Iodine‐transfer polymerization and CuAAC “click” chemistry: A versatile approach toward poly(vinylidene fluoride)‐based amphiphilic triblock terpolymers

ABSTRACT This study presents the synthesis and properties of linear PVDF‐based amphiphilic triblock terpolymers with PS and PEO, [PVDF‐b‐PS‐b‐PEO], by adopting a procedure that involves: (a) iodine‐transfer polymerization (ITP) of VDF with 1‐iodoperfluorohexane (C6F13I) serving as chain‐transfer agent (CTA) to afford C6F13‐PVDF‐I, (b) ITP of styrene with the C6F13‐PVDF‐I macromolecular‐CTA to obtain C6F13‐PVDF‐b‐PS‐I diblock copolymer, (c) end‐group exchange from iodo‐ to azido‐group by nucleophilic substitution reaction with NaN3, and (d) copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) with alkyne‐terminated PEO to achieve C6F13‐PVDF‐b‐PS‐b‐PEO triblock terpolymers. The 1H and 19F NMR spectroscopy confirmed the presence of all blocks, while gel permeation chromatography traces showed the living nature of ITP technique. The self‐assembly of these terpolymers was investigated in films (atomic force microscopy and DSC), as well as in aqueous and organic solvents (DLS). The analysis of crystalline phases based on the FTIR spectroscopy indicated the conversion of PVDF α‐phase into α + β‐phases and β + γ‐phases upon the incorporation of PS and PEO blocks, respectively. The synthesized amphiphilic copolymers were evaluated (fluorescence spectroscopy) as carriers of small hydrophobic molecules in water. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 163–171