Álcoois primários sulfatados de cadeia longa, usualmente na forma de sais de sódio, são tensoativos de grande interesse comercial utilizados em diversas formulações de higiene pessoal e limpeza doméstica. Eles são produzidos comercialmente através da reação de álcoois etoxilados com trióxido de enxofre seguida de imediata neutralização com hidróxido de sódio. O produto formado é uma solução neutra de álcool primário etoxilado sulfatado em água. Sabe-se que a armazenagem desse produto por longos períodos de tempo em temperaturas elevadas pode levar à hidrólise completa, mas, em condições normais de uso e temperatura ambiente é esperado que o produto seja resistente à hidrólise. No entanto observou-se que algumas amostras comerciais de lauril éter sulfato de sódio que foram estocadas por diferentes períodos de tempo em frascos fechados à temperatura ambiente sofreram hidrólise em intervalos de tempo relativamente curtos. Isso leva à hipótese de que o comportamento de hidrólise seria influenciado por outras variáveis além da temperatura e do tempo de estocagem. O presente trabalho consistiu em identificar as variáveis de maior impacto na reação de hidrólise por meio de experimentos planejados. O teor de ativos foi acompanhado ao longo da reação para avaliar o efeito da presença de eletrólitos, de material insulfatado, em diferentes temperaturas, variando-se o pH inicial por meio da adição de ácido clorídrico. O comportamento da reação de hidrólise observado foi compatível com aquele descrito na literatura para o dodecil sulfato de sódio. A hidrólise apresentou-se como sendo autocatalítica, com a aceleração da taxa de reação provavelmente causada pela presença de íons hidrogênio liberados na reação. Foi possível identificar que as variáveis de maior efeito na reação foram: pH inicial, o teor de cloreto de sódio e a temperatura. O modelo de troca iônica em pseudo-fase foi utilizado para o tratamento dos resultados experimentais e mostrou-se adequado tendo sido, portanto, utilizado para prever o comportamento de estabilidade do produto à temperatura ambiente e nas condições em que o produto é normalmente comercializado. Um modelo empírico de redes neurais foi desenvolvido com sucesso para prever o comportamento do pH ao longo do tempo para as condições estudadas. / Long-chain primary alkyl sulfuric acids, usually as their sodium salts, are important commercial surfactants used in a large number of household and personal care formulations. They are commercially produced by treatment of mixtures of ethoxylated fatty alcohols with sulfur trioxide followed by immediate neutralization with sodium hydroxide, a neutral aqueous mixture of sodium primary alkyl ether sulfate is obtained. It is known that prolonged storage of the material at elevated temperature can lead to complete hydrolysis but under normal use and typical environmental conditions the product is expected to be resistant to hydrolysis. In spite of that it has been observed that some commercial samples of sodium lauryl ether sulfate stored for different periods of time in sealed containers at room temperature have undergone hydrolysis in a relatively short period of time which leads to the hypothesis that the hydrolysis behavior would be strongly influenced by variables other than temperature and storage time. The present work consisted of identifying the process variables with the most significant effect on the acid hydrolysis by using experimental design. The rate of hydrolysis has been followed acidimetrically to evaluate the effect of electrolytes as well as the concentration of unsulfated matter at different temperatures, over a wide initial pH range, under the presence of added hydrochloric acid. The pattern of kinetic behaviour observed was broadly the same as previously described for the sodium dodecyl sulfate. The hydrolysis presented the characteristic autocatalytic form, the catalysis presumably arising from the production of hydrogen sulfate ions. It was possible to observe that the most significant effects on the rate of hydrolysis were the initial pH, the total amount of sodium chloride and the temperature. The results were also discussed in terms of the ion-exchange pseudophase model of the micelle reaction. Accordingly to the fitting of parameters that was carried out it is possible to conclude that the pseudo-phase ion-exchange theory is found to account satisfactorily for the results reported and it was used to predict the stability behavior of the product at room temperature and under normal commercial conditions. A neural network based model was also successfully developed in order to predict the pH behavior in the conditions studied.

