Controlled radical polymerization of styrene in the presence of nitronyl nitroxides

Abstract
Bulk radical polymerization of styrene in the presence of nitronyl nitroxides (2‐(4‐substituted phenyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydroimidazolyl‐1‐oxyl 3‐oxide) was studied. All nitronyl nitroxides, like other nitroxyl radicals such as 2,2,6,6‐tetramethylpiperidine 1‐oxyl radical (TEMPO), act as reversible radical scavengers. The efficiency of controlling the polymerization is affected by the substituent at the 4′‐position. The efficiency increases with electron donating strength of 4′‐substituents, at least at the beginning of the reaction. However, the thermal stability of nitronyl nitroxides decreases in the same order. Thus, TEMPO is more suitable than nitronyl nitroxides for controlled/“living” radical polymerization of styrene.

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