Synthesis of poly(vinylidene fluoride)‐<i>b</i>‐poly(styrene sulfonate) block copolymers by controlled radical polymerizations

Abstract

Abstract Block copolymers based on poly(vinylidene fluoride), PVDF, and a series of poly(aromatic sulfonate) sequences were synthesized from controlled radical polymerizations (CRPs). According to the aromatic monomers, appropriate techniques of CRP were chosen: either iodine transfer polymerization (ITP) or atom transfer radical polymerization (ATRP) from PVDF‐I macromolecular chain transfer agents (CTAs) or PVDF‐CCl 3 macroinitiator, respectively. These precursors were produced either by ITP of VDF with C 6 F 13 I or by radical telomerization of VDF with chloroform, respectively. Poly(vinylidene fluoride)‐ b ‐poly(sodium styrene sulfonate), PVDF‐ b ‐PSSS, block copolymers were produced from both techniques via a direct polymerization of sodium styrene sulfonate (SSS) monomer or an indirect way with the use of styrene sulfonate ethyl ester (SSE) as a protected monomer. Although the reaction led to block copolymers, the kinetics of ITP of SSS showed that PVDF‐I macromolecular CTAs were not totally efficient because a limitation of the CTA consumption (56%) was observed. This was probably explained by both the low activity of the CTA (that contained inefficient PVDF‐CF 2 CH 2 I) and a fast propagation rate of the monomer. That behavior was also noted in the ITP of SSE. On the other hand, ATRP of SSS initiated by PVDF‐CCl 3 was more controlled up to 50% of conversion leading to PVDF‐ b ‐PSSS block copolymer with an average number molar mass of 6000 g·mol −1 . © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011