In situ generation of nitroxide from alkoxyamines for controlled acrylate polymerization

Abstract

AbstractA general strategy for the controlled nitroxide‐mediated polymerization of acrylates from alkoxyamines without addition of excess free nitroxide is outlined. 2,2‐Dimethyl‐3‐(1‐phenylethoxy)‐4‐phenyl‐3‐azapentane (1), prepared in one pot by the addition of 1‐phenylethyl radicals to 2‐methyl‐2‐nitrosopropane, is heated prior to the addition of monomer to afford a mixture of alkoxyamine 1, free nitroxide, and 2,3‐diphenylbutane. With a 30 min preheating period at temperatures up to 125 °C, the kinetics of the subsequent polymerization of n‐butyl acrylate at 125 °C appear largely unaffected, though the ultimate molecular weight of the polymers is dependent upon the preheating temperature. The poly(n‐butyl acrylate) samples, that result from this process, have much narrower molecular weight distributions than those which result in the absence of the preheating process. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5128–5136, 2006