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Self-assembly of poly(vinylidene fluoride)-block-poly(2-(dimethylamino)ethylmethacrylate) block copolymers prepared by CuAAC click coupling

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Abstract

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 (PVDF40-b-PDMAEMA23, PVDF40-b-PDMAEMA69, PVDF40-b-PDMAEMA162, Đ < 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, PVDF40-b-PDMAEMA69 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.

Graphical abstract: Self-assembly of poly(vinylidene fluoride)-block-poly(2-(dimethylamino)ethylmethacrylate) block copolymers prepared by CuAAC click coupling

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Publication details

The article was received on 01 Mar 2017, accepted on 04 May 2017 and first published on 12 May 2017


Article type: Paper
DOI: 10.1039/C7PY00346C
Citation: Polym. Chem., 2017, Advance Article
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    Self-assembly of poly(vinylidene fluoride)-block-poly(2-(dimethylamino)ethylmethacrylate) block copolymers prepared by CuAAC click coupling

    M. Guerre, M. Semsarilar, C. Totée, G. Silly, B. Améduri and V. Ladmiral, Polym. Chem., 2017, Advance Article , DOI: 10.1039/C7PY00346C

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