Conjugated polymers and oligomers have been widely studied based on their wide range of useful properties and applications. Given the importance of self-assembly and charge transfer in the development of conjugated materials for use in electronic applications, it is crucial to: (i) prepare functional materials by molecular design, (ii) evaluate the structure-property relationships of new materials, and (iii) develop fundamental understanding of electronic structure and charge transport behavior. The use of conjugated polymeric materials in electronic applications relies on control of the assembly and orientation of the polymer chains in the solid state. Conjugated polymers with liquid crystalline behavior could be used to implement an additional level of control over orientation and resultant properties. Substitution of the conjugated polythiophene backbone with semifluoroalkyl side chains (i.e., the diblock -(CH2)m(CF2)nF) has afforded materials with unusual properties. The mutual immiscibility of the aromatic backbone, the alkyl side-chain segments, and the fluoroalkyl side-chain termini provides control over supramolecular packing. A series of eight polymers has been synthesized, in which the lengths of the alkyl (m) and fluoroalkyl (n) segments are varied. One regiorandom analogue and two poly(3-alkylthiophene)s were also synthesized for comparative purposes. The structure, molecular weight, and regioregularity of the polymers were evaluated using a variety of techniques. The semifluoroalkyl-substituted polymers have been systematically studied to determine the effect of side chain length and m:n block ratios on their solution state, liquid crystalline, and solid state properties. The effect of side chains on conjugation was determined, where solubility allowed, by solution-state UV-visible and fluorescence spectroscopy. The thermal and liquid crystalline properties of the homopolymers were evaluated by DSC, variable-temperature X-ray diffraction, and polarized optical microscopy. Several semifluoroalkyl-substituted polythiophene homologues show liquid crystalline behavior. Molecular packing and charge transport are key factors governing the use of conjugated materials in electronic applications. A wide variety of oligomers have been studied as models for charge migration in conjugated polymers. One-dimensional models do not adequately represent two-dimensional charge transport; thus, a variety of two-dimensional, covalently-linked models have been developed. Previous work by our group, and others, led to the proposal of bis(oligothienyl) compounds as models to study the interaction of the ð-conjugated chains. Previous reports by other researchers described the synthesis and characterization of hydrogen-terminated analogues of 1,8-bis(oligothienyl)naphthalenes. However, these materials proved to be unsuitable for use as charge transport models, as they were subject to irreversible polymerization upon oxidation. Installation of methyl groups at the terminal a-positions of 1,8-bis(oligothienyl)naphthalenes allowed us to create a series of models in which conjugated chains are held in close proximity. This provides access to multiple redox states, and future systems based on these molecules may be used as models for charge transport or as functional materials for incorporation into devices.

Oligomers and polymers based on functionalized Rf-amides were successfully synthesized for the fabrication of hydrophobic surfaces with either linear or network structure. Firstly, new functionalized Rf-amides (RfCONH-, Rf is a perfluoroalkyl segment) were developed in most cases by a one step reaction and a simple work-up procedure. The reaction behaviors of synthesized Rf-amides in polyreactions were well understood. New fluorinated oligoester polyols, blocked IPDI's, and end-hydroxyl terminated oligo(urea urethane)s have been synthesized, the detail structures and properties are well understood. These materials could be suitable components of powder coatings. On the other hand, the end-hydroxyl terminated oligo(urea urethane)s could be used as reactive additives in high solid content and water-borne coatings. Hydrophobic smooth surfaces based on linear polymers, poly(urea urethane)s and alternating MI copolymers, containing fluorinated side groups were successfully constructed. The