No description available.

For the first time stabilizer-free vinylidene fluoride (VDF) polymerizations were carried out in homogeneous phase with supercritical CO₂. Polymerizations were carried out at 140°C, 1500 bar and were initiated with di-tert-butyl peroxide (DTBP). In-line FT-NIR (Fourier Transform- Near Infrared) spectroscopy showed that complete monomer conversion may be obtained. Molecular weights were determined via size-exclusion chromatography (SEC) and polymer end group analysis by 1H-NMR spectroscopy. The number average molecular weights were below 104 g∙mol−1 and polydispersities ranged from 3.1 to 5.7 depending on DTBP and VDF concentration. To allow for isothermal reactions high CO₂ contents ranging from 61 to 83 wt.% were used. The high-temperature, high-pressure conditions were required for homogeneous phase polymerization. These conditions did not alter the amount of defects in VDF chaining. Scanning electron microscopy (SEM) indicated that regular stack-type particles were obtained upon expansion of the homogeneous polymerization mixture. To reduce the required amount of initiator, further VDF polymerizations using chain transfer agents (CTAs) to control molecular weights were carried out in homogeneous phase with supercritical carbon dioxide (scCO₂) at 120 °C and 1500 bar. Using perfluorinated hexyl iodide as CTA, polymers of low polydispersity ranging from 1.5 to 1.2 at the highest iodide concentration of 0.25 mol·L-1 were obtained. Electrospray ionization- mass spectroscopy (ESI-MS) indicates the absence of initiator derived end groups, supporting livingness of the system. The “livingness” is based on the labile C-I bond. However, due to the weakness of the C-I bond perfluorinated hexyl iodide also contributes to initiation. To allow for kinetic analyses of VDF polymerizations the CTA should not contribute to initiation. Therefore, additional CTAs were applied: BrCCl3, C6F13Br and C6F13H. It was found that C6F13H does not contribute to initiation. At 120°C and 1500 bar kp/kt0.5~ 0.64 (L·mol−1·s−1)0.5 was derived. The chain transfer constant (CT) at 120°C has been determined to be 8·10−1, 9·10−2 and 2·10−4 for C6F13I, C6F13Br and C6F13H, respectively. These CT values are associated with the bond energy of the C-X bond. Moreover, the labile C-I bond allows for functionalization of the polymer to triazole end groups applying click reactions. After substitution of the iodide end group by an azide group 1,3 dipolar cycloadditions with alkynes yield polymers with 1,2,3 triazole end groups. Using symmetrical alkynes the reactions may be carried out in the absence of any catalyst. This end-functionalized poly (vinylidene fluoride) (PVDF) has higher thermal stability as compared to the normal PVDF. PVDF samples from homogeneous phase polymerizations in supercritical CO₂ and subsequent expansion to ambient conditions were analyzed with respect to polymer end groups, crystallinity, type of polymorphs and morphology. Upon expansion the polymer was obtained as white powder. Scanning electron microscopy (SEM) showed that DTBP derived polymer end groups led to stack-type particles whereas sponge- or rose-type particles were obtained in case of CTA fragments as end groups. Fourier-Transform Infrared spectroscopy and wide angle X-ray diffraction indicated that the type of polymorph, α or β crystal phase was significantly affected by the type of end group. The content of β-phase material, which is responsible for piezoelectricity of PVDF, is the highest for polymer with DTBP-derived end groups. In addition, the crystallinity of the material, as determined via differential scanning calorimetry is affected by the end groups and polymer molecular weights. For example, crystallinity ranges from around 26 % for DTBP-derived end groups to a maximum of 62 % for end groups originating from perfluorinated hexyl iodide for polymers with Mn ~2200 g·mol–1. Expansion of the homogeneous polymerization mixture results in particle formation by a non-optimized RESS (Rapid Expansion from Supercritical Solution) process. Thus, it was tested how polymer end groups affect the particles size distribution obtained from RESS process under controlled conditions (T = 50°C and P = 