Poly(vinylidene fluoride)-b-poly(styrene) Block Copolymers by Iodine Transfer Polymerization (ITP): Synthesis, Characterization, and Kinetics of ITP

Abstract

The syntheses of poly(vinylidene fluoride)-b-poly(styrene) (PVDF-b-PS) block copolymers, from the iodine transfer polymerization (ITP) of styrene, in the presence of PVDF−I, are presented. In a first step, considering that the radical polymerization of vinylidene fluoride can lead to two different isomeric oligomers, bearing either −CH2I or −CF2I end groups, the kinetics of ITP of styrene in the presence of two chain transfer agents, C6F13−CH2CF2−I and HCF2−CF2CH2−I, were achieved as model reactions. The characterization of sampled aliquots by 19F NMR spectroscopy could monitor the average degree of polymerization in number (DPn) vs styrene conversion (αStyrene). ITPs of styrene with both these chain transfer agents showed two opposite behaviors, also confirmed by MALDI−TOF spectroscopy and SEC chromatography. (i) on the one hand, in the presence of C6F13−CH2CF2−I, the controlled character of ITP of styrene was evidenced (a linear dependence of DPn vs αStyrene was observed), theoretical DPn values were cl...