Abstract This study concentrates on the preparation and characterization of some ionic liquids and their use in dimerization reaction of 2-methylpropene. Ionic liquids consist of cations and anions, and are commonly understood as green solvents. By definition their melting points should be lower than 100 °C. Prepared ionic liquids were used as catalytic solvents in dimerizations of 2-methylpropene to a high octane compound, isooctene. The monograph consists of two parts: the literature survey and the practical work. The literature survey reviews the preparation and characterization of ionic liquids as well as their environmental aspects, such as toxicity, biodegradability and recyclability. In addition, the acid catalyzed dimerization of butenes is discussed together with the dimerizations of light olefins carried out in ionic liquids. The practical work consists of three entities: The environmentally benign preparation of 1-alkyl-3-methylimidazolium-based ionic liquids under microwave activation, the characterization of ionic liquids and the use of the ionic liquids in the dimerization reaction. Ionic liquids absorb efficiently microwave irradiation and the most beneficial aspect in the microwave-assisted preparations was the considerably shortened reaction time compared to the conventional methods. In addition to the microwave-assisted preparations, [Cnmim][InCl4] ionic liquids were prepared successfully without microwave irradiation. A special attention was paid to the characterization of ionic liquids since impurities are known to affect on the properties of the ionic liquids. Ionic liquids were analysed with the following methods: 1H and 13C NMR, MS(ESI+ and ESI-), GC and elemental analysis. Characterization of ionic liquids was done by determining the thermal stability, the melting point and the crystal structure of each solid ionic liquid. The determination of the liquid range of ionic liquid is necessary in order to know the temperature limits for each ionic liquid. Novel InCl3-based ionic liquids revealed to be the more efficient than Brønsted acidic ILs as a catalytic reaction media in the dimerization of 2-methylpropene. It was preferable to apply [C6mim]Cl/InCl3 (x(InCl3) = 0.55) as a catalytic IL since then the conversion of 2-methylpropene and the product distribution revealed to be good. In order to maximize the production and the separation of dimers reaction should be carried out continuously at temperature high enough, such as 160 °C. Neutral InCl3-based ionic liquid did not catalyze reaction of 2-methylpropene, but it had to be acidic x(InCl3) > 0.5. Excess of InCl3 did not leach out from the IL and the recycling of IL was possible.

Au cours de cette thèse, des dispositifs électrochromes à base de polymères conducteurs électroniques ont été développés pour obtenir des systèmes pouvant passer d’un état coloré cyan, magenta ou jaune à un état incolore. Les polymères électrochromes sont des dérivés du poly(3,4-propylènedioxythiophène) (PProDOT) et du poly(3,4-éthylènedioxythiophène) (PEDOT). Un réseau de polyéthylène glycol incorporant un liquide ionique 1-éthyl-3-méthylimidazolium bis(trifluorométhylsulfonylimide) (EMITFSI) a été utilisé en tant que gel d’électrolyte. Dans un premier temps, les polymères cyan, magenta et jaunes ont été étudiés. La relation entre structure et propriétés colorimétriques des polymères cyan et jaunes a été étudiés par des calculs théoriques avec la théorie de fonctionnelle de densité, la spectroscopie UV/Vis et la colorimétrie. Ces deux dernières techniques ont également été utilisées pour l’étude des polymères magenta. Les polymères présentant les meilleures propriétés optiques ont ensuite été intégrés dans des dispositifs à deux électrodes. Ceux-ci ont été étudiées par des mesures électrochimiques pour évaluer les effets sur le fonctionnement du système et sa durée de vie. Grâce aux données obtenues, nous avons pu montrer que la stabilité des dispositifs était liée à l’efficacité coulombique des polymères cyan, magenta ou jaunes. Pour contourner l’effet de l’efficacité coulombique sur les systèmes en 2 électrodes, nous avons développé des dispositifs intégrant une pseudo-référence. L’application de ces systèmes à 3 électrodes avec un polymère cyan permet de multiplier la gamme de stabilité par 7. Finalement des démonstrateurs ont été produits avec plusieurs dispositifs de chaque couleur. / During the course of this work, electrochromic devices integrating electronically conductive polymers have been developed to obtain systems that could switch from a cyan, magenta or yellow color to an almost colorless one. The electrochromic polymers are derivatives of poly(3,4-propylenedioxythiophene) (PProDOT) and poly(3,4-ethylenedioxythiphene) (PEDOT). A network of polyethyleneglycol swollen with an ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide) (EMITFSI) was used as a gel polymer electrolyte. As a first step, the cyan, magenta and yellow polymers were studied. The relationship between structure and colorimetric properties of the cyan and yellow polymers have been studied with theoretical calculation using the density functional theory, UV/Vis spectroscopy and colorimetry. These last two techniques have also been used to study the magenta polymers. The polymers with the best optical properties have then been integrated inside two electrode devices. They have been characterized with electrochemical measurement to evaluate the effects on the system and its lifetime. The data showed that the stability of the devices was linked to the reversibility of the cyan magenta or yellow polymers. As a workaround to the coulombic efficiency limitation on the 2 electrode systems, we have developed devices with a pseudo-reference. The application of those 3 electrode systems with a cyan polymer leads to a 7 fold increase of the device lifetime. Finally demonstrators have been produced with several devices of each color.