attachment of fluorinated side groups into polymers can dramatically alter the surfaces of corresponding polymers from more hydrophilic to hydrophobic due to the enrichment of fluorinated side groups on the top of the surface. The backbone configuration, the polarity of backbones, and the thermal treatment on surfaces can influence the surface properties of corresponding materials. Finally, hydrophobic surfaces of cross-linked polyurethanes as model top coatings were constructed under melt condition at high temperature (180 and 190 oC) using the combination of fluorinated oligouretdiones and non-fluorinated oligoester polyols. It was found that the hydrophobicity of resulting cured films is a matter of the competition between the formation of cross-linking network and the segregation of fluoromoieties on the top of the surface.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-10T18:55:15Z No. of bitstreams: 1 VANESSA SENA CORREIA LIMA - DISSERTAÇÃO PPG-CEMat 2014..pdf: 2636512 bytes, checksum: 9ac482edb8899e0ace77f9887e1dd23e (MD5) / Made available in DSpace on 2018-04-10T18:55:15Z (GMT). No. of bitstreams: 1 VANESSA SENA CORREIA LIMA - DISSERTAÇÃO PPG-CEMat 2014..pdf: 2636512 bytes, checksum: 9ac482edb8899e0ace77f9887e1dd23e (MD5) Previous issue date: 2014-09-15 / Biomaterial é um termo usado para indicar os materiais que constituem as peças de implantes médicos, dispositivos extracorporais, e descartáveis que têm sido utilizados em medicina bem como em todos os aspectos de saúde do paciente. As aplicações dos biomateriais são muitas e variadas, incluindo desde dispositivos de uso prolongado, como veias e válvulas artificiais, a dispositivos de exames, como endoscópios. Endoscopia, que significa olhar por dentro, trata-se de uma especialidade médica que se utiliza de um equipamento chamado de endoscópio para diagnóstico e tratamento de enfermidades. Através da endoscopia podem-se diagnosticar enfermidades, efetuar biópsias de lesões, extrair corpos estranhos, realizar dilatações, fazer acompanhamentos após cirurgias, passar sondas ou cateteres, tratar sangramentos, retirar pólipos e acessar a via biliar para realizar procedimentos cirúrgicos. Os endoscópios flexíveis possuem em sua ponta flexível uma borracha conhecida como Fluoroelastômero Viton®. Os fluorelastômeros são elastômeros sintéticos fluorados, conhecidos como Borracha Fluorada para serviços em temperaturas elevadas e ambientes quimicamente agressivos. Baseado no exposto este trabalho teve como objetivo estudar o fluorelastômero Viton® utilizado no revestimento de ponteiras dos equipamentos endoscópicos. Foram verificadas três grupos de amostras de ponteiras de endoscópios constituídas de Viton® denominadas G, M e P, em sua forma virgem e tratadas com álcool etílico e HCl, ambos concentrados, onde estas amostras foram caracterizadas por Microscopia Óptica (MO), Microscopia Eletrônica de Varredura (MEV), Espectroscopia na Região de Infravermelho com Transformada de Fourier (FTIR), Espectroscopia por Energia Dispersiva de raios X (EDS), Difração de raios X (DRX), Ensaio de Ângulo de Molhabilidade e Ensaio de Citotoxicidade. Verificou-se para todas as amostras (G, M e P) uma superfície com morfologia granulada e irregular, com presença de elementos contaminantes e imperfeições, com bandas características de fluorelastômeros, difratogramas amorfos típicos de elastômeros, caráter hidrofílico e toxicidade em meio celular exceto para a amostra M. Observou-se que o tratamento com álcool etílico não provocou alteração estrutural no fluorelastômero agindo apenas como eliminador de impurezas superficiais. O tratamento com HCl provocou alterações na morfologia e estrutura química do elastômero. Verificou-se a necessidade de adaptação da rota de produção deste fluorelastômero para utilização como biomaterial. Foi proposta a utilização de revestimentos a base siloxanos que possam aumentar a vida útil do fluorelastômero Viton®. / Biomaterial is a term used to indicate the materials constituting the parts of medical implants, extracorporeal devices, disposable and which have been used in medicine as well as in all aspects of patients' health. The applications of biomaterials are many and varied, ranging from extended use devices such as artificial valves and veins, the devices exams such as endoscopes. Endoscopy, which