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

Abstract

Novel amphiphilic PVDF-based triblock copolymer (PVDF50-b-PEG136-b-PVDF50) is synthesized using RAFT polymerization and a one-pot thia-Michael addition. Self-assembly of this ABA copolymer resulted in formation of original crystalline structures.

Evaluation of Self-Assembly Pathways to Control Crystallization-Driven Self-Assembly of a Semicrystalline P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) Triblock Copolymer

“…Differential scanning calorimetry (DSC) of the BCP and of its precursors revealed an exothermic peak corresponding to the crystallization of P(VDF-co-HFP) at 119.2 • C ( Figures S9 and S10). As expected, the melting and crystallization temperatures of the P(VDF-co-HFP) segment are lower than those of a PVDF homopolymer segment (103.1 • C and 133.5 • C, respectively) of similar molar mass and linked to the same PEG central block [37]. P(VDF-co-HFP) copolymers are less crystalline than PVDF, but remain semicrystalline and behave as thermoplastics up to 19 mol% of HFP.…”

“…1 H NMR (300 MHz (CD 3 ) 2 CO, δ (ppm), Figure S1): 1. Polyethylene glycol diacrylate (PEG-DA) synthesis was prepared following the protocol described elsewhere [37]. One equivalent of PEG 6000 and an excess of ten equivalents of acryloyl chloride were dissolved in DCM in a round bottom flask at room temperature.…”

“…Only a few studies describe the self-assembly in solution of BCPs containing a fluoropolymer block [ 29 , 30 , 31 , 32 , 33 ]. Our team has been developing the Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization of VDF over the last years [ 34 , 35 , 36 ], and has described several synthetic routes for fluoropolymer-based BCPs among other architectures [ 29 , 30 , 31 , 33 , 37 , 38 , 39 , 40 ]. Due to the relative rarity of such BCPs, only a few examples of their CDSA behavior have been reported.…”

“…He also showed that PVDF- b -PDMAEMA (DMAEMA = 2-(dimethylamino)ethylmethacrylate) BCP could form cylindrical structures by self-assembly in water, likely via CDSA [ 31 ]. Folgado and coworkers prepared an amphiphilic PVDF- b -PEG- b -PVDF triblock copolymer and observed the formation of spindle-shaped crystalline structures in THF: ethanol mixtures [ 37 ]. They also showed that PVDF crystalized in its α-phase in such aggregates.…”

Polymerizations by RAFT: Developments of the Technique and Its Application in the Synthesis of Tailored (Co)polymers

“…The resulting ABA triblock copolymer was then self‐assembled using different solvent mixtures (N‐methyl‐2‐pyrrolidone (NMP) or tetrahydrofuran (THF)/H 2 O or ethanol) and assembly methods (micellization and nanoprecipitation) to produce a range of crystalline morphologies from spheres to bundled rods. [ 150 ] Well‐defined xanthate capped short PVDF chains were also converted to macromonomer using aminolysis/thia‐Michael addition via a one pot reaction. The resulting methacrylate macromonomer (PVDF‐MA) was used to prepare well controlled copolymers with methyl methacrylate.…”