Self-assembly of poly(vinylidene fluoride)-block-poly(2-(dimethylamino)ethylmethacrylate) block copolymers prepared by CuAAC click coupling. Issue 34 (23rd May 2017)

• Record Type: Journal Article
• Authors: Guerre, Marc; Semsarilar, Mona; Totée, Cedric; Silly, Gilles; Améduri, Bruno; Ladmiral, Vincent
• Is Part Of: Polymer chemistry. Volume 8:Issue 34(2017)
• Page Start: 5203
• Page End: 5211
• Publication Date: 2017-05-23
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/c7py00346c
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : Self-assembly of PDMAEMA- b -PVDF block copolymers. 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.