CHAPTER 4: Controlled/Living Radical Polymerization Mediated by Stable Organic Radicals
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Published:04 Apr 2013
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Series: Polymer Chemistry Series
P. Nesvadba, in Fundamentals of Controlled/Living Radical Polymerization, ed. N. V. Tsarevsky and B. S. Sumerlin, The Royal Society of Chemistry, 2013, pp. 112-167.
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The development of stable-radical mediated polymerization (SRMP) from its origins with focus on nitroxide-mediated radical polymerization (NMP) is reviewed. The underlying persistent radical effect, mechanistic steps, fundamental kinetic equations and side reactions of NMP are discussed. The most important nitroxides and alkoxyamine initiators for NMP are presented, along with the parameters influencing the rate constants of cleavage and reformation of alkoxyamines. Applications of NMP for synthesis of complex polymeric structures and in industry are shown, and advances in nitroxide-mediated photopolymerization (NMPP) are discussed. SRMP with the most important non-nitroxide stable organic radicals as well as the organometallic-mediated radical polymerization (OMRP) are briefly mentioned.