Nitroxide Mediated Polymerization: From Fundamentals to Applications in Materials Science
Chapter 3: Synthesis of Nitroxides and Alkoxyamines
Published:08 Dec 2015
Special Collection: 2015 ebook collectionSeries: Polymer Chemistry Series
J. P. Blinco, S. E. Bottle, K. E. Fairfull-Smith, E. Simpson, and K. Thomas, in Nitroxide Mediated Polymerization: From Fundamentals to Applications in Materials Science, ed. D. Gigmes, The Royal Society of Chemistry, 2015, ch. 3, pp. 114-152.
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The persistent radical effect (PRE) established in the presence of a nitroxide has been widely investigated for the preparation of macromolecules with narrow molar mass distribution through radical polymerization (both in a bi-molecular fashion employing a nitroxide and radical initiator, and uni-molecularly using a thermally unstable alkoxyamine to supply both fragments). This chapter examines synthetic techniques available for designing both nitroxide free radicals as well alkoxyamines—the key mediating species in uni-molecular, nitroxide mediated polymerization. In both sections, a number of literature examples will be highlighted, with the aim being to provide the reader with a workable selection of design tools for the modification of both nitroxide and R-group moieties.