Self-assembly of poly(vinylidene fluoride)-block-poly(2-(dimethylamino)ethylmethacrylate) block copolymers prepared by CuAAC click couplingElectronic supplementary information (ESI) available: Functionality calculation equations, additional 1H, 19F and DOSY NMR spectra, SEC chromatograms, FTIR spectra, DSC thermograms, DLS size distribution, TEM micrographs of self-assembled nanostructures. See DOI: 10.1039/c7py00346c

Poly(vinylidene fluoride) (PVDF) is a very important fluoropolymer which possesses remarkable physico-chemical properties such as high thermal and chemical resistances as well as ferroelectricity, for example. To date, only iodine transfer polymerization and RAFT polymerization have enabled the preparation of well-defined PVDF and of some PVDF-based block copolymers (BCPs). However, these reversible deactivation radical polymerization techniques suffer from undesired reactions which impair the synthesis of a wide range of PVDF-containing BCPs. Here, unprecedented poly(vinylidene fluoride)- block -poly(2-(dimethylamino)ethylmethacrylate) (PVDF- b -PDMAEMA) BCPs were prepared by CuAAC click coupling of azide-functionalized PVDF synthesized by RAFT polymerization and alkyne-functionalized PDMAEMA synthesized by ATRP. This strategy was quite efficient and afforded three relatively well-defined BCPs (PVDF 40 - b -PDMAEMA 23 , PVDF 40 - b -PDMAEMA 69 , PVDF 40 - b -PDMAEMA 162 , < 1.55). These amphiphilic BCPs were self-assembled in water at pH 2, 8 (native pH) and 10. The morphologies obtained were mainly polydisperse (20-500 nm), roughly spherical aggregates. However, at pH 8, PVDF 40 - b -PDMAEMA 69 also formed micrometer-long rigid cylindrical micelles. These morphologies are likely the first examples of PVDF-containing BCP nanostructures produced by crystallization-driven self-assembly. Self-assembly of PDMAEMA- b -PVDF block copolymers.