First nitroxide-mediated controlled/living free radical polymerization in an ionic liquid

The controlled/living-radical polymerizations of methyl acrylate in 50% v/v of an ionic liquid initiated by the alkoxyamine generated in situ from 4-oxo-2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (4-oxo-TEMPO) and 2,2'-azoisobutyronitrile (AIBN) at 140-155degreesC are reported. The number-average molecular weights increased linearly with conversion, and polydispersity indices are approximately 1.4 in the best case. The rates of polymerization were greater than in anisole, and similar to the rate of spontaneous polymerization in the ionic liquid.