A practical approach to the living polymerization of functionalized monomers: application to block copolymers and 3-dimensional macromolecular architectures

The tolerance of living free radical procedures to reactive functional groups, coupled with their ability to prepare well-defined random and block copolymers is demonstrated by the use of novel α-hydrogen alkoxyamine derivatives instead of the traditional TEMPO-based systems. This refinement in the nitroxide structure overcomes many limitations typically associated with TEMPO and has permitted a dramatic increase in the range of monomers, which can be polymerized under controlled conditions. The ability to prepare well-defined multi-arm star polymers from a variety of alkoxyamine terminated vinyl and non-vinyl linear polymers are major benefits when compared to traditional living procedures, such as anionic polymerizations.