Orientador: Marcos Nogueira Eberlin / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T13:08:08Z (GMT). No. of bitstreams: 1 Corilo_YuriEberlimde_M.pdf: 973329 bytes, checksum: 0e8a6362dd2a94d8ce4185376aa8bde3 (MD5) Previous issue date: 2009 / Resumo: A técnica de ionização a pressão atmosférica por electrospray (ESI) se tornou rapidamente a mais utilizada nas áreas de química e bioquímica, em estudos mecanísticos e em análises por ¿fingerprinting¿. ESI é versátil devido a sua alta sensibilidade e capacidade de transferir espécies iônicas da solução para a fase gasosa de forma branda, permitindo inclusive que espécies de alto peso molecular fracamente ligadas permaneçam intactas. Entre os líquidos iônicos (LI) já conhecidos, destacam-se os compostos heterocíclicos da classe dos cátions imidazólios. A espectrometria de massas não era capaz de detectar e analisar essa classe de compostos devido à baixa volatilidade que estes LI apresentam. Entretanto, com o desenvolvimento da técnica de ESI tornou-se possível à transferência desses compostos para a fase gasosa de uma forma bastante branda e eficaz. Estas espécies, podem ser detectadas por espectrometria de massas mesmo sofrendo modificações como fragmentações, rearranjos e reações, pelo fato de um ou dois anéis imidazóis funcionarem como uma ¿âncora¿ de carga, permitindo o estudo de propriedades intrínsecas destes compostos, como reatividade bimolecular. Através de experimentos com ESI em tandem (ESI-pseudo-MS, e ESIMS/ MS) utilizando a técnica de dissociação induzida por colisão (CID), foi possível formar, selecionar e identificar várias novas espécies de carbenos e radicais com sítios afastados de cargas múltiplas e arinos imidazólios / Abstract: The ionization technique, atmospheric pressure electrospray (ESI) has become rapidly the most used in the fields of chemistry and biochemistry, mechanistic studies and in analysis by fingerprint. ESI is versatile due to its high sensibility and capability to transfer ionic species from the solution to the gas phase in a soft way, allowing, inclusively, that species of high molecular weight weakly bonded remain intact. Among the ionic liquids (IL¿s) known, heterocyclic imidazolium cations stand out. Mass spectrometry was not able to detect and analyze this class of compounds due to the low volatility of these compounds. However, with the development of the ESI technique has become possible the transfer of these compounds to the gas phase. These species may be detected by mass spectrometry even when they suffer modifications such as fragmentations, rearrangements or other reactions, due to the fact that one or two imidazolium rings work as a charge ¿anchor¿, allowing the study of intrinsic proprieties of these compounds, such as bimolecular reactivity. Through tandem ESI experiments (ESI-psedo-MS, and ESI-MS/MS) using the collision induced dissociation (CID) technique, it was possible to form, select and identify several new species of multiply charged carbenes, radicals and arynes / Mestrado / Quimica Organica / Mestre em Química