means looking inside, it is a medical specialty that uses a device called endoscope for diagnosis and treatment of diseases. By endoscopy can be diagnosed illnesses, perform biopsies of lesions, extracting foreign bodies, perform dilations, do follow ups after surgery, spend probes or catheters, to treat bleeding, remove polyps and access to the surgical procedures biliary. Flexible endoscopes have in your flexible rubber tip one known as Viton® fluoroelastomer. The fluoroelastomers are synthetic fluorinated elastomers, known as Rubber Fluorinated services to high temperatures and chemically aggressive environments. Based on the above this work was to study the Viton® fluoroelastomer coating used on tips of endoscopic equipment. Three groups of samples from the tips of endoscopes consist of Viton® called L, M and P, in its virgin form and treated with HCl and ethyl alcohol, both concentrated where these samples were characterized by Optical Microscopy (OM), Electron Microscopy Were Verified (SEM), Spectroscopy in the Region of Fourier Transform Infrared (FTIR) Spectroscopy Energy Dispersive X-ray (EDS), diffraction (XRD), test of Angle Wettability and Cytotoxicity Assay rays. It was found for all samples (L, M, P) and a surface irregular with granular morphology, presence of contaminants and imperfections, characteristic bands of fluoroelastomers, typical XRD of amorphous elastomers, hydrophilic, and toxicity in cell except for M. In the sample was observed that treatment with ethanol did not cause structural changes in the fluoroelastomer as scavenger only surface impurities. Treatment with HCl caused changes in the morphology and chemical structure of the elastomer. There was a need to adapt the production of fluoroelastomer route for use as a biomaterial. The use of coatings siloxanes base that can increase the life of Viton® fluoroelastomer was proposed.

Les glycosylamines sont des précurseurs très utiles pour préparer une grande diversité de produits naturels et leurs analogues d’intérêts biologiques. Elles ont été particulièrement utilisées comme imines latentes dans des réactions avec différents nucléophiles principalement organométalliques pour former des imino-C-glycosides. Considérant les avantages des t-butanesulfinyl imines d’Ellman en tant qu’électrophiles pour l’addition stéréocontrôlée de différents réactifs pour former des amines, nous avons synthétisé puis exploré la réactivité des t-butanesulfinyl glycosylamines encore peu connues. Nous rapportons ici nos résultats sur la préparation de plusieurs glycosylamines et leur réactivité vis-à-vis de dérivés de magnésium et de lithium, y compris des réactifs fluorés, pour former des amines sous forme de chaîne ouverte. Des détails sont donnés sur les effets de stéréochimie à l’oeuvre dans cette méthode. Nous présentons également la transformation des amines intermédiaires en imino-C-glycosides, incluant des composés importants comme des mimes de glycosyl phosphates portant une aglycone fluorée. L’évaluation biologique de plusieurs de ces composés a été réalisée sur la GlfT2, une cible enzymatique ayant fort un potentiel pour le traitement de la tuberculose. / Glycosylamines are convenient precursors of a diversity of natural products and analogs of biological interest. In particular they have been used as latent imine equivalents in reactions with various organometallic nucleophiles to prepare imino-C-glycosyl compounds. Considering the advantages of Ellman t-butanesulfinyl imines as convenient electrophiles for the stereocontrolled addition of various groups to form amines, we explored the synthesis and reactivity of yet little known t-butanesulfinyl glycosylamines. We report herein our results on the preparation of various glycosylamines and their reactivity towards magnesium and lithium derivatives, including fluorinated reagents, to give open-chain amines. Details are given on the stereochemical effects involved in this process. We also present the transformation of the intermediate amines into imino-C-glycosyl products, including such significant compounds as glycosyl phosphate mimics bearing a fluorinated aglycone. Biological evaluation of number of compounds has been performed on GlfT2, an enzyme of importance regarding to its potential as target for the treatment of tuberculosis disease.

Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / In this work a theoretical study was carried out to investigate the spectroscopic properties of trivalent europium complexes. The study was divided into two parts. The first one was the study of the luminescent efficiency of five complexes which had as ligands β-diketones and pyrazole. Pyrazole modifications were made promoting a gradual increase in the amount of fluorine atoms in the search for systems with greater luminescence. The second part was the study of structural elucidation and luminescent efficiency of two Eu3+ complexes, which showed as ligand the molecule of ibuprofen and methylbipyridine. The difference between the two systems was that in one complex the methyl group of bipyridine was in the meta position and in the other in the para position. Semiempirical methodologies such as the Sparkle models, the INDO/S-CIS method, the Judd-Ofelt theory and the energy transfer models proposed by Malta et al were used to certify this. The theories and models used to treat the spectroscopic properties of these systems are implemented in the LUMPAC - Luminescence Package, which was used in this study. In the first part, an evaluation of calculation models of the ground state geometry more suitable for the study and from comparisons with crystallographic structures the model that presented smaller error was the Sparkle/PM3. From the results obtained, it has been seen that the luminescence intensity of the Eu3+ complexes increases when the C-H bonds are replaced by C-F bonds, and more strongly when CF2 groups are added. Further extension in the length of the fluorinated chain greatly decreases the rate of nonradiative decay and increases the rate of radiative decay, thereby increasing the quantum efficiency of the complex. The results obtained were theoretically compared with the experimental results and showed good agreement. In the second part of the work, no evaluation of the geometry calculation model was performed, since it is a system that does not have certain crystallographic structures. Thus, the RM1 model was used to optimize the geometry, since it is a recent model that satisfactorily treats lanthanide systems. The results obtained did not show much difference, that is, the position of the methyl group in the meta or para position in the bipyridine linker does not cause considerable effect on the coordination polyhedron. However, they presented higher radiative decay rates than the rates of non-radiative decay and high quantum efficiency. Finally, the good agreement between the theoretical results and the experimental results is a strong indicatio / Neste trabalho foi realizado um estudo teórico para a investigação das propriedades espectroscópicas de complexos de európio trivalente. O estudo foi dividido em duas partes. Na primeira foi feito o estudo da eficiência luminescente de cinco complexos os quais tinham como ligantes β-dicetonas e pirazol, sendo que no pirazol foram realizadas modificações promovendo um aumento gradativo na quantidade de átomos de flúor na busca por sistemas com maior luminescência. Na segunda parte foi feito o estudo de elucidação estrutural e da eficiência luminescente de dois complexos de Eu3+, os quais apresentavam como ligante a molécula de ibuprofeno e a metilbipiridina. A diferença entre os dois sistemas era que em um complexo o grupo metil da bipiridina estava na posição meta e no outro na posição para. Para isto, foram utilizadas metodologias semiempíricas, tais como os modelos Sparkle, o método INDO/S-CIS, a teoria de Judd-Ofelt e os modelos transferência de energia propostos por Malta e colaboradores. As teorias e modelos utilizados para tratar das propriedades espectroscópicas destes sistemas, estão implementados no pacote computacional LUMPAC – Luminescence Package, o qual foi utilizado neste estudo. Na primeira parte, fez-se uma avaliação dos modelos de cálculo da geometria do estado fundamental mais adequada para o estudo e a partir de comparações com estruturas cristalográficas o modelo que apresentou menor erro foi o Sparkle/PM3. A partir dos resultados obtidos, foi visto que a intensidade de luminescência dos complexos de Eu3+ aumenta quando as ligações C-H são substituídas por ligações C-F, e mais fortemente quando grupos CF2 são adicionados. A extensão adicional no comprimento da cadeia fluorada diminui fortemente a taxa de decaimento não radiativo e aumenta a taxa de decaimento radiativo, aumentando dessa maneira a eficiência quântica do complexo. Os resultados obtidos teoricamente foram comparados com os resultados experimentais e apresentaram boa concordância. Na segunda parte do trabalho, não foi realizado avaliação de modelo de cálculo de geometria, por se tratar de sistemas que não apresentam estruturas cristalográficas determinadas. Assim, foi utilizado o modelo RM1 para otimização da geometria, por se tratar de um modelo recente que trata de maneira satisfatória sistemas lantanídicos. Os resultados obtidos não apresentaram muita diferença, ou seja, a posição do grupo metil na posição meta ou para no ligante bipiridina não causa efeito considerável sobre o poliedro de coordenação. No entanto, apresentaram taxas de decaimento radiativo maiores do que as taxas de decaimento não radiativo e elevada eficiência quântica. Por fim, a boa concordância entre os resultados teóricos e os resultados experimentais é um forte indício que as estruturas propostas correspondem aos sistemas sintetizados. / São Cristóvão, SE

