This Perspective summarizes the features and limitations of reversible addition−fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process, from both a mechanistic and an application point of view, has matured over the past 20 years. It is aimed at both experts in the field and newcomers, including undergraduate and postgraduate students, as well as nonexperts in polymerization who are interested in developing their own polymeric structures by exploiting the simple setup of a RAFT polymerization.

Among the living radical polymerization techniques, reversible addition-fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in terms of the reaction conditions, the variety of monomers for which polymerization can be controlled, tolerance to functionalities, and the range of polymeric architectures that can be produced. This review highlights the progress made in RAFT/MADIX polymerization since the first report in 1998. It addresses, in turn, the mechanism and kinetics of the process, examines the various components of the system, including the synthesis paths of the thiocarbonyl-thio compounds used as chain-transfer agents, and the conditions of polymerization, and gives an account of the wide range of monomers that have been successfully polymerized to date, as well as the various polymeric architectures that have been produced. In the last section, this review describes the future challenges that the process will face and shows its opening to a wider scientific community as a synthetic tool for the production of functional macromolecules and materials.

His Ph.D. was in collaboration with Solvay-Solexis and devoted to the synthesis of new graft copolymers using grafting "to". In 2005, he undertook a postdoctorate position with Dupont Performance and Elastomers (Willmington, United States) and Dr. B. Ameduri dealing with the synthesis of original fluorinated elastomers using controlled radical polymerization (e.g., iodine transfer polymerization). Since October 2006, he has been a senior research fellow under the direction of Prof. Thomas Davis in the Centre of Advanced Macromolecular Design (CAMD), University of New South Wales. His research interests mainly cover the preparation of well-defined polymers, protein-polymer conjugates, and hybrid organic-inorganic nanoparticles using controlled radical polymerization. He has coauthored over 40 peer-reviewed research papers, including 2 book chapters, and 2 patents. Volga Bulmus received her B.E. and M.Sc. in Chemical Engineering and her Ph.D. in bioengineering (Hacettepe University, Turkey), in 2000. She worked as a postdoctoral research fellow in the Bioengineering Department at the University of Washington between 2001 and 2003. In 2004, she was granted a highly competitive The University of New South Wales (UNSW) Vice Chancellor's Research Fellowship (Australia). In 2008, she was appointed as a Senior Lecturer at the School of Biotechnology and Biomolecular Sciences (UNSW). She is also an adjunct member of The Centre for Advanced Macromolecular Design (CAMD) at UNSW. Dr. Bulmus leads a group of 5-10 researchers working on the development of advanced polymers for biotechnology and biomedical applications. She has published over 45 peer reviewed research papers. Her research interests include design, synthesis, and evaluation of well-defined polymeric systems for nanobiotechnology and drug delivery applications ranging from antitumor chemotherapy and gene silencing to bioseparations and biosensors. Tom Davis has been an academic at UNSW for 17 years following a stint in industry as a research manager at ICI in the U.K. He has coauthored 315+ reviewed papers, patents, and book chapters. He is the Director of the Centre for Advanced Macromolecular Design (CAMD) at UNSWsa Centre with expertise in bio/organic polymer synthesis and polymerization kinetics. He is also a visiting Professor at the Institute for Materials Research & Engineering (IMRE) in Singapore. In 2005 he was awarded a Federation Fellowship by the Australian Research Council. He serves (or has served) on the editorial advisory boards of Macromolecules,