CHAPTER 7: Living Radical Polymerizations with Organic Catalysts

This chapter introduces fundamental features of two new families of living radical polymerizations that use organic catalysts for reversible activation. The polymerizations are based on new reversible activation mechanisms, reversible chain transfer (RT) and reversible complexation (RC), and have been proposed to be termed RT catalyzed polymerization (RTCP) and RC mediated polymerization (RCMP). The catalysts are germanium, tin, phosphorus, nitrogen, oxygen, and carbon-centered molecules. They include such common compounds as phosphites (P), imides and amines (N), phenols (O) and dienes (C). Low-polydispersity polymers were obtained in the homopolymerizations and random and block copolymerizations of styrene, methyl methacrylate, acrylonitrile, and several functional styrenics and methacrylates. Attractive features of the catalysts include their good polydispersity controllability, good tolerance to functional groups, inexpensiveness, low toxicity, and ease of handling (robustness). The backgrounds, performances, and kinetic features of RTCP and RCMP are described.