Ce travail porte sur la synthèse et la caractérisation de membranes polymères échangeuses d'anions, destinées à la protection de l'électrode à air dans une batterie lithium-air (en vue d'une application pour véhicule électrique). Ces matériaux à architecture de réseaux interpénétrés de polymères (RIP) associent un réseau polyélectrolyte cationique hydrocarboné, la poly(épichlorohydrine) (PECH), à un réseau de polymère neutre qui peut être soit hydrocarboné, soit fluoré. Tout d'abord, la synthèse du réseau polyélectrolyte et son assemblage sur l'électrode à air ont été optimisés. Une première série de RIP associant ce réseau PECH à un réseau de poly(méthacrylate d'hydroxyéthyle) a été synthétisée. Une seconde série de matériaux combinant ce même réseau PECH à un réseau de polymère fluoré a été développée. L'ensemble de ces matériaux a été caractérisé, et pour chaque série de RIP, la méthode de synthèse et la composition ont été optimisées. Les membranes RIP présentent des propriétés améliorées par rapport au réseau simple de PECH. L'électrode à air protégée par ces nouvelles membranes échangeuses d'anions présente une stabilité améliorée dans les conditions de fonctionnement de la batterie lithium-air. Plus précisément, une durée de vie de 1000 h est obtenue lorsque l'électrode à air a été modifiée avec un RIP fluoré, soit une augmentation d'un facteur 20 de la durée de vie de l'électrode non modifiée. / This work focuses on the synthesis and characterization of polymer membranes to be used as anion exchange membranes for protection on an air electrode in a new lithium–air battery for electric vehicle. In these materials showing interpenetrating polymer networks (IPN) architecture, a hydrogenated cationic polyelectrolyte network, the poly(epichlorohydrin) (PECH), is associated with a neutral network, which can be either hydrogenated or fluorinated. First, the synthesis of the polyelectrolyte network and the membrane/electrode assembly were optimized. Second, a first IPN series associating the PECH network with a poly(hydroxyethyl methacrylate) network was synthesized. Third, the same PECH network was associated with a fluorinated polymer network. All the materials were characterized, and optimal synthesis methods as well as an optimal composition were determined for each association. The IPNs show improved properties compared with the single PECH network. The air electrode protected by these new anion exchange membranes shows improved stability in the working conditions of the lithium-air battery. Specifically, a lifetime of 1000 h was obtained when the electrode was modified with a fluorinated IPN, a 20-fold increase in the lifetime of the non-modified electrode.

The goal of this study is to present kinetic studies of (co)polymerization as well as the synthesis and characterization of amphiphilic copolymers with a fluorinated segment. Copolymers were obtained by RAFT (co)polymerizations using one-pot and miniemulsion methods. Different monomers were used to obtain stable selforganized systems, being that one of them was always fluorinated. The resulting copolymers showed different properties, especially when evaluating their selforganization. For this reason, different methodologies for self-organization were used, depending on the synthetic route by which the copolymers were obtained. The self-organization systems formed by the fluorinated amphiphilic copolymers were analyzed by dynamic light scattering (DLS) to determine the size and distribution of the species. The micellar systems analyzed showed great potential for the use in diagnostic imaging, which makes it possible to identify the presence of fluorine in the interior of the micelles through 19F NMR analysis. Relaxation times T1 were measured and values were similar to those reported in the literature. To reinforce the above statement, we performed cell viability assays, which demonstrated the biocompatibility of fluorinated amphiphilic copolymers. / O objetivo deste trabalho é apresentar estudos cinéticos de (co)polimerizações bem como a síntese e a caracterização de copolímeros anfifílicos contendo um segmento fluorado, os quais foram obtidos através de (co)polimerizações RAFT pelos métodos one-pot e miniemulsão. Diferentes monômeros foram utilizados para a obtenção de sistemas auto-organizados estáveis, sendo um deles sempre fluorado. Os copolímeros resultantes apresentaram propriedades distintas, principalmente quando se avalia a autoorganização dos mesmos. Por este motivo, diferentes metodologias para autoorganização foram utilizadas, dependendo da rota sintética pela qual os copolímeros foram obtidos. Os sistemas auto-organizados formados pelos copolímeros anfifílicos fluorados foram analisadas por espalhamento de luz dinâmico (DLS) para determinação de tamanho e distribuição das espécies. Os sistemas micelares analisados apresentaram grande potencial para utilização em diagnósticos por imagens sendo possível identificar a presença de flúor no interior das micelas através de análises por RMN 19F. Os tempos de relaxação T1 foram medidos e os valores encontrados foram semelhantes aos reportados na literatura. Para reforçar a afirmação acima, foram realizados ensaios de viabilidade celular que demonstraram a biocompatibilidade dos copolímeros anfifílicos fluorados.

