L'utilisation de la réaction de cycloaddition 1,3 de Huisgen afin d'optimiser les propriétés de polymères fluorés constitue l'objectif de ce travail. Cette cycloaddition a été étudiée selon deux stratégies spécifiques. La première consiste en une cycloaddition, réalisée entre un groupe azidé et une fonction nitrile, non catalysée, tandis que la seconde concerne la cycloadditon, catalysée par le cuivre, entre un groupe azido et une fonction alcyne dont la réaction est classiquement appelée « click chemistry ». Le premier chapitre est consacré à une étude bibliographique sur la réticulation et la post-réticulation chimiques des polymères à température ambiante et à des températures inférieures à 150 °C. Cette étude décrit de façon quasi-exhaustive les différentes réactions chimiques permettant de réaliser une réticulation, et ce en les classant par fonctions clés. Le second chapitre décrit la réticulation d'un élastomère fluoré commercial, porteur de fonction nitrile par cycloaddition 1,3 de Huisgen non catalysée à l'aide d'un agent réticulé fluoré téléchélique bisazidé. Une étude modèle de la réaction de cycloaddition mettant en jeu une réaction nitrile-azide à l'aide de composés moléculaires afin de déterminer les meilleures conditions de réaction. Le troisième chapitre concerne le greffage d'un composé phthalocyanine sur un copolymère fluoré (de type poly(chlorotrifluoéthylène-co-2-iodoethyl vinyl éther) par cycloaddition de Huisgen catalysée au cuivre, ou « click chemistry », dans le but d'obtenir un composé possédant des propriétés photovoltaïques intéressantes. / The objective of this work deals with the Huisgen 1.3 cycloaddition reaction to optimize the properties of fluoropolymers. This cycloaddition is investigated using two main strategies. The first one concerns a cycloaddition performed between an azide group and a nitrile function, and non-catalyzed, while the second one is a copper-catalyzed cycloadditon, involving a group azide and an alkyne function and this reaction is conventionally called "click chemistry". The first chapter is devoted to a non-exhaustive literature review on the chemical crosslinking and post-crosslinking polymers carried out at room temperature and at temperatures below 150 ° C. This study describes a list of different chemical reactions to achieve a crosslinking, and that classifying them by key functions. The second chapter describes the crosslinking of commercially available, fluoroelastomer, bearing nitrile groups by 1,3 Huisgen uncatalyzed cycloaddition using a telechelic fluorintaed bisazido crosslinking agent. This chapter exhibits first a model study of the cycloaddition involving a nitrile-azide reaction to determine the best reaction conditions. The third chapter concerns the grafting of an alkyne phthalocyanine compound onto a fluorinated copolymer (poly(chlorotrifluoethylene-co-2-iodoethyl vinyl ether) by 1,3 Huisgen cycloaddition catalyzed by copper, or "click chemistry", to obtain a compound having good photovoltaic properties.