Orientador: Marcos Nogueira Eberlin / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T14:25:38Z (GMT). No. of bitstreams: 1 Nachtigall_FabianeManke_D.pdf: 3920782 bytes, checksum: 88d49f1c9eaf6b17b3567019b6df9444 (MD5) Previous issue date: 2009 / Resumo: Com o objetivo de entender as propriedades intrínsecas dos líquidos iônicos imidazólios, foram desenvolvidos trabalhos de investigação dos mecanismos de dissociação e destilação, força intrínseca de ligações de hidrogênio e formação e caracterização de carbenos a partir destes compostos. Tais estudos foram realizados através da espectrometria de massas com técnicas API (Atmospheric Pressure Ionization) como ESI-MS(/MS) (Eletrospray Ionization Mass Spectrometry) e APCI-MS(/MS) (Atmospheric Pressure Chemical Ionization Mass Spectrometry) que são técincas de ionização branda que permitem a análise dos compostos por infusão direta da solução de interesse. Para estes estudos foram escolhidos cátions imidazólios com diferentes substituintes nas posições N-1, N-3 e C-2, além de diferentes ânions como contra-íons. O objetivo do trabalho foi testar como essas modificações na cadeia iriam afetar as porpriedades intrínsecas estudadas. A partir dos resultados obtidos nos trabalhos realizados foi possível propor mecanismos de fragmentação para uma vasta gama de líquidos iônicos imidazólios, e propor um mecanismo de destilação para alguns destes compostos. Foram realizadas medidas onde foi possível ordenar e medir a magnitude intrínseca das ligações de hidrogênio para diferentes cátions. Além disso foram obtidas informações a respeito da formação e caracterização de carbenos a partir de líquidos iônicos di, tri e tetraimidazólios. / Abstract: In order to understand the intrinsic properties of imidazolium ionic liquids, studies of dissociation and distillation mechanisms were developed. The intrinsic strength of hydrogen bonds and formation and characterization of carbenes from these compounds were also investigated. Such studies were conducted by API (Atmospheric Pressure Ionization) mass spectrometry techniques such as ESI-MS(/MS) (Electrospray Ionization Mass Spectrometry) and APCI-MS(/MS) (Atmospheric Pressure Chemical Ionization Mass Spectrometry) which are soft ionization techniques allowing the analysis of compounds by direct infusion of the solution of interest. For these studies, imidazolium cations with different substituent at positions N-1, N-3 and C-2 and different anions as counter ions were selected. The objective was to test how these changes in the chains would affect the intrinsic properties studied. From the results of the work fragmentation mechanisms for a wide range of imidazolium ionic liquids were proposed, as well as a mechanism for the distillation of some of these compounds. Measurements were made to order the intrinsic strength of hydrogen bonding for different cations. Further information was obtained about the formation and characterization of carbenes from di-, tri-and tetra-imidazolium ionic liquids. / Doutorado / Quimica Organica / Doutor em Ciências

Orientador: Carlos Roque Duarte Correia / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T14:22:36Z (GMT). No. of bitstreams: 1 Pastre_JulioCezar_D.pdf: 10159507 bytes, checksum: 4f4f32c2c414df354e1d53179d9ebe18 (MD5) Previous issue date: 2009 / Resumo: Neste trabalho, efetuou-se um estudo da reação de Heck de acrilatos substituídos com sais de arenodiazônio. Um protocolo estereosseletivo para a preparação de acrilatos b,b-diarilssubstituidos foi desenvolvido, baseando-se na arilação Heck do cinamato de metila com sais de arenodiazônio, catalisada por Pd(OAc)2, em metanol. A diastereosseletivade da reação de Heck apresentou uma acentuada dependência com a natureza eletrônica do sal de arenodiazônio empregado. A metodologia ainda forneceu uma rota conveniente para 3-arilindanonas e 4-ariltetralonas, permitindo as sínteses formais totais da (±)-indatralina (4 etapas, 54 % de rendimento global) e da (±)-sertralina (7 etapas, 49 % de rendimento global). A extensão da metodologia para acrilatos mais substituídos (inclusive para acrilatos cíclicos) foi feita com sucesso para a maioria dos casos e os adutos de Heck foram obtidos em bons rendimentos e seletividades, independente do padrão de substituição do sal de arenodiazônio empregado. Esta metodologia foi aplicada à síntese total da (±)-paroxetina (8 etapas, 15 % de rendimento global) e da (±)-nocaína (6 etapas, 20 % de rendimento global). Verificou-se ainda que a reação de arilação de Heck empregando sais de arenodiazônio ocorre de maneira eficiente em meios reacionais alternativos, como PEG e líquidos iônicos. Uma série de líquidos iônicos quirais inéditos do tipo piridínio, imidazolínio e imidazólio foi preparada e testada, não revelando nenhuma incidência no curso estereoquímico da reação. Os resultados obtidos demonstram o enorme potencial sintético do emprego de sais de arenodiazônio em reações de Heck, constituindo uma metodologia bastante versatil em Síntese Orgânica. / Abstract: In this work, we present a study of the Heck reaction of substituted acrilates with arenediazonium salts. A stereoselective protocol for the preparation of b,b-disubstituted acrylates in good yields by means of a Heck-Matsuda reaction was accomplished. The method employs a base- and ligand-free Heck reaction of methyl cinnamate using arenediazonium salts as electrophiles. The Heck reaction displays a remarkable electronic dependence regarding the diastereoselectivity of the arylation process, which correlates with the electronic nature of the arenediazonium salts employed. The overall methodology provides a convenient route to 3-arylindanones and 4-aryltetralones allowing the concise formal total syntheses of the therapeutically important psychoactive compounds (±)-indatraline (4 steps, 54 % global yield) and (±)-sertraline (7 steps, 49 % global yield). The methodology was also successfully extended to more substituted acrylates and the Heck adducts were obtained in good to excellent yields, regardless of the substitution pattern of the arenediazonium salt employed. This methodology was applied to the total synthesis of (±)-paroxetine (8 steps, 15 % global yield) and (±)nocaine (6 steps, 20 % global yield). We also verified that the Heck reaction using arenediazonium salts occurs in an efficient way in alternative reaction media, like PEG and ionic liquids. A series of new chiral ionic liquids was prepared and evaluated in the Heck reaction. In spite the overall performance of the Heck reaction, in all the cases studied no asymmetric induction was detected. Our results demonstrate the enormous synthetic potential of the Heck reaction using arenediazonium salts, constituting a versatile methodology in Organic Synthesis. / Doutorado / Quimica Organica / Doutor em Ciências

