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Síntese de derivados do ácido quínico, genisteína e cluvenona, potenciais agentes antimicrobianos, antitumorais e contra a esclerose múltiplaRezende Júnior, Celso de Oliveira 18 July 2014 (has links)
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Previous issue date: 2014-07-18 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho são descritas as sínteses e avaliações biológicas de diferentes
classes de compostos orgânicos e está dividido em três capítulos. O primeiro
deles descreve a síntese de derivados da genisteína com distintas
propriedades físico-químicas, a fim de avaliar a influência dessas
propriedades na atividade biológica contra a esclerose múltipla. Foram
sintetizados compostos condensados a carboidratos derivados da D-glicose e
D-galactose e derivados lipofílicos com cadeias alquila ou acila lineares de
doze ou quatorze carbonos. Esses compostos foram submetidos a ensaios de
citotoxicidade e anti-inflamatórios in vitro e os compostos mais ativos foram
avaliados quanto a sua atividade na modulação da resposta imune in vivo no
modelo de encefalomielite auto-imune experimental (EAE). Na síntese dos
drivados éteres verificaram-se diferentes reatividades: os compostos com
cadeias alquila lineares foram obtidos em rendimentos melhores, seguido dos
derivados da D-glicose e D-galactose, respectivamente. A regiosseletividade
obtida na síntese dos derivados éteres foi sugerida por nOe, enquanto que
nos derivados ésteres foi sugerida por RMN de 1H. Os ensaios biológicos
revelaram que todos os compostos apresentaram atividade in vitro e os
derivados de carboidrato foram mais citotoxicicos que os derivados com
cadeias lipofílicas lineares. Após os ensaios in vivo, o composto 13 foi
considerado um protótipo para o tratamento da esclerose múltipla. O
segundo capítulo descreve a síntese e avaliação das propriedades
antimicrobianas de surfactantes derivados do ácido quínico condensados a
diaminas N-alquiladas, variando-se o tamanho da cadeia alquila (parte apolar)
e a estrutura do ácido quínico (parte polar), estabelecendo-se uma relação
estrutura e atividade. Foram sintetizados 32 compostos através de reações de
amidação entre uma lactona derivada do ácido quínico com diaminas Nalquiladas
em rendimentos satisfatórios. 17 compostos apresentaram
atividades semelhantes ou melhores do que a droga de referência. Também
estão sendo realizados alguns ensaios antiparasitários e anti-inflamatórios
com esses compostos. O terceiro capítulo descreve a síntese e avaliação das
propriedades antitumorais de derivados de xantonas Garcinia,
especificamente de cluvenona. Foram sintetizados diversos compostos com
grupos retiradores e doadores de eletróns, hidrofílicos e contendo a unidade
sal de trifenilfosfônio no anel A de hidroxicluvenonas, que auxiliarão no
entendimento da relação estrutura e atividade para essa classe de
compostos. Sintetizou-se também um composto derivado da 6-
hidroxicluvenona condensada com o BODIPY com potencial atividade
antitumoral e propriedades fluorescentes com o objetivo de realizar estudos
de localização celular e mecanismo de ação. A etapa chave para a síntese
desses compostos foi uma reação em cascata de Claisen/Diels-Alder. / In this work the synthesis and biological evaluation of different classes of
organic compounds are described and it is divided into three chapters. The
first chapter describes the synthesis of genistein derivatives with different
physicochemical properties in order to assess the influence of these properties
in biological activity against multiple sclerosis. Carbohydrate derivatives from
D-glucose and D-galactose and compounds condensed with lipophilic alkyl or
acyl linear chains of twelve or fourteen carbons were synthesized. Cytotoxicity
and anti-inflammatory activities in vitro were performed and the most active
compounds were evaluated in modulating the immune response in vivo model
of experimental autoimmune encephalomyelitis. Reactivity of ethers
derivatives was different: compounds with linear alkyl chains were obtained in
higher yields, followed by the derivatives of D-glucose and D-galactose,
respectively. The regioselectivity obtained in the synthesis of ether derivatives
were suggested by nOe, while the ester derivatives were suggested by 1H
NMR. All compounds showed in vitro activity and carbohydrate derivatives
were more cytotoxic than lipophilic derivatives. After in vivo tests, compound
13 was considered a prototype for the treatment of multiple sclerosis. The
second chapter describes the synthesis and evaluation of the antimicrobial
properties of surfactants derived from quinic acid (popar part) condensates
with N-alkylated diamines (nonpolar part). The size of the alkyl chain and the
structure of quinic acid were altered, settling a relationship structure and
activity. 32 compounds were synthesized by amidation reactions between a
lactone derivative of quinic acid with N-alkylated diamines in satisfactory
yields. 17 of these compounds showed equal or better equal activities than the
drug reference. Some antiparasitic and anti-inflammatory tests are also being
conducted for these compounds.
