Synergistic Interaction Between ATRP and RAFT: Taking the Best of Each World*

Yungwan Kwak; Renaud Nicolaÿ; Krzysztof Matyjaszewski

doi:10.1071/CH09230

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Synergistic Interaction Between ATRP and RAFT: Taking the Best of Each World*

Yungwan Kwak ^A , Renaud Nicolaÿ ^A and Krzysztof Matyjaszewski ^A ^B

+ Author Affiliations

- Author Affiliations

^A Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA.

^B Corresponding author. Email: km3b@andrew.cmu.edu

Dr. Yungwan Kwak, born in Yeosu, South Korea, received his undergraduate degree in Engineering from Sunchon National University, South Korea. After receiving MEXT Japanese Government Scholarship, he moved to Japan and obtained his Master’s degree in 2003 and Ph.D. in 2006 from Kyoto University in the field of kinetics of controlled radical polymerizations (CRPs) under the supervision of Professor Takeshi Fukuda. Currently, he is working as a postdoctoral researcher with Professor Krzysztof Matyjaszewski at Carnegie Mellon University since 2006. His research areas include polymer synthesis, the mechanistic study of ATRP and RAFT, and the development of new CRP techniques. He has published 23 peer-reviewed papers and two book chapters.

Dr. Renaud Nicolaÿ, born in Clamart, France, completed his undergraduate studies in Chemistry at the Ecole Supérieure de Chimie Organique et Minérale (ESCOM) in France, where he received an ‘Ingénieur’ degree in 2003. He then joined Pierre & Marie Curie University, where he obtained his Master’s degree in 2004 and Ph.D. in 2008 under the supervision of Professor Patrick Hémery. In 2005, he also joined Carnegie Mellon University where he is currently a fifth year graduate student in Professor Matyjaszewski’s group. His research areas include the development of new approaches to macromolecular architectures, the synthesis of mediating agents for nitroxide-mediated polymerization, RAFT and ATRP, and the development of new CRP techniques. He has published seven peer-reviewed papers and was awarded the Excellence in Graduate Polymer Research Award (2009) and the Astrid and Bruce McWilliams Fellowship (2009).

Professor Krzysztof (Kris) Matyjaszewski, born in Poland in 1950, obtained his Ph.D. degree in 1976 at Polish Academy of Sciences in Lodz, Poland, working with Prof. S. Penczek. Since 1985 he is at Carnegie Mellon University (CMU) where he has served as Chemistry Department Head (1994–1998) and is currently J. C. Warner University Professor of Natural Sciences. He is an editor of Progress in Polymer Science and Central European Journal of Chemistry. His main research interests include controlled/living polymerization, catalysis, environmental chemistry and synthesis of advanced materials for optoelectronic and biomedical applications. In 1995 he developed atom transfer radical polymerization (ATRP), one of the most successful methods for controlled/living radical polymerization. His first paper on ATRP and first review were cited over 2000 times each. During the past 10 years his group has published over 500 papers on ATRP. He holds over 30 US and over 100 international patents. Close industrial interactions have been maintained via the ATRP and CRP Consortia with over 40 industrial members. Research of Matyjaszewski group has received wide recognition, as evidenced by ACS Carl S. Marvel Award for Creative Polymer Chemistry (1995), ACS Award in Polymer Chemistry (2002), ACS Hermann F. Mark Senior Scholar Award (2007), UK Macro Group Medal for Outstanding Achievements in Polymer Science (2005), and Prize of Polish Science Foundation (2004). He received honorary degrees from University of Ghent, Belgium (2002), Russian Academy of Sciences (2006), Lodz Polytechnic (2007), University of Athens, Greece (2008), and l’Institut Polytechnique, Toulouse, France (2009). He is a foreign member of Polish Academy of Sciences (2005) and US National Academy of Engineering (2006).

Australian Journal of Chemistry 62(11) 1384-1401 https://doi.org/10.1071/CH09230
Submitted: 18 April 2009 Accepted: 24 June 2009 Published: 20 November 2009

Abstract

This review covers recent developments on the combination of atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer (RAFT) polymerization to produce well controlled (co)polymers. This review discusses the relative reactivity of the R group in ATRP and RAFT, provides a comparison of dithiocarbamate (DC), trithiocarbonate (TTC), dithioester (DTE), and xanthate versus bromine or chlorine, and an optimization of catalyst/ligand selection. The level of control in iniferter polymerization with DC was greatly improved by the addition of a copper complex. New TTC inifers with bromopropionate and bromoisobutyrate groups have been prepared to conduct, concurrently or sequentially, ATRP from Br-end groups, ATRP from the TTC moiety, and RAFT polymerization from the TTC moiety, depending on the combination of monomer and catalyst employed in the reaction. The use of concurrent ATRP/RAFT (or copper-catalyzed RAFT polymerization or ATRP with dithioester leaving groups), resulted in improved control over the synthesis of homo- and block (co)polymers and allowed preparation of well-defined high-molecular-weight polymers exceeding 1 million. Block copolymers that could not be prepared previously have been synthesized by sequential ATRP and RAFT polymerization using a bromoxanthate inifer. A simple, versatile, and one-step method involving atom-transfer radical addition–fragmentation (ATRAF) for the preparation of various chain transfer agents (including DC, DTE, and xanthate) in high purity is discussed and a one-pot, two-step polymerization starting with a RAFT agent synthesized by ATRAF, followed by polymerization, is demonstrated.

Acknowledgements

The authors thank the NSF (CHE-07-15494 and DMR-0549353) and the members of the CRP Consortium at Carnegie Mellon University for their financial support. R.N. acknowledges Dr and Mrs. McWilliams (Astrid and Bruce McWilliams Fellowship).

References

^* Dedicated to Professor Ezio Rizzardo on the occasion of his 65th birthday.

Synergistic Interaction Between ATRP and RAFT: Taking the Best of Each World*

Abstract

Acknowledgements

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