La quinocarcine, la tétrazomine et la lémonomycine constituent une sous-famille appartenant à la famille des tétrahydroisquinoléines trisubstituées naturelles. Ce sont des puissants agents cytotoxiques et possèdent de nombreuses activités biologiques telles qu’antitumorales et antibiotiques. Leur complexité structurale, leurs intérêts biologiques ainsi que leur faible rendement d’extraction du milieu naturel font de ces molécules des cibles attrayantes pour les chimistes de synthèse.Ces trois molécules sont constituées d’une tétrahydroisoquinoléine différemment substitué fusionnée avec un diazabicycle[3.2.1]octane commun. Le but de ce projet était de mettre au point une stratégie commune à cette sous-famille et divergente grâce à la synthèse du diazabicyclooctane en premier. Une première stratégie faisant intervenir une aziridine n’a pas permis de construire le bicycle. Cet objectif a été réalisé grâce à une seconde stratégie. Elle repose sur une première cyclisation d’un hémiaminal puis d’une cyclisation par addition nucléophile d’un éther d’énol silylé sur un N-acylimmonium formé in situ au départ d’un N,S-acétal.Parallèlement à cette étude synthétique, nous avons mis au point une réaction multicomposant séquentielle qui permet l’accès rapide et général aux a-amidosulfures, comblant un manque dans la littérature. Ensuite nous avons étudié la réactivité de ces composés en tant que précurseurs simples de N-acylimines en conditions acides douces. Trois conditions réactionnelles, nous ont permis d’accéder à cette objectif : l’utilisation stœchiométrique d’acétate d’argent, catalytique d’acide phosphorique ainsi que le NIS en quantité stœchiométrique et catalytique. Cette dernière réaction est très attrayante. En effet, ce réactif doux et neutre permet l’élimination efficace du thiol formant la N-acylimine puis son activation pour se faire piéger in situ par un nucléophile. Les rendements atteints sont très hauts en moins de 5 minutes. / Quinocarcin, tetrazomin and lemonomycin constitute a subfamily belonging to the family of natural trisubstituted tetrahydroisquinolines. These are powerful cytotoxic agents and have many biological activities such antitumor and antibiotics. Their structural complexity, biological interests and their low efficiency of extraction of the natural environment make these molecules attractive targets for synthetic chemists.These three molecules are constituted of differently substituted tetrahydroisoquinoline diazabicycle merged with a [3.2.1] octane common. The purpose of this project was to develop a common strategy in this subfamily and divergent with the synthesis of diazabicyclooctane first.A first strategy involving an aziridine failed to build the bicycle. This objective was achieved through a second strategy. It is based on a first cyclization of hemiaminal followed by cyclization of nucleophilic addition of a silyl enol ether of an N-acylimmonium formed in situ from a N, S-ketal.Along with this synthetic study, we developed a multicomponent reaction sequence that allows quick general access to -amidosulfides, filling a gap in the literature. Then we studied the reactivity of these compounds as simple precursors of N-acylimines in mild acidic conditions. Three reaction conditions allowed us to reach this goal: the use of stoichiometric silver acetate, phosphoric acid as catalyst and NIS in catalytic and stoichiometric amount. This last reaction is very attractive. Indeed, this sof and neutral reagent allows the efficient removal of the thiol forming the N-acylimine and its activation to be trapped in situ by a nucleophile. The yields are very high in less than 5 minutes.

Due to their outstanding properties, poly(arylene ethers) are useful as toughness modifiers in epoxy resins (EP). Furthermore, these polymers show rather low intrinsic fire risks. According to recent research it has been incorporated that poly(arylene ether phosphine oxides) [PAEPO’s] can further improve the fire behavior. Increasing phosphorous content of the PAEPO can influence the fire behavior too. Fire retardants containing phosphorus – regardless of whether an additive or reactive approach is used – show different mechanisms in the condensed and gas phase. In the present study PSU Control (BPA based polysulfone) with four different PAEPO’s and their corresponding blends with an EP were investigated. All poly(arylene ether phosphine oxides) were synthesized by nucleophilic aromatic polycondensation. The polymers obtained covered a wide range of weight average molar masses (6,000 – 150,000 g/mol) as determined by size exclusion chromatography with multi-angle light scattering detection (MALLS). FTIR, NMR spectroscopy and MALDI-TOF revealed formation of the desired polymer structure of the linear poly(arylene ethers). All polymers were easily soluble in common organic solvents, thus enabling processing from solution.The pyrolysis and the fire retardancy mechanisms of the polymers and blends with epoxy resin (EP) were tackled by means of a comprehensive thermal analysis (thermogravimetry (TG), TG-evolved gas analysis) and fire tests [PCFC, limiting oxygen index (LOI), UL-94, cone calorimeter]. The Mitsunobu reaction of Dimethyl-5-hydroxyisophthalate and a long chain semifluorinated alcohol requires triphenyl phosphine as a reactant. Identical, in some case higher yield was obtained in the usual conditions, with triphenyl phosphine and with trivalent phosphorus containing polymers, which was prepared in solvent free bulk (melt) polymerization technique from trivalent phosphorus monomer and a silylated diphenol in presence of CsF. Purification and the recovery of the final product which is always a big challenge in case of Mitsunobu reaction, was far more easier using polymer compared to triphenyl phosphine. During polymerization there was a possibility to have polymer having repeating unit containing both trivalent phosphorus and phosphine oxide. The trivalent phosphorus content of the polymer can be varied using different molar concentration of CsF.