The third chapter describes the synthesis and evaluation of antitumoral
properties of derivatives of Garcinia xanthones, specifically cluvenone. Several
compounds were synthesized with electron withdrawing and donors groups,
containing hydrophilic and the triphenylphosphonium salt unit in the A ring of
hidroxicluvenonas. These compounds will help in understanding the structure
and activity relationship for this class of compounds. A BODIPY
Hydroxicluvenone conjugate compound with potential antitumor activity and
fluorescent properties was synthesized with the aim of studying the cellular
location and mechanism of action. The key step for the synthesis of these
compounds was a reaction cascade Claisen / Diels-Alder reaction.
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Organic Transformations in Water : Synthetic and Mechanistic Studies towards Green MethodologiesShrinidhi, Annadka January 2013 (has links) (PDF)
This thesis entitled “Organic Transformations in Water: Synthetic and Mechanistic Studies towards Green Methodologies” is in two parts. Part-I describes various synthetic studies aimed at developing improved methodologies; Part-II describes certain mechanistic studies directed towards an improved understanding of phase transfer catalysis and the hydrophobic effect.
Water is uniquely advantageous as a solvent. It is environmentally benign, non-flammable, liquid over a wide temperature range and possesses a high heat capacity that makes it inherently safe. Water also catalyses chemical transformations between insoluble organic reactants. Water thus serves as a reaction medium, a product partitioner and a reaction catalyst.1
Part-I:- Reactions in Water under both Microwave and Ambient Conditions
Part-I is further divided into three chapters.
Chapter II deals with reactions of 2-nitroalcohols (2NAs), and is divided into three sections. Section A describes the synthesis of nitroalkanes via the microwave-assisted, water-mediated chemoselective reduction of 2NAs using tributyltin hydride (Bu Scheme 1 ). The 2NAs, synthesized from nitromethane and aldehydes (aliphatic, alicyclic, heterocyclic or m- & p-substituted aromatic aldehydes), were converted into corresponding nitroalkanes in excellent yields. The 2NAs derived either from substituted nitromethane [nitroethane, (nitromethyl)benzene, etc.] or bulky aldehydes (o-substituted aromatic aldehydes), however, failed to furnish nitroalkanes under these conditions. Also a major solvent effect was observed: the extent of conversion was greater in water than in water-polar 3SnH) as reducing agent. The chemoselective reduction of 2NAs to nitroalkanes was observed accidentally while trying to remove the nitro group of 2NAs in a Bu3SnH-AIBN-water system under microwave conditions. When equimolar quantities of 2NA and Bu3SnH were added to water, microwave irradiation led to nitroalkanes (protic solvent mixtures and the reaction did not occur either in aprotic polar or non-polar solvents.
Scheme 1. Microwave assisted chemoselective reduction of 2NAs to nitroalkanes in Bu3SnH-water
In Section B, the microwave assisted synthesis of nitroalkanes from nitroalkenes has been described. Equimolar quantities of nitroalkene and Bu Scheme 2 ). The nitroalkenes substituted even by bulky groups at C-1 & C-2 were converted into corresponding nitroalkanes. Hence the drawback of the method described in Section A was overcome by employing nitroalkenes as starting materials. 3SnH in water under microwave irradiation, led to excellent yields of corresponding nitroalkanes (Scheme 2). The nitroalkenes substituted even by bulky groups at C-1 & C-2 were converted into corresponding nitroalkanes. Hence the drawback of the method described in Section A was overcome by employing nitroalkenes as starting materials.