200 bar). In all RESS experiments, small primary PVDF with diameters less than 100 nm without the use of liquid solvents, surfactants, or other additives were produced. A strong correlation between particle size and particle size distribution with polymer end groups and molecular weight of the original material was observed. The smallest particles were found for RESS of PVDF with Mn~ 4000 g·mol–1 and PFHI (C6F13I) - derived end groups. / Erstmalig gelang es, stabilisatorfreie Vinylidenfluorid (VDF)-Polymerisationen in homogener Phase mit überkritischem CO₂ (scCO₂) bis zu vollständigem Monomerumsatz durchzuführen. Die Homogenität während der Polymerisation wurde durch in-line Fourier-Transform Nahinfrarot Spektroskopie beobachtet. Für Polymerisationen bei 140 °C und 1500 bar wurde Di-tert-butylperoxid (DTBP) als Initiator verwendet. Es wurden Polymere mit einem Zahlenmittel der Molmasse kleiner 104 g·mol–1 und Polydispersitäten zwischen 3.1 und 5.7. erhalten. Um isotherme Reaktionen zu ermöglichen, wurden CO₂-Gehalte zwischen 61 und 83 wt.% verwendet. Die für die homogene Reaktionsführung erforderlichen hohen Drücke und Temperaturen haben keinen Einfluss auf die Mikrostruktur des Polymers. Zur Verringerung der Initiatorkonzentration wurden weitere Polymerisationen unter Verwendung von Kettentransferreagenzien (CTA) bei 120 °C und 1500 bar in homogener Phase mit scCO₂ durchgeführt. Perfluoriertes Hexyliodid als CTA ermöglicht kontrollierte radikalische Polymerisationen, wobei Polymere mit geringer Polydispersität zwischen 1.5 und 1.2 erhalten wurden. Endgruppenanalyse mit Elektronenspray-Ionisations-Massen¬spektro¬metrie (ESI-MS) zeigte, dass keine Initiatorendgruppen im Polymer enthalten sind. Diese Beobachtung unterstützt den lebenden Charakter der Polymerisationen und basiert auf einer labilen C-I-Bindung im Polymer. Aufgrund der schwachen C-I-Bindung trägt das perfluorierte Hexyliodid (C6F13I) auch zur Initiierung bei. Polymerisationen in Gegenwart von BrCCl3, C6F13Br und C6F13H zeigten, dass nur C6F13H keinen Beitrag zur Initiierung leistet. Bei 120 °C und 1500 bar wurde ein kp/kt0.5 von ~ 0.64 (L·mol−1·s−1)0.5 bestimmt, wobei kp der Wachstums- und kt der Terminierungsgeschwindigkeitskoeffizient sind. Die Kettentransfer¬konstanten (CT) bei 120°C betragen 8·10−1, 9·10−2 und 2·10−4 für C6F13I, C6F13Br und C6F13H. Die Änderung der CT-Werte lässt sich mit der zunehmenden Bindungsenergie in der Reihe C-I, C-Br und C-H erklären. Die labile C-I-Bindung ermöglicht eine Funktionalisierung des Polymers durch Click-Reaktionen. Nach Substitution der Iodid-Endgruppe durch eine Azidgruppe erfolgte eine katalysatorfreie 1,3-dipolare Cyclaoaddition mit Alkinen zu Polymeren mit 1,2,3-Triazol-Endgruppen. Dieses endfunktionalisierte PVDF besitzt im Vergleich zu konventionellem PVDF eine höhere thermische Stabilität. Nach der Expansion der Polymerisationsmischung mit scCO₂ auf Umgebungsbedingungen lag das Polymer als weißes Pulver vor, das im Hinblick auf z.B. Polymerendgruppen, Kristallinität, Gestalt und Größe der Partikel untersucht wurde. Rasterelektronenmikroskopie zeigte, dass Polymere mit DTBP-Endgruppen zu stapelförmigen Partikeln führen, während bei CTA-Fragmenten als Endgruppen schwamm- oder rosenartige Partikel erhalten wurden. Ergebnisse der FT-IR Spektroskopie und Weitwinkelröntgenbeugung zeigten, dass der höchste Gehalt an β-phasigem Material, der für die Piezoelektrizität des PVDF verantwortlich ist, für PVDF mit Initiatorendgruppen erhalten wurde. DSC (Differential Scanning Calorimetry) Messungen ergaben zudem, dass der Kristallinitätsgrad durch Endgruppen und Polymermasse beeinflusst wird. Die Expansion der homogenen Polymermischung kann als nicht-optimierter RESS-Prozess (Rapid Expanison from Supercritical Solution,) angesehen werden. Aus RESS Experimenten unter kontrollierten Bedingungen wurden jeweils nanoskalige primäre PVDF-Partikel ohne Verwendung von Lösungsmitteln, Tensiden oder anderen Additiven erhalten. Es besteht ein enger Zusammenhang zwischen einerseits der Partikelgröße und der Partikelgrößenverteilung und andererseits der Polymerkonzentration in scCO₂ vor der Expansion, bestimmt durch Polymerendgruppen und Molmassen der eingesetzten Materialien.

