Recent advances in controlled/living radical polymerization in emulsion and dispersion

Effective ways to conduct controlled/living radical polymerization (CRP) in emulsion systems are necessary for commercial latex production without significant modification of current industrial facilities. Conducting CRP in emulsion media is more complicated and more challenging than its application in homogeneous bulk. These challenges come from the intrinsic kinetics of emulsion polymerization. They include mass transport, slow chain growth mechanism, and exit of short radicals from polymeric particles. This review describes the recent developments of CRP in heterogeneous dispersion, including miniemulsion, microemulsion, dispersion, and especially emulsion. Various approaches for conducting emulsion CRP are detailed, including controlled seeded emulsion polymerization, nanoprecipitation, use of short oligomers as macroinitiators for in situ block copolymerization, and RAFT‐mediated self‐assembly. In addition many remaining challenges of the current methods barring wide spread industrial application of emulsion CRP are also suggested. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6983–7001, 2008