All Poly(ionic liquid)-Based Block Copolymers by Sequential Controlled Radical Copolymerization of Vinylimidazolium Monomers

The organometallic-mediated radical polymerization (OMRP) of <i>N</i>-vinyl-3-alkyl­imidazolium-type monomers, featuring the bis­(trifluoromethyl­sulfonyl)­imide counteranion (Tf₂N^–), in the presence of Co­(acac)₂ as controlling agent, is reported. Polymerizations of monomers with methyl, ethyl, and butyl substituents are fast, reaching high monomer conversion in ethyl acetate as solvent at 30 °C, and afford structurally well-defined hydrophobic poly­(ionic liquid)­s (PILs) of <i>N</i>-vinyl type. Block copolymer synthesis is also achieved by sequential OMRP of <i>N</i>-vinyl-3-alkylimidazolium salts carrying different alkyl chains and different counteranions (Tf₂N^– or Br^–). These block copolymerizations are carried out at 30 °C, either under homogeneous solution in methanol or in a biphasic medium consisting of a mixture of ethyl acetate and water. Unprecedented PIL-<i>b</i>-PIL block copolymers are thus prepared under these conditions. However, anion exchange occurs at the early stage of the growth of the second block. Finally, diblock copolymers generated in the biphasic medium can be readily coupled by addition of isoprene, forming all PIL-based and symmetrical ABA-type triblock copolymers in a one-pot process. Such a direct block copolymerization method, involving vinylimidazolium monomers bearing different alkyl chains, thus opens new opportunities in the precision synthesis of all PIL-based block copolymers of tunable properties