Precision synthesis of poly(ionic liqui)s in aqueous media by cobalt-mediated radical polymerization

Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in many fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecules, and provide novel attractive functions. Recently, the precision design of novel PILs by controlled/living polymerization (CLP) techniques was intensively searched for developing emerging applications, such as those based on the self-assembly of block copolymers (BCPs). Indeed, combining the physicochemical properties of PILs with the self-assembly of BCPs is a route to easily produce innovative functional nanostructures that have a huge potential for many applications, e.g. for electrochemical devices, gas membranes, nanostructures materials, etc. Among the panel of poly(ionic liquid)-based block copolymers (PIL BCPs) that is available, vinyl imidazolium-based derivatives are highly attractive due their high charge density, the possibility to easily tune their properties by the nature of the alkyl chain, etc. However, when this PhD thesis started, their synthesis by direct polymerization of N-vinyl imidazolium-type monomers was challenging for most of the CLP techniques. Only few examples of vinyl imidazolium-based PIL BCPs were accessible by Reversible Addition Fragmentation Transfer (RAFT) polymerization or Cobalt-Mediated Radical Polymerization (CMRP), and in organic media exclusively.

The aim of this PhD thesis was to develop a controlled radical polymerization technique for N-vinyl imidazolium-type monomers in water that would facilitate the precision synthesis of PIL BCPs in this green solvent under non-demanding experimental conditions. Due to its compatibility to water and to its high versatility, the CMRP process was used for that purpose. The synthetic challenges that we address in this thesis are (1) to perform the CMRP of N-vinyl imidazolium type monomers in water, (2) to prepare hydrosoluble but also amphiphilic all PIL BCPs in this green solvent, and (3) to simplify the process to facilitate its scaling-up. The potential of the innovative PILs developed during this thesis was then explored for applications in energy (as solid electrolytes for battery applications) and environment (as antibacterial coatings/materials).