Living-Radical Polymerizations, an Overview

Like other overnight discoveries, the present success of living-radical polymerization is built on the work of pioneers in the field who laid the groundwork for what was to come. The first indication that a terminated polymer prepared by a free-radical polymerization could chain extend was reported by Braun [2] in 1981. Thus, a purified oligomeric methyl methacrylate, terminated with a primary radical from 

Living-radical polymerizations are essentially conventional radical polymerizations performed in the presence of some species that react reversibly with the 

At any given time most of the polymer chains are in the dormant form and the concentration of the active chains is so low (10 M) that the probability of two chains colliding with each other and terminating is dramatically reduced. Although some termination continues to occur throughout the course of the polymerization 

---

At the time of the first edition of this book (1995), this field was still very much in its infancy. NMP was described, though little had been published in the open literature, and methods such as ATRP and RAFT had not been reported. Since 1995, the area has expanded dramatically and by themselves living/ controllcd/mcdiatcd processes now account for a very substantial fraction of all research on radical polymerization (Chapter 1). The development of this field over this period can be followed in the publications following successful ACS symposia held in 1997/ 2000 and 2002 and SML meetings held in 1996 and 2001. Publications continue to appear at a rapid rate. Matyjaszewski has provided an overview of the history and development of living radical polymerization through 2001 in the Handbook of Radical Polymerization ... 

The first chapter in this volume provides an overview of the current status of controlled/living radical pol5mierization (CRP) systems. The following three chapters discuss important issues relevant to all radical polymerization methods. The mechanistic and kinetic topics of ATRP are... 

The book contains 22 chapters, logically organized into an overview chapter with three other subsections Part one The synthesis of functional polymers by direct methods, such as anionic, cationic, free radical and coordination polymerization. Part two The synthesis of functional polymers by postpolymerization functionalization. Part three Novel approaches and structures. Special emphasis is given to more modem techniques Aat allow for controlled and directed functionalization via living polymerization. 

---