Les sulfoximines sont une famille de composés dont les domaines d’applications sont très variés. Elles sont utilisées comme auxiliaires, ou ligands pour la synthèse asymétrique et répertoriées comme groupements à forts potentiels dans des composés biologiquement actifs. Les sulfoximines fluorées sont bien plus rares et difficiles d’accès, mais de par les propriétés spéciales induites par le fluor, ont récemment attirées l’attention. Elles ont notamment été utilisées avec succès en tant que réactifs de (per)-fluoroalkylation ou comme groupements super-électroattracteurs. Cependant, il n’y a que de rares exemples de sulfoximines fluorées dans des composés bioactifs. De plus, à notre connaissance, les S-perfluoroalkyl sulfoximines n’ont encore jamais été utilisées comme ligands de métaux ou organocatalyseurs.La thèse porte sur le développement de la synthèse et la fonctionnalisation des sulfoximines fluorées pour la préparation de ligands et d’organocatalyseurs, notamment en version énantiopures. Elle est divisée en 3 chapitres.Le premier chapitre porte sur la synthèse des sulfoximines et des sulfilimines fluorées énantiopures. Sur différentes étapes de la synthèse de ces composés, plusieurs méthodes ont été utilisées, par exemple, la séparation de diastéréoisomères par l’acide de camphorsulphonique, l’oxydation asymétrique de Kagan, Modena, Uemura et aussi l’imination oxydante asymétrique. La CFS (Chromatographie par Fluide Supercritique) semi-préparative a permis de séparer les différents énantiomères des sulfilimines fluorées. L’oxydation des sulfilimines a permis d’obtenir les sulfoximines énantiopures avec de bons rendements. Ces sulfilimines et sulfoximines ont des configurations absolues stables, leurs caractéristiques optiques ont été mesurées ainsi que leurs structures ont été déterminées par diffraction des rayons-X. Le deuxième chapitre est principalement axé sur la N-fonctionnalisation des sulfoximines et leurs développements comme ligands et organocatalyseurs pour la catalyse. Nous avons pu montrer que l’utilisation des micro-ondes pour activer le couplage entre les sulfoximines libres et les aromatiques halogénés permettait d’obtenir de bons résultats et même de diminuer le temps de réaction par rapport à la méthode de chauffage conventionnel. Ce développement a également été utilisé pour préparer des ligands/organocatalyseurs chiraux. Ces nouveaux ligands, sulfoximines fluorées chirales, ont été appliqués dans des procédés de catalyse pour la réaction de Friedel-Crafts, de Biginelli et même comme réactif de Shibata asymétrique pour la trifluoromethylation. Nous avons montré également que ces composés peuvent être utilisés comme ligands ou organocatalyseurs chiraux dans la réaction de Mukaiyama ou de cycloaddition de Diels-Alder conduisant aux produits avec de bons rendements.Le dernier chapitre est basé sur la fonctionnalisation des sulfoximines fluorées par une réaction inédite d’ortholithiation. Dans cette partie, nous démontrons que la fonction sulfoximine fluorée joue le rôle de groupe ortho-directeur. Cela nous a permis d’accéder à une grande variété de sulfoximines orthosubstituées aux structures totalement nouvelles. Les produits dérivés ortho ont été utilisés comme réactifs dans de nombreuses réactions: dans la réaction de Sonogashira, dans la préparation de nouveaux réactif de trifluorométhylation et dans la synthèse d’analogues de composés biologiquement actifs. / Sulfoximines belong to a family of compounds with various application areas. They are used as auxiliaries or ligands for asymmetric synthesis and classified as high potential groups in biologically active compounds. Fluorinated sulfoximines are even more scarce and difficult to access, but special properties induced by fluorine, have attracted particular attention. They have been successfully used as (per)-fluoroalkylating reagent or as super-electron-withdrawing groups. However, there are only a few examples of fluorinated sulfoximines in bioactive compounds. To our knowledge, S-perfluoroalkylated sulfoximines have never been used as ligands of metals or organocatalysts so far.The Thesis focuses on the synthesis and functionalization of fluorinated sulfoximines for the preparation of chiral ligands and/or organocatalysts. It is divided into three chapters.The first chapter deals with the synthesis of enantiopure fluorinated sulfoximines and sulfilimines. During our synthesis, several