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

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‐CCl3 macroinitiator, respectively. These precursors were produced either by ITP of VDF with C6F13I 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‐CF2CH2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‐CCl3 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

Mn2(CO)10-photomediated synthesis of poly(vinylidene fluoride)-b-poly(styrene sulfonate)

“…However, the decrease of molar mass with the conversion, as well as the high polydispersity index of the crude, unprecipitated polymer system is about 2, and indicates a non-living system and presence of conventional radical telomerization. Similar behavior in the IDT polymerization of ethyl styrene sulfonate was also observed with free radical initiators [72]. In our case, while the polymerization should be controlled, the free radical behavior and very fast polymerization is simply a consequence of the large amount of Mn 2 (CO) 10 that was employed (50%).…”

“…As such, sodium styrene sulfonate and ethyl styrene sulfonate were tested in PVDF block copolymerizations by ATRP from a PVDFACCl 3 macroinitiator, as well as by iodine degenerative transfer polymerization from iodine terminated PVDF (PVDF-I), prepared in autoclave at high temperatures [72,73]. Here, while the ATRP initiation can occur from the CCl 3 fragment, as explained above and noted in other VDF-IDT based block copolymerization attempts [56,74], the block copolymerization cannot work effectively under free radical initiation conditions due to the unreactive PVDFACF 2 ACH 2 AI chain ends, which moreover are the dominant species over PVDFACH 2 ACF 2 AI in PVDF-I.…”

Photochemically Enabled Iodine Degenerative Transfer Controlled Radical Homo- and Block Copolymerization of Vinylidene Fluoride at Ambient Temperatures with Mn2(CO)10and Visible Light

“…Earlier attempts at the synthesis of PVDF blocks (148) included VDF initiation from macromolecular R F -I CT agents using free radical initiators (31,149,150) (which inherently produces PVDF homopolymer), or simply assuming that the chain ends of PVDF-X (136,(151)(152)(153) would be radically activated by Cu/ATRP (137)(138)(139) or thermal IDT (136) for the initiation of another monomer, or that both chain ends could be converted to azide groups, which is not the case (154-156). As described earlier, CuX/L hardly activates perfluoroalkyl halides (~10 2 ) (157), and thus, would barely initiate from -CF 2 CF 2 -I, let alone from -CH 2 CF 2 -I, and especially from the unreactive -CF 2 -CH 2 -I chain end.…”

Organometallic‐Mediated Alternating Radical Copolymerization of tert‐Butyl‐2‐Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof

“…Since these pioneering works, interest in fluorinated block copolymers has surged in the last decade. This led to the synthesis of a variety of fluorinated block copolymers prepared using telomerization, conventional radical polymerization from functionalized initiators, click chemistry, and using different RDRP techniques: iodine transfer polymerization (ITP), photoinitiated ITP, reversible addition fragmentation chain transfer (RAFT) polymerization, and atom transfer radical polymerization (ATRP) . However, for all their merits, telomerization only affords oligomers, and functional initiators lead to broad dispersity.…”