Nitroxide Mediated Radical Polymerization

Nitroxide-mediated radical polymerization is a method of radical polymerization that makes use of an alkoxyamine initiator to generate polymers with well controlled stereochemistry and a very low polydispersity index. It is a type of reversible-deactivation radical polymerization.

The initiating materials for nitroxide-mediated radical polymerization (NMP) are a family of compounds referred to as alkoxyamines. An alkoxyamine can essentially be viewed as an alcohol bound to a secondary amine by an N-O single bond. The utility of this functional group is that under certain conditions, homolysis of the C-O bond can occur, yielding a stable radical in the form of a 2-center 3-electron N-O system and a carbon radical which serves as an initiator for radical polymerization. For the purposes of NMP, the R groups attached to the nitrogen are always bulky, sterically hindering groups and the R group in the O- position forms a stable radical, generally is benzylic for polymerization to occur successfully. NMP allows for excellent control of chain length and structure, as well as a relative lack of true termination that allows polymerization to continue as long as there is available monomer. Because of this it is said to be “living".

The living nature of NMP is due to the persistent radical effect (PRE). The PRE is a phenomenon observable in some radical systems which leads to the highly favored formation of one product to the near exclusion of other radical couplings due to one of the radical species being particularly stable, existing in greater and greater concentrations as the reaction progresses while the other one is transient, reacting quickly with either itself in a termination step or with the persistent radical to form a desired product. As time goes on, a higher concentration of the persistent radical is present, which couples reversibly with itself, meaning that any of the transient radical still present tends to couple with the persistent radical rather than itself due to greater availability. This leads to a greater proportion of cross-coupling than self-coupling in radical species.

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