This dissertation reports the synthesis and characterization of semi-fluorinated polymers derived from the polymerization of bisphenols with fluoroalkenes. A series of diverse bisphenols were chosen from popular commercial bisphenols and new polycyclic aromatic hydrocarbon (PAH) derived bisphenols requiring synthesis. Step-growth condensation polymerization of bisphenols with three different fluoroalkene types was performed while probing polymerization conditions and the structure/properties relationship of the resulting fluoropolymers. The fluoroalkene monomers were chosen from bis(trifluorovinyloxy)biphenyl (TFVE), perfluorocyclohexene (PFCH), and perfluoro acyclic monomers, namely, perfluoro(4-methyl-2-pentene) and 1-perfluoroheptene to undergo this chemistry. This work is divided into four parts based on the polymerization methodology. The first section focuses on the development of a new class of fluorinated arylene vinylene ether (FAVE) and their chain extended polymers prepared via base-catalyzed step-growth polymerization of PAH bisphenols with the TFVE monomer. These reactions afforded polymers containing controlled terminal and enchained fluoroalkenylenes for latent reactivity such as post polymerization functionalization, chain extension, and/or crosslinking. In general, these PAH cores resulted in polymers with improved thermal properties The second portion describes the investigation of step-growth addition/elimination polymerizations of PAH bisphenols and PFCH to prepare a new class of fluoropolymers containing alternating rigid PAH linkages and enchained PFCH vinylene ether moieties in the backbone. The third section covers the preparation and characterization of semi-fluorinated poly(aryl ether sulfone)s by nucleophilic addition/elimination reactions of PFCH with sulfone bisphenols. From commercially bisphenols combined with PAH bisphenols, we introduced the industrially valuable and property enhancing diaryl sulfone unit in a series of semi-fluorinated copolymers. This modular approach greatly expands access to partially fluorinated aryl ether sulfone polymers intended for high performance applications in optoelectronics, separation/purification membranes, and composites. Finally, in the fourth section, a new class of semifluorinated polymers was synthesized via nucleophilic addition/elimination reactions of acyclic perfluoroalkenes with bisphenols. In particular, environmental concerns for biopersistent and highly regulated perfluorooctanoic acid (PFOA) is the driver for using perfluoroheptene, which is derived cleanly by the decarboxylation of these pollutants in one step. This provided a new class of semi-fluorinated materials with promising properties including thermal stable, processability, and transparent film formation.

Advanced polymeric materials, such as polyether ether ketones (PEEK), have been placed as direct substitutes for metals and ceramics in diverse applications, such as the machinery industry and biomedical engineering. Moreover, surface treatments allow the emergence of brand-new properties or the improvement of preexisting ones, such as friction, lubrication, wettability, cellular infiltration, or osseointegration. A paramount approach to achieving topographical modifications is by using laser micro/nanoprocessing techniques such as direct laser interference patterning (DLIP). Herein, PEEK foils are structured with DLIP method using ultrashort pulses. The influence of the pulse duration between 266 fs and 15 ps and the pulse-to-pulse overlap on the resulting surface topography and chemistry is assessed. As a result, well-defined line-like textures with a period of 5.8 μm and aspect ratios up to 0.88 are achieved. Furthermore, it is possible to explore and understand the behavior of surface phenomena such as swelling, increase/decrease of laser–material interaction onset, and laser-induced periodic surface structures formation. A comprehensive topographical and chemical characterization study demonstrates that these distinctive topographical features occur because of multiphoton absorption, incubation effects, and heat accumulation. These phenomena allow structuring polymeric substrates that are low-absorbing and challenging to pattern with conventional nanosecond infrared (IR) laser sources.

