Reversible Deactivation Radical Polymerization

Mechanisms and Synthetic Methodologies

Edited by Krzysztof Matyjaszewski, Haifeng Gao, Brent S. Sumerlin, and Nicolay V. Tsarevsky

ACS Symposium Series

Showcases progress made involving the relationship between molecular structure and macroscopic properties
Expands upon new systems discovered involving reversible deactivation radical polymerization

Reversible Deactivation Radical Polymerization

Mechanisms and Synthetic Methodologies

Edited by Krzysztof Matyjaszewski, Haifeng Gao, Brent S. Sumerlin, and Nicolay V. Tsarevsky

Description

This volume comprises the topical reviews and specialists' contributions presented at the American Chemical Society symposium on Controlled Radical Polymerization (the IUPAC preferred term is Reversible Deactivation Radical Polymerization and it is used in the titles of these volumes). This most recent meeting was a sequel to several previous ACS Symposia on controlled/living radical polymerization.

These two volumes are dedicated to mechanisms and techniques (volume 1 consisting of 18 chapters) and materials and applications (volume 2, which consists of 16 chapters). All chapters published in these two volumes show that reversible deactivation radical polymerization has made significant progress within the last two decades. New systems have been discovered, substantial progress has been achieved in understanding the mechanism and kinetics of reactions involved in all reversible deactivation radical polymerization systems. Significant progress has also been made towards developing a comprehensive relationship between molecular structure and macroscopic properties. Several commercial applications of reversible deactivation radical polymerization have been announced and it is anticipated that new products made by controlled/living radical polymerization will soon be on the market.

Reversible Deactivation Radical Polymerization

Mechanisms and Synthetic Methodologies

Edited by Krzysztof Matyjaszewski, Haifeng Gao, Brent S. Sumerlin, and Nicolay V. Tsarevsky

ACS Symposium Series

Preface .............................................................................................................................. ix
1. Reversible Deactivation Radical Polymerization: State-of-the-Art in 2017 ....... 1
Sivaprakash Shanmugam and Krzysztof Matyjaszewski
2. Mechanistic Insights into Lewis Acid Mediated Sequence- and
Stereo-Control in Radical Copolymerization ...................................................... 41
Nicholas S. Hill, Benjamin B. Noble, and Michelle L. Coote
3. Time-Resolved Electron Spin Resonance Observations of the Initial Stages
of Conventional and Controlled Radical Polymerization Processes ................. 63
Atsushi Kajiwara
4. Elements of RAFT Navigation .............................................................................. 77
Joris J Haven, Matthew Hendrikx, Tanja Junkers, Pieter J Leenaers,
Theodora Tsompanoglou, Cyrille Boyer, Jiangtao Xu, Almar Postma, and
Graeme Moad
5. Reducing the Hydrogen Atom Abstraction Efficiencies of
Benzophenone-Based Photosensitive Alkoxyamines ........................................ 105
Jason C. Morris, Jean-Louis Clément, Yohann Guillaneuf, Steven E. Bottle,
Kathryn Fairfull-Smith, and Didier Gigmes
6. Catalyzed Radical Termination (CRT) in the Metal-Mediated
Polymerization of Acrylates: Experimental and Computational Studies ...... 135
Thomas G. Ribelli, S. M. Wahidur Rahaman, Krzysztof Matyjaszewski, and
Rinaldo Poli
7. Electrochemical Procedures To Determine Thermodynamic and Kinetic
Parameters of Atom Transfer Radical Polymerization .................................... 161
Francesca Lorandi, Marco Fantin, Francesco De Bon, Abdirisak A. Isse, and
Armando Gennaro
8. Insights into the Reactivity of Epoxides as Reducing Agents in
Low-Catalyst-Concentration ATRP Reactions ................................................. 191
David C. McLeod, Kapil Dev Sayala, and Nicolay V. Tsarevsky
9. Toward Butadiene-ATRP with Group 10 (Ni, Pd, Pt) Metal Complexes ........ 205
Vignesh Vasu, Joon-Sung Kim, Hyun-Seok Yu, William I. Bannerman,
Mark E. Johnson, and Alexandru D. Asandei
10. Reversible Deactivation Radical Polymerization of Vinyl Chloride ............... 227
Carlos M. R. Abreu, Ana C. Fonseca, Nuno M. P. Rocha, James T. Guthrie,
Arménio C. Serra, and Jorge F. J. Coelho
11. Photoinduced Metal Free Strategies for Atom Transfer Radical
Polymerization ...................................................................................................... 263
G. Yilmaz, C. Kutahya, A. Allushi, C. Aydogan, S. Aykac, and Y. Yagci
12. Recent Developments in External Regulation of Reversible Addition
Fragmentation Chain Transfer (RAFT) Polymerization ................................. 273
Sivaprakash Shanmugam, Cyrille Boyer, and Krzysztof Matyjaszewski
13. How Can Xanthates Control the RAFT Polymerization of Methacrylates? .... 291
Mathias Destarac, Dimitri Matioszek, Xavier Vila, Juliette Ruchmann-Sternchuss,
and Samir Z. Zard
14. Hydroxyl Radical Activated RAFT Polymerization ......................................... 307
Thomas G. McKenzie, Amin Reyhani, Mitchell D. Nothling, and Greg G. Qiao
15. Vinyl Ether/Vinyl Ester Copolymerization by Cationic and Radical
Interconvertible Simultaneous Polymerization ................................................. 323
Kotaro Satoh, Yuuma Fujiki, Mineto Uchiyama, and Masami Kamigaito
16. Catalytic Chain Transfer Polymerization and Reversible Deactivation
Radical Polymerization of Vinyl Acetate Mediated by Cobalt(II)
Phenoxy-imine Complexes .................................................................................. 335
Yi-Hao Chen, Hung-Hsun Lu, Jia-Qi Li, and Chi-How Peng
17. Tailor-Made Poly(vinylamine)s via Thermal or Photochemical
Organometallic Mediated Radical Polymerization ........................................... 349
Pierre Stiernet, Mathilde Dréan, Christine Jérôme, Patrick Midoux, Philippe Guégan,
Jutta Rieger, and Antoine Debuigne
18. Alkyl Bromide as Precursor of Initiating Dormant Species in
Organocatalyzed Living Radical Polymerization ............................................. 365
Feifei Li, Longqiang Xiao, and Atsushi Goto
19. Biocatalytic ATRP ................................................................................................ 379
Jonas Pollard and Nico Bruns
Editors' Biographies .................................................................................................... 395
Indexes
Author Index ................................................................................................................ 399
Subject Index ................................................................................................................ 401