Scheme 2. Microwave assisted reduction of nitroalkenes to nitroalkanes in Bu3SnH-water
In Section C, the synthesis of nitroalkenes via dehydration of 2NAs in a K Scheme 3 ). Thus, the dehydration of 2NAs has been accomplished under relatively mild conditions. (It was observed that the 2NAs bearing bulky groups underwent the retro-Henry reaction rather than dehydration.) 2CO3-water system has been described. This conversion was accomplished at 0-5 °C in 5-30 minutes, the nitroalkenes being isolated in good yields (Scheme 3). Thus, the dehydration of 2NAs has been accomplished under relatively mild conditions. (It was observed that the 2NAs bearing bulky groups underwent the retro-Henry reaction rather than dehydration.)
Scheme 3. Dehydration of 2-NAs in aqueous K2CO3 solution
Chapter III describes the chemoselective reduction of ketoaldehydes. This was serendipitously discovered during attempted enantioselective reduction of prochiral ketones using amino acid-NaBH Scheme 4 ). The method provides a mild and efficient route for the chemoselective reduction of aldehydes under aqueous basic conditions. 4-Na2CO3 in water. When equimolar quantities of aldehyde and ketone were added to a solution NaBH4 in aqueous Na2CO3 at ambient temperature, the aldehydes were selectively reduced. Good yields of primary alcohols were generally observed with excellent chemoselectivities. Extension of this study to the selective reduction of ketoaldehydes under the above reaction conditions furnished ketoalcohols in > 70% yields with > 80% chemoselectivities (Scheme 4). The method provides a mild and efficient route for the chemoselective reduction of aldehydes under aqueous basic conditions.
Scheme 4. Chemoselective reduction of ketoaldehydes with NaBH4-Na2CO3 in water
Chapter IV deals with deprotection of various acetals, thioacetals and tetrahydropyranyl (THP) ethers in hexane under ambient conditions, by employing chloral hydrate as reagent. Chloral hydrate is a crystalline solid with pK2 When a a 9.66.stirred suspension of excess chloral hydrate in hexane was treated with the acetal, thioacetal or THP ether, the corresponding aldehyde, ketone and alcohol were obtained in good to excellent yields (stirred suspension of excess chloral hydrate in hexane was treated with the acetal, thioacetal or THP ether, the corresponding aldehyde, ketone and alcohol were obtained in good to excellent yields (stirred suspension of excess chloral hydrate in hexane was treated with the acetal, thioacetal or THP ether, the corresponding aldehyde, ketone and alcohol were obtained in good to excellent yields (
Scheme 5. Chloral hydrate catalyzed hydrolysis of acetals, thioacetals including THP ethers
Part-II:- Mechanistic Studies on Phase Transfer Catalysis and The Hydrophobic Effect
Part-II is in two chapters.
Chapter V describes a study of the mechanism of the phase transfer catalyzed (PTC) nucleophilic reaction of cyanide ion with alkyl halides in decane ( Scheme 7 ). In the extraction mechanism proposed earlier,3 the PTC forms the mixed species, tributylhexadecylphosphonium cyanide (THPB), which is believed to be more soluble in decane than is the starting cyanide. A problem with this explanation is that the positive free energy of transfer of the cyanide ion from the aqueous to the organic phase, which is unlikely to be offset by solvation energy of the hexadecyl and butyl groups.
Scheme 6. Cyanide displacement reaction of 1-chloro octane3
The present studies explore the possibility that the reaction occurs via the formation of aggregates resembling reverse micelles ( Figure 1 ). In these, the hydrocarbon residues point outwards, with the ionic species ensconced in a deeply embedded interior along with a certain number of water molecules. Thus, the ionic species are not only shielded from the organic medium, but also stabilized in a relatively polar micro-environment (largely via dipolar interactions and hydrogen bonding). It is assumed that this stabilization energy surpasses the positive free energy of transfer of cyanide ion from aqueous to the organic phase.
Figure 1. Typical representation of cyanide displacement reaction in THPB-decane-water micellar pool
In fact, NMR studies on the structural dynamics of THPB in solution offered evidence of aggregation. Also, a correlation between the structures of catalyst and reactant was observed in studies with various other PTC’s.