No description available.

De nouveaux glycopolymères greffés aux paramètres macromoléculaires contrôlés [dextrane-g-poly(acrylate de diéthylène glycol cholestéryle), Dex-g-PADEGChol] ont été préparés en quatre étapes via la stratégie de synthèse « grafting from». L'originalité de ces glycopolymères réside dans la combinaison, et pour la première fois, d'une dorsale polysaccharide hydrophile biocompatible/ biodégradable et de greffons polymères hydrophobes à caractère mésogène. L'ATRP a été utilisée pour contrôler la croissance des greffons PADEGChol en milieu homogène à partir d'un macroamorceur dérivé de dextrane (DexAcBr). Les conditions de polymérisation avaient été préalablement ajustées en étudiant l'homopolymérisation du monomère ADEGChol en présence d'un amorceur modèle et de plusieurs systèmes catalytiques CuIBr/(PMDETA ou OPMI) dans différents solvants (THF ou toluène). Le caractère amphiphile de ces glycopolymères a été évalué et leurs propriétés mésomorphes ont été étudiées par calorimétrie différentielle à balayage, microscopie optique à lumière polarisante et par diffraction des rayons X. Des études préliminaires par microscope électronique à transmission et diffusion dynamique de la lumière polarisée ont démontré que ces glycopolymères adoptent une morphologie vésiculaire appelée « polymersome » en phase aqueuse, lorsque le DMSO est utilisé comme co-solvant. Ces nano-objets pourront être testés ultérieurement pour la formulation d'un nouveau type de vecteurs de principes actifs / New graft glycopolymers with well-defined parameters [dextran-g-poly(diethylene glycol cholesteryl ether acrylate) (Dex-g-PADEGChol)] have been prepared in four steps using the "grafting from" strategy. Challenge of this work arises from the combination for the first time of a hydrophilic, biocompatible/biodegradable polysaccharide backbone with mesogen hydrophobic polymeric grafts. Controlled growth of the grafts (PADEGChol) was obtained using ATRP initiated in homogeneous medium from a dextran derivative (DexAcBr). In order to find the best polymerization conditions, homopolymerization of ADEGChol monomer was investigated using an initiator model and various catalytic systems CuIBr/(PMDETA or OPMI) in two solvents (Toluene and THF). The amphiphilic properties of such glycopolymers were evaluated and their mesomorphic properties have been studied by thermal polarizing optical microscopy, differential scanning calorimetry and X-ray scattering. Using transmission electron microscopy and dynamic light scattering, vesicular morphology called "polymersome" was observed in aqueous medium when DMSO was used as co-solvent. These polymersomes could be tested as new drug delivery systems

Les tétrazoles ont une place importante dans la chimie médicinale contemporaine par leurs caractéristiques spatiales et électroniques uniques. Leur haute teneur en azote leur confère également des qualités requises dans le développement de substances explosives et de haute énergie. Le développement de nouveaux outils synthétiques pour les créer prend donc ici tout son sens. Dans cet ouvrage, il est tout d’abord question d’une nouvelle méthode de synthèse qui génère des tétrazoles bicycliques en conditions douces par l’entremise d’azidonitriles aliphatiques séparés par trois ou quatre atomes de carbone (effet de proximité) et d’acides de Lewis. De plus, cette méthode de synthèse présente une réaction tandem qui génère des tétrazoles oxabicycliques 1,5-dialkylés via une cycloaddition 1,3-dipolaire diastéréosélective à partir d’azidoacétals ou d’azidocétals arborant un azoture proximal. La réaction s’effectue dans le nitrométhane de 0 °C à la température ambiante avec du TMSCN et est promue par une variété d’acides de Lewis dont le BF3OEt2. Les aspects mécanistiques de la réaction (l’ouverture des acétals, l’équilibre entre les éthers de cyanhydrine, la cycloaddition 1,3-dipolaire diastéréosélective et le réarrangement de Boyer-Schmidt-Aubé) ainsi que les paramètres réactionnels (solvants, acides de Lewis, stœchiométrie, sources de cyanure, etc.) seront en outre abordés. Ensuite, le