Reversible Deactivation Radical Polymerization

Mechanisms and Synthetic Methodologies

Edited by Krzysztof Matyjaszewski, Haifeng Gao, Brent S. Sumerlin, and Nicolay V. Tsarevsky

ACS Symposium Series

Author Information

Edited by Krzysztof Matyjaszewski, J.C. Warner University Professor of Natural Sciences, Carnegie Mellon University, Edited by Haifeng Gao, Associate Professor of Chemistry and Biochemistry, University of Notre Dame, Edited by Brent S. Sumerlin, George Bergen Butler Professor of Polymer Chemistry, University of Florida, and Edited by Nicolay V. Tsarevsky, Associate Professor of Chemistry, Southern Methodist University

Kris Matyjaszewski is the J.C. Warner University Professor of Natural Sciences at Carnegie Mellon University. He discovered Cu-mediated atom transfer radical polymerization in 1995. He has co-authored >1000 publications (>90,000 citations) and holds 56 US patents. Matyjaszewski has received the 2017 Franklin Medal in chemistry (with Prof. Sawamoto), 2015 Dreyfus Prize in Chemical Sciences, 2011 Wolf Prize in Chemistry, 2009 Presidential Green Chemistry Challenge Award, 2015 Overberger Prize, 2013 AkzoNobel North America Science Award, 2011 Applied Polymer Science Award, and the 2002 Polymer Chemistry Award. He is a member of the National Academy of Engineering, National Academy of Inventors, and the Polish and Russian Academies of Sciences. Haifeng Gao is an Associate Professor at the Department of Chemistry and Biochemistry, University of Notre Dame. He earned his Ph.D. in 2008 in Chemistry under Prof. Matyjaszewski at Carnegie Mellon University. After two-year postdoc training at University

of California Berkeley, he joined the University of Notre Dame in 2011 as an assistant professor and was promoted to associate professor with tenure in 2017. His research focuses on the design and synthesis of functional polymers with controlled nanostructures by determining their fundamental structure-property relationships. He has co-authored over 80 peer-reviewed papers and 6 book chapters cited more than 4000 times. Brent Sumerlin is the George Bergen Butler Professor of Polymer Chemistry at the University of Florida (UF). He obtained his Ph.D. in polymer science and engineering from the University of Southern Mississippi under Prof. McCormick. After postdoctoral training with Prof. Matyjaszewski at Carnegie Mellon University, he joined the faculty of Southern Methodist University in 2005 before moving to UF in 2012. He is a Fellow of the Royal Society of Chemistry and has won a number of awards, including the Alfred P. Sloan Research Fellowship, NSF CAREER Award, the Journal of Polymer

Science Innovation Award, Biomacromolecules/Macromolecules Young Investigator Award, and the Hanwha-Total IUPAC Award. Nick Tsarevsky obtained a Ph.D. in chemistry in 2005 from Carnegie Mellon University under Prof. Matyjaszewski. He was a visiting assistant professor at the Department of Chemistry, Carnegie Mellon University (2005-2006) and CSO of ATRP Solutions, Inc. (2007-2010). He joined the Department of Chemistry at Southern Methodist University in 2010 as an assistant professor and was promoted in 2016 to tenured associate professor. He has authored and coauthored over 90 peer-reviewed journal articles and book chapters, 1 textbook, and has co-edited 5 books. Research interests include polymerization techniques, functional materials, coordination chemistry, catalysis, hypervalent iodine compounds, and history of chemistry and chemical education.