“One-pot” aminolysis/thia-Michael addition preparation of well-defined amphiphilic PVDF-b-PEG-b-PVDF triblock copolymers: self-assembly behaviour in mixed solvents

Enrique Folgado (1) , Marc Guerre (2) , Antonio Da Costa (3) , Anthony Ferri (4) , Ahmed Addad (5) , Vincent Ladmiral (2) , M. Semsarilar (6)

1 LCC - Laboratoire de chimie de coordination
2 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
3 UCCS - Unité de Catalyse et Chimie du Solide - UMR 8181
4 UCCS Équipe Couches Minces & Nanomatériaux
5 UMET - Unité Matériaux et Transformations - UMR 8207
6 IEM - Institut Européen des membranes

Polyvinylidene fluoride-(PVDF) containing block copolymers are scarce and difficult to prepare. Amphiphilic block copolymers containing PVDF have been rarely reported. In consequence, few studies of the self-assembly of PVDF-based block copolymers exist. Here a new synthetic route to prepare poly(vinylidene fluoride)-block-poly(ethylene glycol)-block-poly(vinylidene fluoride) (PVDF-b-PEG-b-PVDF) ABA triblock copolymer is presented. The synthesis relies on the efficient coupling of a PVDF prepared by RAFT and a PEG diacrylate in one pot via aminolysis of the xanthate moiety and subsequent thia-Michael addition. The novel amphiphilic triblock copolymer was fully characterized by 1 H and 19 F NMR spectroscopies, GPC, TGA, DSC and XRD; and its self-assembly in water and ethanol was studied. Micellization (addition of a selective solvent for PVDF to a solution of the triblock) and nanoprecipitation (addition of a solution of the triblock into a non solvent of PVDF) protocols led to the formation of micelles and vesicles. Surprisingly, under nanoprecipitation conditions (in THF/ ethanol), well-defined crystalline micrometric structures were obtained.

Domaines: Chimie

Enrique Folgado, Marc Guerre, Antonio Da Costa, Anthony Ferri, Ahmed Addad, et al.. “One-pot” aminolysis/thia-Michael addition preparation of well-defined amphiphilic PVDF-b-PEG-b-PVDF triblock copolymers: self-assembly behaviour in mixed solvents. Polymer Chemistry, 2020, 11 (2), pp.401-410. ⟨10.1039/c9py00970a⟩. ⟨hal-02462556⟩