Chapter VI deals with the mechanism of the Diels-Alder reaction (DAR) in water. The concept of the hydrophobic effect (HE)4 and preferential hydrogen bonding of water with the polarized transition state5 have been invoked to explain the apparent acceleration of Diels-Alder reactions in water.
The present studies explore the possibility that the highly polar water microenvironment stabilizes the transition state. Semi-quantitative rate studies of DAR involving water soluble reactants indicate that the possible role of solvation and hydrogen bonding on the polarized transition state as the key factor in the rate enhancement of water mediated DAR. The DAR in the presence of a catalytic amount of water along with the organic solvent catalyzed the reaction more efficiently, as compared to the reaction in pure organic solvent. It was also observed that there was a prominent effect of traces of water on the rate in solvent-free conditions.
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Modification of carbon fiber / epoxy matrix interphase in a composite material : Design of a self-healing interphase by introducing thermally reversible Diels-Alder adducts / Modification de l’interphase du matériau composite fibre de carbone /matrice époxyde : Design d’une interphase auto-réparable basée sur des liaisons Diels-Alder thermiquement réversiblesZhang, Wenyong 11 December 2014 (has links)
Une interphase fibre de carbone/matrice époxy thermiquement auto-réparable a été construite sur la base de liaisons covalentes Diels-Alder (D-A) thermiquement réversibles. L’interphase modifiée par D-A a été formée en greffant des groupes maléimide sur la surface de la fibre de carbone et en introduisant des groupes furane dans le réseau polyépoxy. La capacité d’auto-réparation interfaciale a été caractérisée par le test de déchaussement de la micro-goutte. La surface de la fibre de carbone a subi un traitement en trois étapes : (i) oxydation par l’acide nitrique, (ii) amination par la tétraéthylènepentamine (TEPA) et (iii) greffage de bismaléimide (BMI). Après chaque étape de traitement, les modifications physico-chimiques de surfaces de la fibre ont été caractérisées par microscopies (MEB et AFM) et par spectroscopies (XPS, et ATR-FTIR). La modification de la matrice a été effectuée en copolymérisant le furfuryl glycidyl éther (FGE) au réseau époxy/amine et les propriétés de la matrice ont été évaluées par TGA, DSC, ATR-FTIR, et traction uniaxiale. Le caractère réversible des liaisons Diels-Alder a été également vérifié par DSC, TGA et RMN. Pour caractériser les capacités d'auto-réparation de l’interphase modifiée par D-A, les propriétés mécaniques et les capacités d'auto-réparation de l'interphase construite en combinant la matrice DGEBA-FGE/amine avec une série de fibres de carbone greffés par BMI ont été mesurées en fonction du temps d’oxydation préalable au greffage (gouvernant la réactivité de la fibre de carbone). Enfin, car le FGE joue un double rôle dans le système interfacial modifié par D-A, à la fois dans l’architecture en intervenant comme allongeur de chaîne entre nœuds de réticulation du réseau époxyde et au niveau de l’interphase en contribuant dans la formation des liaisons réversibles, l'influence de la concentration de FGE dans la matrice a été étudiée sur les propriétés mécaniques de l'interphase et également sur les propriétés mécaniques de la matrice. Par conséquent, ce travail a permis d’aboutir à la procédure optimale pour construire une interphase fibre de carbone/époxy thermiquement auto-réparable basée sur des liaisons covalentes Diels-Alder (thermo réversibles). L'interphase ainsi formée possède non seulement des capacités d’auto-réparations multiples, mais également des propriétés mécaniques compatibles avec une approche ‘matériau composite’. En effet, les propriétés mécaniques globales des matériaux composites, comme attendu, sont dépendantes des caractéristiques de cette interphase mais ne seront pas réduites par la présence de celle-ci notamment pour assurer la durabilité du matériau composite. / A thermally self-healable carbon/epoxy interphase was designed based on Diels-Alder (D-A) thermally reversible covalent bonds. The D-A modified interphase was formed between maleimide groups grafted on carbon fiber surface and furan groups introduced into epoxy network. The self-healing ability was characterized by a micromechanical approach using the micro-droplet debonding test. In this work, carbon fiber surface