Living Radical Polymerization: Controlling Molecular Size and Chemical Functionality in Vinyl Polymers

The field of living radical polymerization (LRP) is reviewed, with general outcomes and mechanisms being discussed in a qualitative manner. These polymerizations exhibit living polymerization characteristics, that is, they show linear growth in chain length as a function of monomer conversion, have functional end‐groups, and often have narrow molecular weight distributions. The three main LRP methods, nitroxide‐mediated polymerizations (NMP), atom transfer radical polymerization (ATRP), and reversible addition‐fragmentation chain transfer (RAFT) polymerization, are discussed in terms of their general mechanisms.

Keywords:

• living radical polymerization
• vinyl polymers
• LRP methods
• nitroxide‐mediated polymerizations (NMP)
• atom transfer radical polymerization (ATRP)
• reversible addition‐fragmentation chain transfer (RAFT) polymerization

Notes

*It should be noted that the transition metal species is strictly not a catalyst since some is irreversibly oxidized during the reaction due to radical‐radical termination and the persistent radical effect (see Section 8).