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Dans le cadre d’un projet d’Intensification de Procédés de Rhodia, nous avons développé des dispositifs millifluidiques fonctionnant dans des conditions opératoires inexplorées auparavant au labortoire, jusqu’à 300 °C et 50 bar, pour l’acquisition de données physicochimiques. Ainsi, une étude rhéologique sur des solutions de sel de nylon a été réalisée, ce qui a permis de fournir une nouvelle corrélation utile pour le dimensionnement du procédé industriel de polymérisation du polyamide-6,6. Par ailleurs, une étude cinétique de la polymérisation de l’éthylène glycol avec l’acide adipique a permis de déterminer les coefficients cinétiques de la réaction ainsi que l’énergie d’activation correspondante. Finalement un procédé miniaturisé avec élimination de l’eau produite par la réaction de polycondensation permettant de déplacer l’équilibre atteint par la réaction a été mis en œuvre ainsi que son modèle. / This work originated from a Rhodia’s Process Intensification project, where new physicochemical data are needed. We have developed at the laboratory new millifluidic devices which operate in conditions previously unexplored: up to 300 °C and 50 bar. A rheological study on nylon salt solutions was carried out and a new correlation based on the experimental results was provided. It is now used in the design of the industrial process of polyamide-6,6 synthesis. Moreover, a kinetic study on the polymerization of ethylene glycol with adipic acid allowed us to determine the kinetic coefficients of the reaction and the corresponding activation energy. Finally, a millifluidic process where the water produced by the polymerization reaction is eliminated by stripping and membrane separation was also developed, allowing for the chemical equilibrium to be shifted. A model describing this process has also been proposed.

The objective of this study is to synthesize nematic-thermotropic liquid crystalline polymers (LCP) and determine their possible application areas. In this context, thirty different LCP&rsquo / s were synthesized and categorized with respect to their fiber formation capacity, melting temperature and mechanical properties. The basic chemical structure of synthesized LCP&rsquo / s were composed of p-acetoxybenzoic acid (p-ABA), m-acetoxybenzoic acid (m-ABA), hydroquinone diacetate (HQDA), terephthalic acid (TPA) and isophthalic acid (IPA) and alkyl-diacids monomers. In addition to mentioned monomers, polymers and oligomers were included in the backbone such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) polymers, and polybutylene naphthalate (PBN), polyhexylene naphthalate (PHN) and poly butylene terephthalate (PBT) oligomers that contain different kinds of alkyl-diols. We adjusted the LCP content to have low melting point (180oC-280oC) that is processable with thermoplastics. This was achieved by balancing the amount of linear (para) and angular (meta) groups on the aromatic backbones together with the use of linear hydrocarbon linkages in the random copolymerization (esterification) reaction. LCP species were characterized by the following techniques / Polarized Light Microscopy, Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Analysis (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), X-ray Scattering (WAXS, Fiber diffraction), surface free energy, end group analysis (CEG), intrinsic viscosity (IV) and tensile test. According to these analysis LCPs were classified into five main categories / (I) fully aromatics, (II) aromatics+ PET/PEN, (III) aromatics + oligomers (IV) aromatics + short aliphatic diacids, (V) aromatics + long aliphatic diacids. The foremost results of the analysis can be given as below. DSC analysis shows that some LCPs are materials that have stable LC mesogens under polarized light microscopy. In TGA analysis LCPs that have film formation capacity passed the thermal stability test up to 390oC. NMR results proved that predicted structures of LCPs from feed charged to the reactor are correct. In FTIR due to the inclusion of new moieties, several peaks were labeled in the finger-print range that belongs to reactants. In X-ray analysis, LCP24 (containing PET) was found to be more crystalline than LCP25 (containing PEN) which is due to the symmetrical configuration. Block segments were more pronounced in wholly aromatic LCP2 than LCP24 that has flexible spacers. Another important finding is that, as the amount of the charge to the reactor increases CEG value increases and molecular weight of the product decreases. Selected group V species were employed as reinforcing agent and mixed with the thermoplastics / acrylonitrile butadiene styrene (ABS), nylon6 (PA6), polyethylene terephthalate (PET), polypropylene (PP) and appropriate compatibilizers in micro compounder and twin screw extruder. The blends of them were tested in dog-bone and/or fiber form. In general LCPs do not improve the mechanical properties except in composite application with polypropylene. A significant increase in tensile properties is observed by LCP24 and LCP25 usage. Capillary rheometer studies show that the viscosity of ABS decreases with the inclusion PA6 and LCP2 together. In addition to the composite applications, some LCPs are promising with new usage areas. Such as nano fibers with 200nm diameter were obtained from LCP27 by electrospinning method. The high dielectric constant of LCP29 has shown that it may have application areas in capacitors.

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.