methods were used, for example, separation of diastereoisomers by using camphorsulphonic acid, and the asymmetric oxidation of Kagan, Modena, Uemura as well as the asymmetric oxidizing imination. The SFC (Supercritical Fluid Chromatography) semi-preparative permits to separate the different enantiomers of fluorinated sulfilimines. Oxidation of sulfilimines led to the formation of enantiopure sulfoximines in good yields. These sulfilimines and sulfoximines are stable retaining their absolute configuration. Optical characteristics were measured and their structures were determined by X-ray diffractions. The second chapter focuses mainly on the N-functionalization of sulfoximines and their developments as organocatalysts and/or ligands for catalysis. Coupling reaction of free sulfoximines with halogenated aromatic under microwave activation led to the formation of products in good yields within short reaction time. This development has also been used to prepare chiral ligands/ organocatalysts. These new chiral fluorinated sulfoximines have been applied in catalytic processes for Friedel-Crafts reaction, Biginelli transformation and as Shibata’s asymmetric trifluoromethylation reagent. We also showed that these compounds may be used as chiral ligands or organocatalysts in Mukaiyama reaction or in Diels-Alder cycloaddition affording products in good yields.The last chapter is based on the functionalization of fluorinated sulfoximines by an ortholithiation reaction. In this part, we have demonstrated that the fluorinated sulfoximine function acts as ortho-directing group. This allowed us to access a wide variety of new ortho-substituted sulfoximine structures. Ortho-derivatives were used as reagents in Sonogashira reaction, in the preparation of novel trifluoromethylation reagents and in the synthesis of some biologically active compound analogues.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第23295号 / エネ博第420号 / 新制||エネ||80(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 萩原 理加, 教授 野平 俊之, 教授 坂口 浩司 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

A new material for use as a proton exchange membrane in fuel cells has been developed: a blend of a perfluorocyclobutane-based block ionomer (S-PFCB) and Poly (vinylidene-co-hexafluoropropylene) (Kynar Flex, KF). This thesis details the work done thus far to characterize the morphology of this material, using small angle x-ray scattering, differential scanning calorimetry, atomic force micrscopy, and some other techniques to a lesser extent. Small angle x-ray scattering (SAXS) of pure S-PFCB showed a strong block copolymer- associated phase separation, on the order of 25 nm. Differential scanning Calorimetry (DSC) confirmed this finding. SAXS also revealed the presence of a peak representing individual ionic aggregates on the order of 3 nm. Finally, it was shown with DSC that no crystallinity develops in the S-PFCB block copolymer, while one of the blocks, known as 6F, crystallizes extensively. SAXS of incremental blend compositions of KF and S-PFCB revealed a steady increase in size of the block copolymer phase separation peak in SAXS, demonstrative of the miscibility of KF and the non-sulfonated 6F block of S-PFCB. Furthermore, this incremental study determined the scattering vector range relevant for comparing amounts of KF crystallinity. DSC of incremental blend compositions revealed two phases of KF crystallinity develops upon cooling a membrane, independent of cooling rate. Atomic force microscopy (AFM), small angle x-ray scattering (SAXS), and differential scanning calorimetry (DSC) corroborate to suggest a nonuniform morphology through the thickness of solution cast membranes. Also, the effect of different casting temperatures and after-casting anneals on morphology was assessed. Future work on this project involves morphological studies at various relative humidities and temperatures, as well as following up on discoveries already made. Finally, transmission electron micrscopy (TEM) should be performed to provide a visual analog, which will greatly help in developing an accurate morphological model. / Master of Science

