Abstract
To date, amphiphilic block copolymers (BCPs) containing poly(vinylidene fluoride-co-hexafluoropropene) (P(VDF-co-HFP)) copolymers are rare. At moderate content of HFP, this fluorocopolymer remains semicrystalline and is able to crystallize. Amphiphilic BCPs, containing a P(VDF-co-HFP) segment could, thus be appealing for the preparation of self-assembled block copolymer morphologies through crystallization-driven self-assembly (CDSA) in selective solvents. Here the synthesis, characterization by 1H and 19F NMR spectroscopies, GPC, TGA, DSC, and XRD; and the self-assembly behavior of a P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) triblock copolymer were studied. The well-defined ABA amphiphilic fluorinated triblock copolymer was self-assembled into nano-objects by varying a series of key parameters such as the solvent and the non -solvent, the self-assembly protocols, and the temperature. A large range of morphologies such as spherical, square, rectangular, fiber-like, and platelet structures with sizes ranging from a few nanometers to micrometers was obtained depending on the self-assembly protocols and solvents systems used. The temperature-induced crystallization-driven self-assembly (TI-CDSA) protocol allowed some control over the shape and size of some of the morphologies.
Highlights
The ability of block copolymers (BCPs) to spontaneously organize in solution into different morphologies has attracted a great deal of attention due to the potential use of these morphologies in the development of nanomaterials with controlled structures and tunable properties [1,2]
We showed that the morphologies self-assembled in solution adopted by a Poly(vinylidene fluoride) (PVDF)-b-PEG-b-PVDF are highly path- and solvent-dependent due to the non-ergodicity of such systems [37]
An ABA P(VDF51 -co-HFP4 )-b-PEG136 -b-P(VDF51 -co-HFP4 ) amphiphilic triblock copolymer was synthesized using an efficient one-pot aminolysis/thia-Michael addition of a P(VDF51 -co-HFP4 ) prepared by Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization and PEG diacrylate. This triblock copolymer was characterized by 1 H and, 19 F-Nuclear Magnetic Resonance (NMR) spectroscopies, GPC, as well as Thermogravimetric Analysis (TGA), Differential scanning calorimetry (DSC), and X-Ray Diffraction (XRD)
Summary
The ability of block copolymers (BCPs) to spontaneously organize in solution into different morphologies has attracted a great deal of attention due to the potential use of these morphologies in the development of nanomaterials with controlled structures and tunable properties [1,2]. Reported the formation of crystalline structures, thought to be formed by CDSA of PVAc-b-PVDF diblock copolymer solutions in dimethyl carbonate (DMC), a solvent in which PVDF is soluble at moderate to high temperatures [30]. 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 showed that PVDF crystalized in its α-phase in such aggregates.
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