Os líquidos iônicos, por geralmente apresentar, em sua estrutura, uma cadeia alquílica apolar e uma parte polar, como o cátion imidazólio, podem ser considerados estruturas anfifílicas, e apresentam semelhanças com os tensoativos. Tais estruturas, devido a este caráter anfifílico, podem interagir com estruturas do tipo Lipossomas ou até mesmo com biomoléculas, como a BSA. Neste trabalho, foram sintetizados três líquidos iônicos inéditos, com rendimentos de 52 a 66%, acoplados a sistemas quirais derivados de aminoácidos naturais e de fácil obtenção, como a L-Cisteína, a L-Serina e a L-Treonina. Estes foram caracterizados tanto do ponto de vista estrutural, quanto por suas propriedades fotofísicas. Como procedimento metodológico utilizou-se de ciclocondensação de aminoácidos, esterificação de Steglich e alquilação para inserção de cadeia carbônica ao anel metil-imidazol. Para investigação e confirmação dessas estruturas utilizou-se de estudos de Ressonância Magnética de 1H e de 13C, Infravermelho, além das espectroscopias de absorção na região do UV-Vis e de emissão de fluorescência. Por fim, estes novos líquidos iônicos foram testados com lipossomas e BSA, cujos resultados mostraram boa interação com essas biomoléculas. / Ionic liquids can be considered as amphiphilic structures and have similarities with the surfactants, once they generally have an apolar alkyl chain and a polar moiety, such as the imidazolium cation. Such structures, due to this amphiphilic character, may interact with liposome structures or even with biomolecules, such as BSA. In this work, three new ionic liquids containing chiral systems derived from naturally occurring amino acids, such as L-Cysteine, L-Serine and L-Threonine were synthesized, with yields ranging from 52 to 66%. They were fully characterized both from the structural point of view, and by its photophysical properties. As methodological procedures, amino acid cyclocondensation, Steglich esterification and alkylation were used. In order to investigate and confirm these structures, magnetic resonance studies of 1H and 13C, infrared, as well as absorption spectroscopies in the UV-Vis region and fluorescence emission were used. At last, these new ionic liquids were tested with liposomes and BSA, and the results showed good interaction with these biomolecules.

This work deals with electrolytes and ionic liquids for Li-ion batteries. Following interaction of electrolytes and ionic liquids to electrodes material. In the theoretical part attention is focused on the description of battery electrolytes and ionic liquids for lithium-ion batteries.

