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Keywords:

  • chain-end functionality;
  • controlled radical polymerization;
  • functional alkoxyamines;
  • functionalization of polymers;
  • nitroxide-mediated polymerization;
  • radical polymerization;
  • UV-vis spectroscopy

Abstract

The ester-functional alkoxyamine 2,2-dimethyl-3-(1-(4-(methoxycarbonyl)phenyl)ethoxy)-4-(4-(methoxycarbonyl)phenyl)-3-azapentane (2) was efficiently synthesized for use as a functional initiator in nitroxide-mediated polymerization. Two equivalents of 1-(4-(methoxycarbonyl)phenyl)ethyl radical were added across the double bond of 2-methyl-2-nitrosopropane to form alkoxyamine 2, which was found to control the polymerization of styrene, isoprene, and n-butyl acrylate. The ester moieties were hydrolyzed for subsequent esterification with 1-pyrenebutanol to form a dipyrene-labeled initiator that was used to probe nitroxide end-group fidelity after styrene polymerization. High retention of nitroxide was confirmed by UV-vis studies over a range of monomer conversions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6342–6352, 2009