The influence of domain segregation in ionic liquids upon controlled polymerisation mechanisms: RAFT polymerisation

Recent evidence has suggested that the solvent environment in ionic liquids is dynamic and composed of polar and non-polar domains governed by the summation of weak interactions and self-assembly. Consequently, the effect of a nano-structured solvent environment on chemistries conducted in ionic liquids is coming under increased scrutiny. In this work we investigate how the domain-like structure of ionic liquids affects the kinetics and products of the reversible addition fragmentation chain transfer (RAFT) controlled free radical polymerisation (FRP) of methyl methacrylate in a number of room temperature ionic liquids. By utilising rotating frame Overhauser effect spectroscopy (ROESY) to probe the solvation environment of the 2-cyano prop-2-yl dithiobenzoate (CPDB) RAFT agent, we show that in almost all cases preferential partitioning of the dithiobenzoate-moiety of the RAFT agent into the ionic domain of the ionic liquid occurs.