underwent a three-step treatment to graft maleimide groups, including HNO3 oxidization, tetraethylenepentamine (TEPA) amination, and bismaleimide (BMI) grafting. The fiber surface physico-chemical modifications after each treatment step were characterized by microscopies (SEM, and AFM) and spectroscopies (XPS, and ATR-FTIR). The matrix modification was carried on mixing furfuryl glycidyl ether (FGE) into epoxy/amine network and the properties of modified matrix were studied by TGA, DSC, ATR-FTIR, and tensile tests. The reversible character of Diels-Alder bond was also followed by DSC, TGA, and NMR. The interfacial mechanical properties and the self-healing abilities of the D-A modified interphases, built by combining DGEBA-FGE/amine matrix with a serial of BMI-grafted carbon fibers tuned as a function of the oxidization time were investigated. At last, since FGE plays a double-role in D-A modified interfacial system, i.e. chain extender in epoxy network and self-healing agent in the interphase, the influences of FGE content in matrix on the mechanical properties of interphase and also on the mechanical properties of cured matrix were evaluated. As a consequence, this study allowed to achieve the best process to build a thermally self-healable carbon/epoxy interphase based on thermally reversible Diels-Alder covalent bonds. The formed interphase has not only the successive self-healable abilities but also the required mechanical properties. Additionally, the overall mechanical properties of the composite material based on this interphase will not be weakened significantly after the interfacial modifications.
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Synthetisch interessante Transformationen von Ring-anellierten (E,Z,E)-1,3,5-Hexatrienen / Synthetically interesting transformations of ring-annelated (E,Z,E)-1,3,5-hexatrienesEssen, Regina von 01 July 2004 (has links)
No description available.
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Palladium-katalysierte Domino-Reaktionen zum Aufbau bi- und tricyclischer Systeme / Formation of Bicyclic and Tricyclic Systems by a Domino Process of Palladium-Catalyzed Cyclization and Diels-Alder ReactionKörbe, Stefanie 26 June 2001 (has links)
No description available.
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Développement de nouveaux sels d’imidazolium : application du milieu cristal liquide ionique pour la réaction de Diels-Alder Intramoléculaire et à la préparation des nanoparticules d’Or AnisotropesDo, Tien Dat 03 1900 (has links)
Les liquides ioniques à base de sels d’imidazolium sont une classe très importante de composés, compatibles avec de nombreuses réactions organiques et largement employés dans la synthèse organique en tant que solvants, catalyseurs ou ligands. En particulier, les liquides ioniques peuvent être récupérés à la fin de la réaction. Les sels d’imidazolium présentent également des propriétés d’organisation intéressantes, aussi bien en phase solide, liquide et en solution. Cependant, les liquides ioniques traditionnels présentent certains désavantages lorsqu’utilisés comme solvant dans des réactions intramoléculaires, surtout dans le cas où le réactif est apolaire. La faible solubilité de ce dernier dans le milieu ionique conduit à la formation des produits intermoléculaires. Les travaux présentés dans cette thèse portent sur l’utilisation des propriétés d’organisation des sels d’imidazolium, tout d’abord pour le développement des nouveaux cristaux liquides ioniques, comme le milieu réactionnel pour la réaction de Diels-Alder intramoléculaire, et ensuite pour la préparation des nanparticules d’or anisotropes.
Dans un premier temps, le développement des sels d’imidazolium dicationiques portant des chaînes alkyles flexibles et un cœur rigide, avec des unités imidazolium attachées directement à un noyau naphthalène est rapporté. Par la suite, leurs propriétés thermiques et mésomorphes ont été étudiées. Ces sels sont stables thermiquement et forment une phase cristal liquide de type Smectique T, sur une plage de températures appropriées pour des réactions organiques. En utilisant le milieu cristal liquide comme milieu réactionnel dans la réaction de Diels-Alder, le réactif a été piégé dans la structure organisée de cette phase, ce qui a empêché l’interaction entre deux molecules de réactifs, limitant la formation du produit intermoléculaire. D’ailleurs, le milieu cristal liquide ionique a pu être récupéré et reutilisé à la fin de la réaction.
