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Free radical polymerization with reversible addition–fragmentation chain transfer (RAFT polymerization) is discussed with a view to answering the following questions: (a) How living is RAFT polymerization? (b) What controls the activity of thiocarbonylthio compounds in RAFT polymerization? (c) How do rates of polymerization differ from those of conventional radical polymerization? (d) Can RAFT agents be used in emulsion polymerization? Retardation, observed when high concentrations of certain RAFT agents are used and in the early stages of emulsion polymerization, and how to overcome it by appropriate choice of reaction conditions, are considered in detail. Examples of the use of thiocarbonylthio RAFT agents in emulsion and miniemulsion polymerization are provided.

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