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.