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 grou ps, coupled with their ability to prepare well-defined random and block cop olymers is demonstrated by the use of novel alpha -hydrogen alkoxyamine der ivatives instead of the traditional TEMPO-based systems. This refinement in the nitroxide structure overcomes many limitations typically associated wi th TEMPO and has permitted a dramatic increase in the range of monomers, wh ich can be polymerized under controlled conditions. The ability to prepare well-defined multiarm star polymers from a variety of alkoxyamine terminate d vinyl and non-vinyl linear polymers are major benefits when compared to t raditional living procedures, such as anionic polymerizations.