motif de tétrazole oxabicyclique a été l’objet de diversifications, de fonctionnalisations et de transformations afin d’en valoriser l’utilité. Des réactions d’alkylations, d’azoturations radicalaires, de bêta-éliminations et de diversifications de la chaîne latérale ont été étudiées. De ces mêmes motifs de tétrazoles, la synthèse de tétrazoles azabicycliques et celle de morpholines 2,6-polysubstituées ont aussi été investiguées. La synthèse d’un sel de tétrazolium et l’alkylation de 5-tétrazolyllithiums ont aussi fait l’objet d’études préliminaires. Enfin, une étude théorique en DFT a été effectuée pour mieux comprendre l’équilibre tétrazole-azidoazométhine sur des motifs de types benzo- et pyrido- diazidodiazines parents à la 6-azidotétrazolo[5,1-a]phthalazine, un métabolite toxique du Gymnodinium breve (Ptychodiscus brevis, aussi actuellement connu sous le nom de Karenia brevis). Les aspects thermodynamiques, les états de transition, les orbitales HOMO, les cartes de potentiels d’ionisation locaux, les cartes de densité de la LUMO, les effets de solvant et certains paramètres permettant d’évaluer l’aromaticité (indices de Bird, ordres de liaison minimaux de Jug, indices HOMA et NICS) ont été considérés dans l’étude. Le constat a été que certaines des analyses théoriques peuvent constituer de bons outils prédictifs, particulièrement avec des considérations thermodynamiques, mais que cette approche a aussi ses limites qui sont principalement dues aux incertitudes inhérentes aux calculs théoriques. / Tetrazoles have an important place in contemporary medicinal chemistry due to their unique spatial and electronic characteristics. Their high nitrogen content also gives them the qualities required for the development of explosive and high energy substances. The development of new synthetic tools to create them takes here all its meaning. Therefore, in this work, a new synthesis method that generates bicyclic tetrazoles under mild conditions using aliphatic azidonitriles separated by three or four carbon atoms (proximity effect) and Lewis acids will first be discussed. In addition, a tandem reaction which generates 1,5-dialkylated oxabicyclic tetrazoles via a diastereoselective 1,3-dipolar cycloaddition from azidoacetals or azidoketals bearing a proximal azide will also be disclosed. The reaction is carried out in nitromethane at 0 °C to room temperature with TMSCN and is promoted by a variety of Lewis acids including BF3OEt2. The mechanistic aspects of the reaction (acetal opening, equilibrium between cyanohydrin ethers, diastereoselective 1,3-dipolar cycloaddition and Boyer-Schmidt-Aubé rearrangement) as well as the reaction parameters (solvents, Lewis acids, stoichiometry, cyanide sources, etc.) will be discussed. Furthermore, the oxabicyclic tetrazole unit was involved in diversifications, functionalizations and transformations to enhance its utility. Reactions of alkylations, radical azidations, beta-eliminations and diversifications of the side chain were applied. From these same tetrazole units, the synthesis of azabicyclic tetrazoles and that of 2,6-polysubstituted morpholines was also investigated. The synthesis of a tetrazolium salt and the alkylation of 5 tetrazolyllithiums were also the subject of preliminary studies. Finally, a theoretical DFT study was carried out to have a better understanding of the tetrazole-azidoazomethine equilibrium on benzo- and pyrido- diazidodiazines similar to 6 azidotetrazolo [5,1-a] phthalazine, a toxic metabolite from Gymnodinium breve (Ptychodiscus brevis, actually known as Karenia brevis). Thermodynamic aspects, transition states, HOMO orbitals, local ionization potential maps, LUMO density maps, solvent effects, and some parameters to evaluate the aromaticity (Bird index, Jug minimum bond order, HOMA index and NICS) were considered in the study. It has been noted that some of the theoretical analysis can be good predictive tools, particularly with thermodynamic considerations, but they also have their limits, which are mainly due to the uncertainties inherent in the theoretical calculations.