Poly- och perfluorerade ämnen, även kallad PFAS, har både globalt och i Sverige upptäckts i höga halter i mark samt i yt-och grundvatten de senaste åren. Kemikalierna är svårnedbrytbara och studier visar på att de bland annat är reproduktionsstörande hos djur. Källorna till utsläpp av PFAS är många, men något som uppmärksammats den senaste tiden är fluorvallor som används inom längdskidåkning. I den här studien undersöks hur användningen av skidvalla innehållande PFAS påverkar ett område samt hur dessa ämnen sprids. För att undersöka detta har tidigare mätningar utförda i anslutning till längdskidspår använts, för att se hur spridningen skett vid dem samt vilka koncentrationer som kan påträffas.  Mätningarna var utförda vid skidspår i Oslo, Trondheim, vid Vasaloppet samt vid en tävling i Maine, USA. För att visualisera var i Sverige påverkade områden skulle kunna finnas gjordes dessutom en karta där orter togs ut på två olika sätt. Skidvalla bidrar till att orsaka högre lokala koncentrationer av PFAS, och kan få en stor påverkan i de områden där mycket skidåkning pågår. Samtidigt är det svårt att dra tydliga slutsatser då det finns fåtal studier och många diffusa källor som kan bidra till spridningen av PFAS. / Per- and polyfluoroalkyl substances (PFAS) are man-made chemicals used for their water, grease, and dirt repellent properties. Today these substances are widespread due to their ability to spread through both air and water. PFAS are long-term persistent and have hazardous environmental impact. Among others, affecting the reproduction of animals and has been shown to accumulate in the food chain. One product containing PFAS that has recently gained attention is fluorinated ski wax, due to the ban imposed on fluorinated ski wax by the International Ski Federation (FIS) from the season 2021/2022.  To investigate how the use of ski wax containing PFAS spreads and affects the environment at areas with cross-country skiing, results from previous studies have been analyzed. The previous studies were located at cross-country ski areas in Oslo and Trondheim in Norway, Maine in the USA and at the location of the Swedish competition Vasaloppet. A map has also been made to visualize where in Sweden there might be areas who have been contaminated with per- and polyfluoroalkyl substances by the use of ski wax. To find the locations for these areas two different methods have been used.  The results of the previous studies shows that the use of fluorinated ski waxes gives higher local concentrations of PFAS at the locations of cross-country ski areas that are frequently used. However, it is still difficult to draw clear conclusions about how big the spread of PFAS contamination is, since the substances can be found in many different products and are easily spread. In the future there is a need for more studies and investigation to reach clearer conclusions. In addition, there is a need for more tests around different ski areas to see the impact that competitions have, but also how everyday skiing affects the spread of PFAS.

Hydrophilic/hydrophobic block copolymers as proton exchange membranes (PEMs) has become an emerging area of research in recent years. Three series of hydrophilic/hydrophobic, fluorinated/sulfonated multiblock copolymers were synthesized and characterized in this thesis. These copolymers were obtained through moderate temperature (~100°C) coupling reactions, which minimize the ether-ether interchanges between hydrophobic and hydrophilic telechelic oligomers via a nucleophilic aromatic substitution mechanism. The hydrophilic blocks were based on the nucleophilic step polymerization of 3,3′-disulfonated, 4,4′-dichlorodiphenyl sulfone with an excess 4,4′-biphenol to afford phenoxide endgroups. The hydrophobic (fluorinated) blocks were largely based on decafluoro biphenyl (excess) and various bisphenols. The copolymers were obtained in high molecular weights and were solvent cast into tough membranes, which had nanophase separated hydrophilic and hydrophobic regions. The performance and structure-property relationships of these materials were studied and compared to random copolymer systems. NMR results supported that the multiblock sequence had been achieved. They displayed superior proton conductivity, due to the ionic proton conducting channels formed through the self-assembly of the sulfonated blocks. The nano-phase separated morphologies of the copolymer membranes were studied and confirmed by atomic force microscopy. Through control of a variety of parameters, including ion exchange capacity and sequence lengths, performances as high, or even higher than those of the state-of-the-art PEM, Nafion, were achieved. / Ph. D.

