Polymerization nitroxy-mediated radical

Nitroxyl radicals, stable, 14 298 Nitroxy-mediated polymerization (NMP), 14 297-298... 

The living R-ROP of cyclic ketene acetals was achieved with nitroxy-mediated polymerization (NMP) (29), ATRP (30), and RAFT (31) methods to afford the polyesters with low polydispersities. Recently, it has been reported that the block and random copolymers with vinyl monomers showing low polydispersities could also be obtained by living radical ring-opening copolymerizations (32, 33). 

The in situ approach leads to the formation of multiple nitroxide initiating species and there is not perfect stoicheometry between the initiating and mediating species. With the presynthesis approach, a pure compound can be used to initiate polymerization which should lead to cleaner chemistry. However, it has been believed that excess nitroxy radicals is important to achieve narrow polydis-persity and good end-group purity (249). 

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