Synthesis of ω-Iodo and Telechelic Diiodo Vinylidene Fluoride-Based (Co)polymers by Iodine Transfer Polymerization Initiated by an Innovative Persistent Radical

Abstract

The synthesis of ω-iodo and telechelic diiodo vinylidene fluoride (VDF)-based (co)polymers by iodine transfer polymerization (ITP) of VDF initiated by a trifluoromethyl radical (generated by perfluoro-3-ethyl-2,4-dimethyl-3-pentyl persistent radical, PPFR) is presented. Reactions were carried out in the presence of different chain transfer agents (CTAs, such as trifluoroiodomethane, 1,4-diiodoperfluorobutane, and molecular iodine) with/without tert-butyl 2-trifluoromethacrylate (MAF-TBE). Experimental conditions (nature of the solvents and CTAs, time, temperature, and initial [VDF]0:[CTA]0:[initiator]0 molar ratios) were varied to influence the yield of the reaction (up to 86%), the molar masses (Mn), dispersity values (Đ), chain end functionalities, and microstructures of the obtained polymers. Detailed kinetics study enabled to confirm the well-controlled polymerization: (i) synthesis of iodinated polymers with different molar masses (Mn,SEC = 1110–5800 g mol–1) and low Đ values (≤1.30), just simply by ...