The following studies describe the synthesis and properties of a family of poly(arylene ether ketone)s which are well known to have good thermal stability, mechanical durability, and other film properties. These poly(arylene ether ketone)s were functionalized with fluorine, oxidized, blended, and crosslinked to increase performance with focus on materials for polymeric capacitors and gas separation membranes. There is a need for polymeric capacitors with improved energy storage density and thermal stability. In this work, the affect of polymer molecular structure and symmetry on Tg, breakdown strength, and relative permittivity was investigated. A systematic series of four amorphous poly(arylene ether ketone)s was compared. Two of the polymers had symmetric bisphenols while the remaining two had asymmetric bisphenols. Two contained trifluoromethyl groups while the other two had methyl groups. The symmetric polymers had Tg's of approximately 160 °C while the asymmetric polymers showed higher Tg's near 180 °C. The symmetric polymers had breakdown strengths near 380 kV/mm at 150 °C. The asymmetric counterparts had breakdown strengths near 520 kV/mm even at 175 °C, with the fluorinated polymers performing slightly better in both cases. The non-fluorinated polymers had higher relative permittivities than the fluorinated materials, with the asymmetric polymers being better in both cases. Two amorphous, high glass transition, crosslinkable poly(arylene ether)s for gas purification membranes have been studied. The polymers were polymerized via step growth and contained tetramethyl bisphenol F and either 4,4'-difluorobenzophenone or 4,4'-dichlorodiphenylsulfone. The benzylic methylene group in tetramethyl bisphenol F can undergo oxidation reactions and crosslinking with UV light. The polymers were oxidized under two different conditions, one by chemical treatment using oxone and KBr and one by elevated thermal treatment in air. Thermogravimetric analysis, 1H-NMR and attenuated total reflectance Fourier transform infrared spectroscopy revealed the progress of the thermal oxidation reactions. Both polymers produced tough, ductile films and gas transport properties of the non-crosslinked linear polymers and crosslinked polymer was compared. Crosslinking was performed by irradiating polymer films for one hour on each side in air under a 100W high intensity, long-wave UV lamp equipped with a 365-nm light filter. The O2 permeability of tetramethyl bisphenol F containing non-crosslinked poly(arylene ether ketone) was 2.8 Barrer, with an O2/N2 selectivity of 5.4. Following UV crosslinking, the O2 permeability decreased to 1.8 Barrer, and the O2/N2 selectivity increased to 6.2. Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) is a commercial polymer that is utilized for gas separation membranes. It has a relatively high free volume with high gas permeabilities but suffers from low gas selectivities. In this study, PPO polymers with number average molecular weights of 2000, 6000, 17,000, 19,000 and 22,000 were synthesized and blended with a poly(arylene ether ketone) synthesized from bisphenol A and difluorobenzophenone (BPA-PAEK) to make UV-crosslinkable films. The ketone and benzylic methylene groups on the BPA-PAEK and the PPO polymers respectively formed crosslinks upon exposure to broad wavelength UV light. The crosslinked blends had increased selectivities over their linear counterparts. DSC thermograms showed that the blends with all but the lowest molecular weight PPO had two Tg's, thus suggesting that two phases were present, one high in PBA-PAEK and the other high in PPO composition. The PBA-PAEK blend with the 2000 Mn PPO showed only one Tg between the two control polymers. Despite the immiscibility of these films, the gel fractions after UV exposure were high. Gel fractions as a function of the amount of the 22,000 Mn PPO were explored and did not show any significant change. UV spectroscopy of the individual components and the blends showed that more broad wavelength light was transmitted through the PPO component, so it was reasoned that films that was high in PPO composition crosslinked to deeper depths. The O2/N2 permeabilities and selectivities were measured for the linear and crosslinked films. Between the 33/67, 67/33, and 90/10 22k PPO/BPA PAEK crosslinked blended films, the 90/10 PPO/BPA PAEK gained the most selectivity and maintained a larger amount of its permeability. In comparison to commercial gas separation polymers, the non-crosslinked 33/67 22,000 Mn PPO/BPA PAEK blend outperformed polysulfone and cellulose acetate with a 2.45 degree of acetylation. Overall, we were able to blend a small amount of BPA PAEK with the commercially used PPO to create a mechanically robust crosslinked polymer film. / Ph. D.