Dans un deuxième temps, l’influence de la structure de la mésophase sur la réaction de Diels-Alder intramoléculaire a été étudiée. Des sels d’imidazolium tricationiques ayant une symétrie C3 ont ete développés dans le but d’obtenir des phases colonnaires. Ces sels possèdent un cœur rigide formé par trois cations imidazolium liés à un noyau benzène et des chaînes alkyles flexibles. Des études thermiques et mésomorphes sur ces composés ont été ensuite réalisées. Ces composés possèdent une haute stabilité thermique et forment une phase colonnaire rectangulaire, stable sur une large gamme de températures. L’influence de cette phase sur la réaction de Diels-Alder a ete étudiée. L’utilisation de la phase colonnaire favorise également la réaction intramoléculaire. En particulier, elle s’est avèree plus efficace que la phase Smectique T, probablement dû à sa structure plus organisée, indiquée par une enthalpie de tranisition cristal liquide – liquide isotrope plus élevée.
Dans un dernier temps, nous nous sommes intéressés à l’utilisation des propriétés d’organisation des sels d’imidazolium dans la préparation des nanoparticules d’or anisotropes. Dans cette optique, différents mélanges binaires, composés d’un sel d’imidazolium et le diméthylformamide (DMF), ont été préparés et utilisés comme solvants et stabilisants, dans la synthèse des nanoparticules d’or à température ambiante. L’utilisation de ces milieux nous a permis d’obtenir des particules d’or avec différentes géométries. La forme des nanoparticules d’or obtenus dépend de la structure des sels d’imidazolium utilisés et de la concentration du mélange binaire, à la fois. / Ionic liquids based on imidazolium salts are an important class of compounds, possessing a very
good compatibility with various organic reactions, and are widely used as solvents, catalysts and
ligands in organic synthesis. Moreover, imidazolium salts possess interesting supramolecular
organization in the solid, liquid and solution state. However, ionic liquids present some
disadvantages when used as solvents for intramolecular reactions, especially in the case of apolar
reactants. The low solubility of ionic compounds in ionic media promote the formation of
intermolecular products. The main goal of the research presented in this thesis is to explore the
supramolecular organization of imidazolium salts, first in the development of ionic liquid
crystals as reaction media for intramolecular Diels-Alder reactions and secondly for the
preparation of anisotropic gold nanoparticles.
First, the development of dicationic imidazolium salts having a rigid core and flexible alkyl
chains is reported. The rigid core is forned by direct attachment of two imidazoliums on a
naphthalene moiety. Their thermal and mesomorphic analyses were then carried out. These
dicationic salts show a high thermal stability and form a very ordered smectic T phase, over a
wide range of temperatures. This mesophase was subsequently used as reaction medium for
intramolecular Diels-Alder reactions. In this phase, reactants are trapped in the highly organized
structure of the liquid crystal medium, limiting the formation of intermolecular products.
Moreover, the ionic liquid crystal, was recoved at the end of reaction by simple extraction.
Secondly, the influence of the mesophase’s structure on the Diels-Alder reaction was explored.
Tricationic imidazolium satls having a C3 symmetry were developed in order to obtain columnar
phases. The rigid core of these salts is composed of three imidazolium units directly attached to
the benzene ring. Their thermal stabilities and mesomorphic properties were investigated. The
columnar phase formed by these salts was then used as reaction media for Diels-Alder reactions,
and it proved to be more efficient than the previously used smectic T phase, due to their more
organized structure, as indicated by the higher enthalpy value of the liquid crystal - isotropic
liquid transition.
iv
Finally, the supramolecular organization in solution of two imidazolium salts was explored with
the aim to prepare anisotropic gold nanoparticles. Different binary mixtures composed of an
imidazolium salt and dimethylformamide (DMF) were prepared and used both as solvent and
capping agent in the synthesis of gold nanoparticles, at room temperature. The use of these binary
mixture allowed us to synthesize nanoparticles with various geometries. The form of the gold
nanoparticles prepared in these binary mixtures was influenced by both, the structre and the
concentration of the imidazolium salt used.