Corrosion is one of the most expensive failures in industries that used metal components and other construction materials. In fact, corrosion is responsible for hundreds of billions-dollar loss in the US alone each year. In general, corrosion occurs when metal surfaces are exposed to water, oxygen, acids, bases, or salts. Therefore, metal substrates must be protected by using materials that act as barriers to avoid destructive corrosion attack. Aluminum is one of the most common metals used in the industry; and it is used in many places such as refining and petroleum production equipment, pipelines, and fossil fuel power plants. Aluminum is known to have corrosion resistance due to the forming of an oxide layer that can be reformed rapidly if the surface gets damaged. However, in the long-term the oxide layer cannot protect the aluminum surface from corrosion because it is stable only in neutral mediums and it is soluble in acidic and basic environments. Barrier protection is one of the most effective methods that prevent aluminum surfaces from being exposed to corrosive environments. These barriers can be organic or inorganic coatings that can limit the electron transport or the cathodic and the anodic reactions between aluminum alloys and the surrounding environment. Fluorinated polymers that were used in this study exhibit excellent properties which make them good candidates for corrosion protection applications. These properties include high hydrophobicity which is responsible for repelling oxygen and water and reducing the wettability of the metal surface, strong adhesion to the metal surface allowed for covering and protection of substrates in aggressive environments, and thermal stability that allows for using these polymers in high temperature environments. Overall, the corrosion protection, which was evaluated using electrochemical techniques, and the mechanical properties were improved with these fluorinated polymeric coatings in comparison to the bare aluminum alloys which proves to be advantageous for using these polymeric coatings in many areas including marine environments, oil and gas industries, and fossil fuel power plants.

Fluoropolymers are well-known for their exceptional thermo-oxidative stability, chemical resistance, UV-light resistance, and low surface energy properties, making them essential for high-performance applications across clean energy, medical device, automotive, aerospace, electronics, and telecommunication industries. Since the discovery of poly(tetrafluoroethylene) (PTFE), numerous fluorinated thermoplastics and fluoroelastomers have entered the market. The global fluoropolymer industry is projected to reach $18 billion by 2033. Recent advancements have focused on integrating mainchain fluorocarbon moieties, such as perfluorocyclobutyl (PFCB), perfluorocycloalkenyl (PFCA), fluoroarylene vinylene ether (FAVE), and the hexafluoroisopropylidene (6F) group, into semi-fluorinated polymers. These modifications enhance properties like thermal stability, processability, and optical transparency, while reducing water absorption, thereby enhancing durability. This dissertation introduces a versatile electrophilic aromatic substitution methodology for synthesizing polymer containing the 6F groups, followed by a practical approach for synthesizing semi-fluorinated alcohols and diols. The research explores possibilities for creating novel materials, showcasing the utility of conducting hexafluorohydroxyalkylation by using hexafluoroacetone trihydrate (HFAH) for incorporating the 6F group. An interfacial electrophilic aromatic substitution polymerization using HFAH with aromatic monomers is developed in Chapter 2, which can generate semi-fluorinated polyaryl ethers and polyphenylenes with high regioselectivity and molecular weights up to 60 kDa. These polymers exhibit high solubility in organic solvents and excellent thermo-oxidative stability. The dielectric and optical characterization of these fluoropolymers is presented. Chapter 3 extends this electrophilic substitution methodology to the preparation of random and block semi-fluorinated copolymers, as well as thermoset materials, demonstrating the versatility in polymer design and application through the fluorohydroxyalkylation of aromatic compounds. Chapter 4 details the synthesis and characterization of 4,4’-bis(2-hydroxyhexafluoroisopropyl)diphenyl ether, a semi-fluorinated diol. This monomer was used to prepare the first reported polycarbonate with hexafluoroisopropoxy groups -C(CF3)2O- incorporated in the main chain via polycondensation. Polyesters and polysilyl ethers were also prepared from this diol. Finally, the dissertation explores attempts to form metallocene condensation metallopolymers by reacting the acidic and sterically hindered semi-fluorinated diol with group IVB metallocene dichloride.

