Chapter 4: NMP Under Homogenous Conditions in Bulk, Organic Solvents and Aqueous Systems

Nitroxide mediated polymerization (NMP) as a viable controlled polymerization strategy has grown from being only capable of homopolymerizing styrenic monomers to acrylates, acrylamides and methacrylates under some conditions. Bulk polymerizations have been effective, allowing access to various microstructures (statistical, block, graft) and are the easiest to apply but fall short when solutions become viscous or when monomers are solids. Polymerization in organic solvent in the latter case is especially pertinent for monomers intended for organic electronic or biological applications. Polymerizations in aqueous solution are rarer for NMP, primarily due to stability issues of nitroxides in aqueous media at low pH, but recent results have been particularly encouraging, particularly for tertiary amine monomers, which are of interest for polymerization induced self-assembly (PISA) and CO₂-switchable latexes.