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Iodine‐transfer polymerization and CuAAC “click” chemistry: A versatile approach toward poly(vinylidene fluoride)‐based amphiphilic triblock terpolymers
Author(s) -
Patil Yogesh,
Zapsas George,
Gnanou Yves,
Hadjichristidis Nikos
Publication year - 2020
Publication title -
journal of polymer science
Language(s) - English
Resource type - Journals
eISSN - 2642-4169
pISSN - 2642-4150
DOI - 10.1002/pola.29497
Subject(s) - copolymer , amphiphile , polymer chemistry , polymerization , click chemistry , transfer agent , chemistry , gel permeation chromatography , materials science , polymer , organic chemistry
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 (C 6 F 13 I) serving as chain‐transfer agent (CTA) to afford C 6 F 13 ‐PVDF‐I, (b) ITP of styrene with the C 6 F 13 ‐PVDF‐I macromolecular‐CTA to obtain C 6 F 13 ‐PVDF‐ b ‐PS‐I diblock copolymer, (c) end‐group exchange from iodo‐ to azido‐group by nucleophilic substitution reaction with NaN 3, and (d) copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) with alkyne‐terminated PEO to achieve C 6 F 13 ‐PVDF‐ b ‐PS‐ b ‐PEO triblock terpolymers. The 1 H and 19 F 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