115 Nitroxide-Mediated Polymerization

DOI: 10.1201/9781003161318-115

Nitroxide-mediated polymerization (NMP) is a method of radical polymerization that makes use of a nitroxide initiator to generate polymers with well-controlled stereochemistry and a very low dispersity. It is a reversible-deactivation radical polymerization based on sterically hindered alkoxyamines having a thermally labile alkoxyamine bond (C-ON) to control the addition of vinyl monomers to the growing polymer chains.

R single bond O single bond N R, 1 R 2, alkoxyamine (initiator) sign of reversible reaction R free radical up arrow R single bond R, initiating radical + free radical O single bond N R, 1 R 2, nitroxyl (mediating radical) in presence of M gives R (M) n single bond O single bond N R 1 R 2.
Figure 115.1 A simplified scheme of nitroxide-mediated polymerization (NMP). Source: Scheme 10.4 from page 257 of Handbook of Vinyl Polymers 2nd Ed. CRC Press ...

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