This book describes strategies and mechanism of reversible deactivation radical polymerization (RDRP) to synthesize functional polymers. Several approaches such as atom transfer radical polymerization and the combination of click chemistry and RDRP are summarized. Contributors from interdisciplinary fields highlight applications in nanotechnology, self-healing materials, oil and water resistant coatings and controlled drug delivery systems.

Reversible deactivation radical polymerization (RDRP), also known as controlled radical polymerization (CRP), has been a significant area of polymer research for more than 20 years, allowing the facile synthesis of complex macromolecules previously unattainable by conventional free radical polymerization (FRP). However, industrial adoption of RDRP has been minimal largely due to the significant economic barrier to commercialization, with complex synthesis of the mediating agents required and the necessary post polymerization processing to recover the mediating agent. In an effort to overcome this obstacle to industrial adoption, the mediating agent concentration can be significantly reduced, such as the copper level in activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP), or the mediating agent can be incorporated into the polymer as in nitroxide-mediated polymerization (NMP), where no post polymerization processing is required other than removal of residual monomer. This thesis presents a study of these two chemistries towards industrially relevant conditions. To build upon recent developments of continuous ARGET ATRP, a systematic batch study is conducted to pursue decreased copper levels in the generation of short chain acrylic and methacrylic polymers of interest to the coatings industry. The limitations to reducing copper levels are understood with the development of a kinetic model, with the improved understanding of the ARGET ATRP system suggesting that a reduction in copper loading must be accompanied by an increase in reducing agent loading in order to maintain an appreciable polymerization rate. Alternatively, NMP does not require a reduction in mediating nitroxide level as it reversibly terminates the polymer chain end, and may present a smaller barrier to commercialization. Indeed, certain nitroxides are currently produced at pilot scale. However, limited research has been conducted into continuous operation which is commonly used in industry to improve productivity. A batch NMP study at elevated temperatures demonstrates the effectiveness of a novel alkoxyamine to mediate the polymerization of styrene and butyl acrylate under industrially relevant conditions. A kinetic study is developed to understand the novel system, and the polymerization is implemented in a continuous stirred-tank reactor (CSTR), the first demonstration of NMP in an existing industrial process.

The IUPAC-sponsored International Symposium on "Radical Polymerization: Kinetics and Mechanism" was held in Il Ciocco (Italia) during the week September 3-8, 2006. It was the fourth within the series of so-called SML conferences, which are the major scientific forum for addressing kinetic and mechanistic aspects of free-radical polymerization and of ontrolled radical polymerization. Top international authors like K. Matyjaszewski, T. P. Davis, T. Fukuda and others present their latest research. The five major themes covered were: Fundamentals of Free-Radical Polymerization, Heterogeneous Polymerization, Controlled Radical Polymerization, Polymer Reaction Engineering, and Polymer Characterization. SML IV again marked an important step forward toward the better understanding of the kinetics and mechanism of radical polymerization, which is extremely relevant for both conventional and controlled radical polymerization and for people in academia as well as in industry.

This book and the following volume (1188: Controlled Radical Polymerization: Materials) are addressed to chemists and polymer scientists interested in radical processes, and especially in controlled/living radical polymerization. The chapters in this first volume summarize the most recent advances in the field, including mechanistic, materials, and applications aspects. Controlled/living radical polymerization (CRP) or reversible-deactivation radical polymerization (RDRP, as recommended by IUPAC) is among the most rapidly expanding areas of chemistry and polymer science. This first volume provides an overview of the current status of controlled/living radical polymerization (CRP) systems, and also discusses important issues relevant to all radical polymerization methods. The mechanistic and kinetic aspects of ATRP are also covered, as well as more complex mechanisms such as "hybrid" processes. Thirty-seven chapters published in two volumes show that there have been significant developments in CRP over the last 15 years. New systems have been discovered; substantial progress has been achieved in understanding the mechanism and kinetics of reactions involved in all CRP systems. As a result of these advances, significant progress has been made towards developing a comprehensive relationship between molecular structure and macroscopic properties. Several commercial applications of CRP have been announced and it is anticipated that new products made by CRP will soon be on the market.

In reversible deactivation radical polymerization, some chemical links are dormant.