Chapter 13: Organocatalyzed Controlled Radical Polymerizations

Radical polymerizations are responsible for a significant amount of the World's total polymer production. Free-radical polymerization provides a relatively inexpensive and facile route to produce bulk plastic products, however, it fails in the synthesis of precisely defined macromolecules. To address this issue, controlled radical polymerizations have been developed, which utilize a reversible deactivation mechanism for the synthesis of advanced polymeric architectures. In this chapter, we discuss the mechanisms and applications of organocatalyzed controlled radical polymerizations, specifically atom transfer radical polymerization, photo mediated reversible addition fragmentation chain-transfer polymerization, and reversible complexation mediated radical polymerization, as powerful new methods for precision polymer synthesis.