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            <title xml:lang="en">State of the art PVDF-based architectures from RAFT/MADIX polymerization of VDF : synthesis, self-assembly and potential membrane application</title>
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                <title xml:lang="en">State of the art PVDF-based architectures from RAFT/MADIX polymerization of VDF : synthesis, self-assembly and potential membrane application</title>
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                <authority type="supervisor">Vincent Ladmiral</authority>
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              <p>This thesis presents new approaches for the preparation of PVDF-based architectures. The synthesis and characterization of different PVDF-based amphiphilic block copolymers and cyclic peptide-PVDF conjugates are described. RAFT/MADIX polymerization of gaseous VDF monomer and different chemistries were employed for the preparation of the BCPs. PVDF and P(VDF-co-HFP) ABA triblock copolymers were obtained through Thia-Michael addition by a “one-pot” strategy involving both PVDF-Xanthate (or P(VDF-co-HFP)-Xanthate) and PEG-diacrylates. PNIPAM-b-PVDF diblock copolymers were prepared by RAFT polymerization of VDF using PNIPAM macroCTAs. The synthesis of peptide sequences, cyclic peptide (CP) preparation and the synthesis of PVDF-CP conjugates is also described. The self-assembly in solution of all the novel PVDF-based BCPs and CPs was also studied. Finally, PVDF blend membranes were prepared by non-solvent induced phase-separation (NIPS) process using one of the amphiphilic BCPs as an additive. The performance of the membrane and evolution of membrane properties over a period of 9 months was also studied.</p>
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              <p>Cette thèse présente de nouvelles approches pour la préparation d’architectures basées sur le PVDF. La synthèse et la caractérisation de différents copolymères amphiphiles à base de PVDF et de peptides cycliques-PVDF conjugués sont décrites. La polymérisation RAFT/MADIX du monomère VDF gazeux et différentes chimies ont été utilisées pour la préparation des copolymères à bloc. Des copolymères triblock ABA à base de PVDF ont été obtenus par addition de Thia-Michael grâce à une stratégie « one-pot » impliquant à la fois des PVDF-Xanthate (ou P(VDF-co-HFP)-Xanthate) et des PEG-diacrylates. Des copolymères dibloc PNIPAM-b-PVDF ont été préparés par polymérisation RAFT de VDF à l’aide de macroCTAs PNIPAM. La synthèse des séquences peptidiques, la préparation des peptides cycliques (PC) et la synthèse des conjugués PVDF-CP sont également décrites. Enfin, des membranes à base de PVDF ont été préparées par un procédé de séparation de phase (NIPS) utilisant un des copolymères a bloc amphiphiliques comme additif. La performance de la membrane et l’évolution des propriétés de la membrane sur une période de 9 mois ont également été étudiées.</p>
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