Les études présentées dans le cadre de cette thèse visent à copolymériser l'ԑ-caprolactame (CL) avec différents dérivés de l'α-amino-ԑ-caprolactame (qui possèdent une amine primaire fonctionnalisable) par polymérisation anionique par ouverture de cycle. En utilisant cette stratégie, nous décrivons; (i) la préparation de polyamides 6 fluorés thermiquement plus stables, et ayant une surface hydrophobe; (ii) la synthèse de polyamides 6 portant des groupes pendants cinnamoyl thermo et photosensibles. Une réticulation réversible est observée ainsi que l'amélioration des propriétés thermo-mécaniques; (iii) la copolymérisation anionique par ouverture de cycle de CL avec un bis-monomère issu de l'α-amino-ԑ-caprolactame comme contrôle de la réticulation du polyamide 6. Enfin, dans le cadre de notre intérêt continu pour la chimie du polyamide 6, nous avons mis en évidence la possible combinaison de la polymérisation anionique par ouverture de cycle de CL avec la polycondensation en chaîne de l'éthyl-4-butylaminobenzoate pour obtenir en une étape un polyamide aliphatique/aromatique / The studies presented in this thesis aim to copolymerize ԑ-caprolactam (CL) with different derivatives of α-amino-ԑ-caprolactam (which has a functionalizable primary amine) via anionic ring-opening polymerization. By using this strategy, we describe: (i) the synthesis of thermally more stable fluorinated polyamide 6 having a hydrophobic surface; (ii) the synthesis of polyamides 6 bearing pendant cinnamoyl groups, which are thermo-and photoresponsivechromophore groups, and demonstrating their reversible crosslinking as well as improved thermo-mechanical properties; (iii) the copolymerization ofCL with a crosslinker (N-functionalized α-amino-ԑ-caprolactambis-monomers) into crosslinked polyamides 6.As part of our continuing interest in polyamide 6 chemistry, we developed the combination of anionic ring-opening polymerization of CL and chain-growth condensation polymerization of ethyl 4-butylaminobenzoate in order to obtain aliphatic/aromatic polyamides in one-step.

Ce travail s’inscrit dans le cadre du projet Saveurs Vapeurs du Groupe SEB qui vise à développer une nouvelle gamme de cuiseurs vapeur. Cette thèse porte ainsi sur l’analyse des propriétés fonctionnelles de matériaux polymères soumis à deux types de vieillissement rencontrés lors de la cuisson à la vapeur. D’une part, la résistance à la coloration de ces derniers en présence de substances alimentaires colorantes a été évaluée, à 60°C et 100°C. Un colorimètre a été utilisé pour l’analyse de la couleur des échantillons, dans l’espace Lab. Les résultats montrent que seuls les polymères totalement fluorés résistent à la coloration après 1000 heures passées à 100°C. D’autres polymères, comme le polycarbonate, le PET et les polymères partiellement fluorés, ne présentent pas de coloration après 1000 heures à 60°C. La théorie de la solubilité a été utilisée pour la prévision des résultats, et semble fiable dans de nombreux cas. Son application nécessite cependant un approfondissement, car d’autres molécules présentes dans les substances peuvent interférer avec la sorption des molécules colorantes. D’autre part, la résistance de ces polymères au vieillissement hydrothermique a été étudiée, à des températures de 100°C, 120°C et 140°C. Les températures caractéristiques (par DSC, TGA et DMA) et les propriétés mécaniques par DMA ont été mesurées. La reprise d’eau des polymères a également été évaluée. La plupart des polymères, excepté le PE, le PET et les polyamides, ne présentent pas de modifications de leurs propriétés après un vieillissement de 1000 heures à 100°C. Après un vieillissement de 1000 heures à 140°C, seuls les polymères totalement fluorés, le polysulfone et l’ETFE ne montrent aucun signe de changement de propriétés. Ces premiers résultats nécessitent cependant une analyse plus poussée. Une étude des molécules éventuellement libérées durant le vieillissement permettrait de vérifier l’innocuité de ces matériaux / This work is incorporated within the framework of the project Saveurs Vapeurs (Steam Flavors) from the SEB Group, aimed at developing a new assortment of steam cooking devices. This PhD thus deals with the analysis of the functional properties of polymer materials subjected to two types of ageing found during steam cooking. First, coloration resistance of the latter in presence of coloring alimentary substances was evaluated, at 60°C and 100°C. A chromameter was used for the analysis of samples color, in the Lab color space. Results show that only fully fluorinated polymers resist to coloration after 1000 hours spent at 100°C. Some other polymers, like polycarbonate, PET and partially fluorinated polymers, do not show any coloration after 1000 hours at 60°C. The solubility theory was used for anticipation of the results, and seems to be reliable in many cases. However its use needs an in-depth study, because some other molecules found in the substances can interfere with the sorption of colored molecules. Second, hydrothermal ageing resistance of these polymers was studied, at temperatures of 100°C, 120°C, and 140°C. Parameters measured were the characteristic temperatures (by DSC, TGA and DMA) and mechanical properties by DMA. Water mass uptake was also evaluated. Most of the polymers, excepted PE, PET and polyamids, do not show any modification of their properties after 1000 hours ageing at 100°C. After ageing 1000 hours at 140°C, only fully fluorinated polymers, polysulfone and ETFE do not show any sign of properties change. These first results need however a further analysis. A study of possibly liberated molecules during ageing could allow to verify the inoffensiveness of these materials