows the possibility of synthesis by reactive extrusion. The catalytic activity of triazabicyclo-1.5.7 [4.4.0] dec-5-ene for the alcoholysis reaction without solvent and by reactive extrusion has been confirmed. The extrusion conditions for optimum rate of grafting were determined and the effect of temperature has been confirmed. The rate of grafting can be obtained by 1H-NMR analysis. These results combined with scanning electron microscopy and transmission, have determined the optimum characteristics of polymers to form nanostructured blends. The same synthesis conditions applied to other materials such as polymethylmethacrylate, polylactic acid and poly (3-hydroxybutyrate-co-3-hydroxyvalerate) allowed the preparation of graft copolymers for biomedical applications

L’objectif de cette thèse est le développement des matériaux polymères injectables innovants issus de ressources renouvelables et répondant aux exigences techniques automobiles. Pour cela, des mélanges à base de polyoléfines (POs) et du poly(3- hydroxybutyrate-co-hydroxyvalérate) (PHBV) ont été étudiés. Ces mélanges polymères étant non-miscibles, l’optimisation de leurs propriétés par compatibilisation a été réalisée selon différentes approches. Dans un premier temps, la synthèse de polypropylène fonctionnel original avec des taux de greffage relativement élevés et sans perte de masses molaires a permis, par réaction in-situ, la compatibilisation des mélanges PP/PHBV. Dans une deuxième partie, le poly(éthylène-co- alcool vinylique) greffé-poly(3- hydroxybutyrate-co- hydroxyvalérate) a été synthétisé par extrusion réactive, ce copolymère a été utilisé ensuite comme compatibilisant pour les mélanges PE/PHBV. L’ajout de ces compatibilisants a permis d’obtenir des matériaux ayant des propriétés optimisées et une morphologie nettement plus fine que les systèmes non compatibilisés démontrant ainsi leur efficacité / The main objective of this work is the development of innovative materials from renewable resources for the automotive industry. Polymer blends of polyolefins (POs) and poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) were prepared through twin screw extruder process and studied. These polymer blends are non-miscible, then in order to optimize their final properties, compatibilizing agents were synthesized by reactive extrusion. On the one hand, functionalized polypropylene with various polar monomers and without significant molecular weight loss was synthesized with the aim to compatibilize PP/PHBV blends, on the other hand, poly(ethylene-co- vinylalcohol)-graft- poly(3-hydroxybutyrate-co-hydroxyvalerate) was obtained by exchange reactions in the presence of an efficient catalyst and those in order to compatibilize PE/PHBV blends. Efficiency of these compatibilizers was investigated in the last part of this study which is dedicated to POs/PHBV polymer blends compatibilization. Materials with improved properties and finer morphologies than the non- compatibilized systems were obtained thanks to the compatibilizers

The theoretical part summarizes the chemical recycling processes of polyurethane and polyisocyanurate insulation foams and methods of polyols preparation from their alcoholysates. Emphasis is placed on the use of microwave heating during depolymerization, as a perspective energy source for chemolysis processes. The practical part is focused on optimization of recyclates preparation derived from polyisocyanurate foams and polyethylene terephthalate by microwave enhanced glycerolysis. Recyclates obtained were verified for their workability and applicability in blends with virgin polyols in polyisocyanurate foam manufacture process.