Proton exchange membrane fuel cells (PEMFCs) have been extensively studied as clean, sustainable and efficient power sources for electric vehicles, and portable and residential power sources. As one of the key components in PEMFC system, proton exchange membranes (PEMs) act as the electrolyte that transfers protons from the anode to the cathode. The state-of-art commercial PEM materials are typically based on perfluorinated sulfonic acid containing ionomers (PFSAs), represented by DuPont's Nafion®. Despite their good chemical stability and proton conductivity at high relative humidity (RH) and low temperature, several major drawbacks have been observed on PFSAs, such as high cost, high fuel permeability, insufficient thermo-mechanical properties above 80°C, and low proton conductivity at low RH levels. Therefore the challenge lies in developing alternative PEMs which feature associated ionic domains at low hydration levels. Nanophase separated hydrophilic-hydrophobic block copolymer ionomers are believed to be desirable for this purpose Three series of hydrophobic/hydrophillic, partially fluorinated/sulfonated multiblock copolymers were synthesized and characterized in this thesis. The hydrophilic blocks were based upon the nucleophilic step polymerization of 3, 3′-disulfonated, 4, 4′-dichlorodiphenyl sulfone (SDCDPS) with an excess 4, 4′-biphenol (BP) to afford phenoxide endgroups. The partially fluorinated hydrophobic blocks were largely based on 4, 4′-hexafluoroisopropylidenediphenol (6F-BPA) and various difluoro monomers (excess). These copolymers were obtained through moderate temperature (~130-150°C) coupling reactions, which minimize the ether-ether interchanges between hydrophobic and hydrophilic telechelic oligomers via a nucleophilic aromatic substitution mechanism. The copolymers were obtained in high molecular weights and were solvent cast into tough membranes, which had nanophase separated hydrophilic and hydrophobic regions. The performance and structure-property relationships of these materials were studied and compared to random copolymer systems. NMR results supported that the multiblock sequence had been achieved. They displayed superior proton conductivity, due to ionic, proton conducting channels formed through the self-assembly of the sulfonated blocks. The nano-phase separated morphologies of the copolymer membranes were studied and confirmed by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). Through control of a variety of parameters, including ion exchange capacity and sequence lengths, performances as high, or even higher than those of the state-of-the-art PEM, Nafion®, were achieved. Another series of semi-crystalline hydrophobic poly(ether ether ketone)-hydrophilic sulfonated poly(arylene ether sulfone) (PEEK-BPSH100) multiblock copolymers was first synthesized and characterized. However due to their semi-crystalline structure, PEEK blocks are insoluble in most organic solvents at relatively low reaction temperatures, which prevents the coupling reaction between PEEK and BPS100. In order to facilitate the synthesis and processing, removable bulky ketimine was introduced to synthesize amorphous pre-oligomers poly(ether ether ketimine) (PEEKt). The synthetic procedure first involves the synthesis of hydrophobic poly(ether ether ketimine)-hydrophilic sulfonated poly(arylene ether sulfone) (PEEKt-BPS100) multiblock pre-copolymers via coupling reactions between phenoxide terminated hydrophilic BPS100 and fluorine terminated hydrophobic PEEKt blocks. The membranes cast from PEEKt-BPS100 were boiled in 0.5M sulfuric acid water solution to hydrolyze the amorphous PEEKt blocks to semi-crystalline PEEK blocks and acidify BPS100 blocks to BPSH100 blocks simultaneously. FT-IR spectra clearly showed the successful hydrolysis and acidification. The proton conductivity, water uptake and other membrane properties of the acidified semi-crystalline PEEK-BPSH100 membranes were then evaluated and compared with those of the state-of-the-art PEM, Nafion®. / Ph. D.

No description available.

Fluorinated stationary phase in Rtx-200MS column have been characterized by determination of system constants of Abraham equation. Retention on this phase is driven by dispersive and orientation/induction forces. Significant interaction contribution of lone pair electrons or π- electrons provides unique selectivity for analytes with excess of electron density. Unusual behavior of this phase have been determined by study of separation mechanism of polar and nonpolar analytes, in comparison of their separation on polar and nonpolar phases. This behavior is due to medium polarity of the phase (system constant s), which is not so pronounced to cancel separation of nonpolar analytes due to induction forces. In some cases contribution of lone pair electrons or π-electrons can contribute to this separations. Key words fluorinated stationary phase Rtx-200MS, inverse gas chromatography, LFER method, Abraham's equation