In this thesis, we focused on the understanding of the synthesis and texturization processes of hydrophobic and (super)hydrophobic fluorinated surfaces by atmospheric plasmas.<p><p>First, we focused on the surface modifications of a model surface, the polytetrafluoroethylene (PTFE), by the post-discharge of a radio-frequency plasma torch. The post-discharge used for the surface treatment was characterized by optical emission spectroscopy (OES) and mass spectrometry (MS) as a function of the gap (torch-sample distance), and the helium and oxygen flow rates. Mechanisms explaining the production and the consumption of the identified species (N2, N2+, He, O, OH, O2m, O2+, Hem) were proposed. <p><p>The surface treatment was then investigated as a function of the kinematic parameters (from the motion robot connected to the plasma torch) and the gas flow rates. Although no change in the surface composition was recorded, oxygen is required to increase the hydrophobicity of the PTFE by increasing its roughness, while a pure helium plasma leads to a smoothing of the surface. Based on complementary experiments focused on mass losses, wettability and topography measurements coupled to the detection of fluorinated species on an aluminium foil by XPS, we highlighted an anisotropic etching oriented vertically in depth as a function of the number of scans (associated to the treatment time). Atomic oxygen is assumed to be the species responsible for the preferential etching of the amorphous phase leading to the rough surface, while the highly energetic helium metastables and/or VUV are supposed to induce the higher mass loss recorded in a pure helium plasma.<p><p>The second part of this thesis was dedicated to the deposition and the texturization of fluorinated coatings in the dielectric barrier discharge (DBD). The effects of the nature of the precursor (C6F12 and C6F14), the nature of the carrier gas (argon and helium), the plasma power, and the precursor flow rate were investigated in terms of chemical composition, wettability, topography and crystallinity by SIMS, XPS, WCA, AFM and XRD. We showed that hydrophobic surfaces with water contact angles (WCA) higher than 115° were obtained only in the presence of argon and were assumed to be due to the roughness created by the micro-discharges. Plasma-polymerized films in helium were smooth and no WCA higher than 115° was observed. We also studied the impact of the deposition rate and the layer thickness in the hydrophobic properties as well as the polymerization processes through the gas phase characterization.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Au cours de ces trente dernières années, les allylboranes, une classe particulière de composés organoborés, ont pris une place particulièrement importante en synthèse organique, principalement dans la synthèse stéréocontrôlée d'alcools homoallyliques par addition sur un aldéhyde. C'est dans ce contexte que s'inscrit mon travail de thèse qui a pour objectif la mise au point de voies d'accès originales à deux familles d'allylboronates alpha-hétérosubstitués et à l'étude de leur réactivité. Pour cela, nous nous sommes intéressés dans un premier temps au comportement de gamma-borylallylsilanes vis à vis de diverses espèces électrophiles, ce qui a permis d'accéder notamment à des alpha-fluoroallylboronates, précurseurs de (Z)-1-fluoro-1-alcènes et à des fluorures allyliques. D'autres électrophiles, hétéroatomiques ou carbonés, peuvent être utilisés pour conduire après refonctionnalisation par addition sur des aldéhydes à des alcools insaturés de structures variées. Dans une seconde partie, nous avons synthétisé des alpha-isocyanatoallylboronates par réarrangement sigmatropique [3,3] d'allylcyanates borylés. Ces intermédiaires réactionnels, particulièrement intéressants pour accéder en série optiquement active à des ènecarbamates cycliques à sept chaînons, sont également précurseurs de pyrrolidines tétrasubstituées selon un réarrangement jusqu'alors non décrit dans la littérature. / Over the last thirty years, allylboranes, a particular class of organoboron compounds, have found many valuable applications in organic synthesis, mainly in the stereoselective synthesis of homoallylic alcohols via addition to aldehydes. In this context, we have developed two novel families of alpha-heterosubstituted allylboronates. We first studied the behavior of gamma-borylallylsilanes towards various electrophilic species in order to access to alpha-fluoroallylboronates which are versatile precursors of various fluorinated molecules. Other heteroatom or carbon electrophiles could also be used to afford after refunctionalization with aldehydes structurally diverse unsaturated alcohols. In the second part of this thesis, we studied the reactivity of alpha-isocyanatoallylboronates prepared by [3,3] sigmatropic rearrangement of borylated allylcyanates. These intermediates have proven to be particularly useful to synthesize optically active cyclic seven membered enecarbamates and tetrasubstituted pyrrolidines.