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Développement d'un système réactif pour composites acryliques par procédé RTM / Acrylic thermoplastic-based composites as processed by RTMFontanier, Jean-Charles 27 March 2017 (has links)
Le contexte environnemental actuel conduit les constructeurs automobiles à diminuer les émissions globales de CO2. Afin de répondre à cet objectif, plusieurs voies sont accessibles mais l’allègement de la structure du véhicule apparaît comme la solution la plus prometteuse grâce à la substitution des pièces métalliques par des matériaux composites et plus particulièrement des composites thermoplastiques à matrices acryliques. Cette étude s’est donc intéressée à développer et caractériser plusieurs formulations à base acrylique afin d’identifier les différents leviers (choix du monomère / condition de polymérisation) permettant d’atteindre une polymérisation rapide (< 3 à 5 min) adaptée aux hautes cadences de l’industrie automobile. Le moulage par transfert de résine (RTM) ayant été choisi comme procédé de mise en œuvre, une seconde étape de travail a été de caractériser l’évolution de la viscosité au cours de la polymérisation. En disposant des mesures cinétiques et rhéologiques, il a aussi été possible, par modèle inverse, de proposer un suivi in-situ de la polymérisation via la corrélation des données par des mesures diélectrométriques. Puis, dans une optique d’amélioration de la tenue chimique du PMMA, la synthèse d’un polymère réversible présentant alternativement une structure tridimensionnelle et une structure linéaire a été réalisée. Ainsi, grâce à la préparation d’un comonomère présentant des fonctions Diels-Alder, il a été possible d’obtenir un polymère ayant la capacité d’emprunter les propriétés de résistance chimique des réseaux thermodurcissables tout en conservant l’aptitude à la transformation des thermoplastiques. Enfin, une dernière étude s’est portée sur le renforcement du PMMA par mélange avec différents polymères. Ainsi, grâce à un choix judicieux de polymères présentant des caractéristiques physico-chimiques intéressantes, il a été possible d’améliorer significativement la tenue en température mais également la résistance au choc de la matrice acrylique développée. / Nowadays, polymer matrix composites are widely used for aerospace, automotive, railway and sport industries. For similar structural properties, these materials coul be very attractive since they could be 30 to 40% lighter than metallic counterparts. In the current context of environmental development issues, thermoplastic-based composites, (in our case acrylic matrix based one), can be considered as they can be easily recycled as opposed to thermoset-based ones. Furthermore, they could exhibit good mechanical properties, i.e. stiffness and impact resistance, enabling them to be relevant for many applications. Manufacturing structural composites requires to produce parts without defects having complex geometries. For this purpose Resin Transfer Molding (RTM) has been selected to process such composites. Indeed, it corresponds to a low temperature closed-mold process allowing for manufacturing complex continuous fiber-based-reinforced parts. However, it requires precursors with a very low viscosity (η < 1 Pa.s) to ensure a good impregnation of the dry preform. To be cost effective, fast reactive systems have also to be selected. Thermoplastic polymers which own a very high viscosity in molten state cannot be directly used. Our strategy is to design an acrylic-based reactive formulation exhibiting a very low initial viscosity, i.e. about 100 mPa.s and which can subsequently polymerizes via a free radical mechanism once the mold is filled and the preform fully impregnated. Therefore, our main objective is to optimize curing conditions (especially thermal initiator ratios and temperature) of RTM-compatible acrylic-based reactive formulations to lead to suitable composite parts with high conversion rate, low residual monomer content and relevant process cycles.
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β-Aminosubstituted α,β-Unsaturated Fischer Carbene Complexes as Precursors for Complex Oligocyclic Molecules - Basics and Applications / β-Amino-substituierte α,β-Ungesättigte Fischer Carben-Komplexeals Vorläufer für Kompexe Oligocyclische Moleküle - Grundforschung und AnwendungenWu, Yao-Ting 03 July 2003 (has links)
No description available.
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Die Iromycine und das Collinolacton: Synthese mikrobieller Naturstoffe aus Streptomyces sp. / The Iromycins and the Collinolacton: synthesis microbial natural products from Streptomyces sp.Shojaei, Heydar 02 May 2007 (has links)
No description available.
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