Isoporous membranes are attractive for the regulation and detection of transport at the molecular level. A well-defined asymmetric membranes from diblock copolymers with an ordered nanoporous membrane morphologies were fabricated by the combination of block copolymer self-assembly and non-solvent-induced phase separation (NIPS) technique. This is a straightforward and fast one step procedure to develop integrally anisotropic (“asymmetric”) membranes having isoporous top selective layer. Membranes prepared via this method exhibit an anisotropic cross section with a thin separation layer supported from underneath a macroporous support. These membrane poses cylindrical pore structure with ordered nanopores across the entire membrane surfaces with pore size in the range from 20 to 40 nm. Tuning the pore morphology of the block copolymer membranes before and after fabrication are of great interest. In this thesis, we first investigated the pore morphology tuning of asymmetric block copolymer membrane by complexing with small organic molecules. We found that the occurrence of hydrogen-bond formation between PS-b-P4VP block copolymer and –OH/ –COOH functionalized organic molecules significantly tunes the pore morphology of asymmetric nanoporous membranes. In addition, we studied the complexation behavior of ionic liquids with PS-b-P4VP block copolymer in solutions and investigated their effect on final membrane morphology during the non-solvent induced phase separation process. We found that non-protic ionic liquids facilitate the formation of hexagonal nanoporous block copolymer structure, while protic ionic liquids led to a lamella-structured membrane. Secondly, we demonstrated the catalytic activity of the gold nanoparticle-enhanced hollow fiber membranes by the reduction of nitrophenol. Also, we systematically investigated the pore morphology of isoporous PS-b-P4VP using 3D imaging technique. Thirdly, we developed well-distributed silver nanoparticles on the surface and pore walls of PS-b-P4VP block copolymer membranes and then investigated the biocidal activity of the silver nanoparticles grown membranes. Finally, a novel photoresponsive nanostructured triblock copolymer membranes were developed by phase inversion technique. In addition, the photoresponsive behavior on irradiation with light and their membrane flux and retention properties were studied.

Depuis le début du 21ème siècle, les liquides ioniques (LIs) représentent une importante source d'innovation dans la recherche académique et industrielle en chimie puisqu'ils peuvent être synthétisés, modulés puis utilisés dans de nombreuses applications. De par leurs avantages, les LIs font l'objet d'un véritable engouement dans le domaine des matériaux polymères. Ainsi, ce travail décrit la synthèse de sels organiques originaux pour le développement de polyélectrolytes inédits. Pour cela, nous avons développé de nouvelles voies d'accès à des imidazoliums fonctionnalisés par des fonctions époxydes par l’utilisation d'une méthodologie d'oxydation efficace, flexible et transposable sur une échelle de plusieurs grammes. L'analyse thermique de ces sels a dévoilé une excellente stabilité thermique jusqu'à 400 °C et une température de transition vitreuse basse généralement comprise entre -60 °C et -26 °C. A la suite de ces résultats, la stratégie a été élargie aux anions afin de proposer des fonctions époxydes associées à des sulfonimides inédits. Au cours de cette deuxième phase, l'insertion de fonctions époxydes sur l'anion sulfonimide a été réalisée avec succès permettant un accès à différents prépolymères comme un cation/anion triépoxyde. Dans une deuxième partie, nous avons réalisé une étude mécanistique en utilisant un sel monoépoxyde en présence de différentes amines pour identifier les principaux sites actifs lors de la polymérisation. Grace à ces informations, nous avons confirmé la stabilité de l’imidazolium et la très bonne réactivité de l’époxyde vis-à-vis de diverses amines conduisant à une meilleure compréhension de l'architecture globale du réseau. A partir de ces travaux, un réseau époxy inédit a été mis en œuvre en collaboration avec le laboratoire d'ingénierie des matériaux polymères (IMP) de l'INSA de Lyon. Pour cela, un sel diépoxyde a été sélectionné puis copolymérisé avec un durcisseur diamine (Jeffamine D230) afin de concevoir des réseaux époxy/amine flexibles présentant des propriétés très intéressantes par rapport aux réseaux époxy classiques. / Since the beginning of the 21th century, Ionic liquids (ILs) have been an important source of innovation in chemical academic and industrial research because they can be synthesized, modulated and used then in many applications. Because of their advantages, ILs are of great interest in the field of polymer materials. Thus, this work describes the synthesis of original organic salts to develop innovative polyelectrolytes. For this, we have developed new routes to access to imidazolium salts functionalized by reactive epoxide functions thanks to the development of an effective and flexible oxidative methodology, feasible on a large scale. The thermal analysis of this salts revealed a very good thermal stability up to 400°C and a low glass transition temperature between -60 °C and -26 °C generally. Following these results, the study was extended to anions to provide epoxides associated with novel sulfonimides. During this second phase, the insertion of epoxide functions on the sulfonimide anion was successfully carried out allowing access to different prepolymers such as a triepoxide cation/anion. In a second part, we carried out a mechanistic study using a monoepoxide salt in the presence of different amines to identify the main active sites during the polymerization. According to this information, we have confirmed the stability of the imidazolium and the very good reactivity of the epoxide with various amines leading to a better understanding of the overall architecture of the network. From this work, a novel epoxy network was prepared in collaboration with the polymer materials engineering laboratory (IMP) of INSA of Lyon. For this, a diepoxide salt was selected and copolymerized in the presence of a diamine hardener (Jeffamine D230) in order to design flexible epoxy/amine networks having very interesting properties in comparison with conventional epoxy networks.

No description available.