Différentes membranes conductrices anioniques ont été développées pour protéger une électrode à air fonctionnant dans une batterie Zinc-Air alimentée par de l’air ambiant. Dans ces conditions, le dioxyde de carbone contenu dans l’air, en contact avec l’électrolyte basique, se transforme en carbonate de potassium qui précipite dans la structure poreuse de l’électrode. Cela provoque l’augmentation de sa résistance et la perte de son étanchéité, et l’électrode n’est alors stable que 80 heures. L’objectif de cette étude est donc de rendre stable une électrode à air pendant 3000 heures de fonctionnement.Pour cela, différents réseaux (semi-)interpénétrés de polymères ont donc été développés en associant un polyélectrolyte et un réseau partenaire neutre. La polyépichlorhydrine greffée avec du 1,4-diazabicyclo(2,2,2)octane et un polyélectrolyte fluoré ont été choisis comme polymère conducteur anionique. Des réseaux neutres à base de poly(méthacrylate de 2-hydroxyéthyle), d’alcool polyvinylique et de perfluoropolyéther leur ont été, tour à tour, associés. Les propriétés physico-chimiques des différentes membranes développées ont été caractérisées selon leur densité de charges et leur composition. Les membranes présentant les meilleures propriétés requises (conductivité anionique, prise en masse limitée, sélectivité, …) ont ensuite été assemblées sur des électrodes à air dont le potentiel et la stabilité ont été évalués au cours du fonctionnement en demi-cellule. Ainsi, une électrode à air modifiée avec de telles membranes peut présenter un potentiel stable pendant 6800 heures de fonctionnement à -30mA/cm². / Different anionic conducting membranes have been developed to protect an air electrode operating in a Zinc-Air battery fed with ambient air. Under those conditions, carbon dioxide from atmospheric air reacts with the alkaline electrolyte, and is then transformed into potassium carbonate. The precipitate of this carbonate inside the electrode porous structure leads to the increase of the system resistance and the loss of its sealing after 80 h of operation. The objective of this study focuses on the improvement of the stability of an air electrode for 3000 h of operation, by protecting it from carbonation reaction with a polymer membrane.For this, different (semi-)interpenetrating polymer networks have therefore been developed combining a polyelectrolyte and a neutral network partner. Polyepichlorohydrin grafted with 1,4-diazabicyclo (2,2,2) octane and a fluorinated polyelectrolyte were chosen as anionic conductive polymer. Neutral networks based on poly (2-hydroxyethyl methacrylate), polyvinyl alcohol and perfluoropolyether were then, alternately, associated to the polyelectrolyte. The physico-chemical properties of the various developed membranes were characterized according to their charge density and composition. The membranes with the best required properties (anionic conductivity, limited weight uptake, selectivity ...) were then assembled on air electrodes whose potential and stability have been evaluated during the operation in half-cell. Thus, an air electrode modified with such membranes maintains a stable potential during 6800 hours of running at -30mA / cm².