SEARCH

SEARCH BY CITATION

Keywords:

  • atom transfer radical polymerization;
  • functionalization;
  • telechelic polymers;
  • tertiary amine groups;
  • amination;
  • 1,1-diphenylethylenes;
  • functionalized polystyrene

Abstract

The quantitative synthesis of tertiary amine-functionalized polymers by atom transfer radical polymerization is reported. Tertiary amine-functionalized polystyrene was prepared with the adduct of 1-(bromoethyl)benzene with 1-(4-dimethyl-aminophenyl)-1-phenylethylene as an initiator in the atom transfer radical polymerization of styrene in the presence of a copper (I) bromide/2,2′-bipyridyl catalyst system. The polymerization proceeded via a controlled free-radical polymerization process to afford quantitative yields of the corresponding tertiary amine-functionalized polystyrene with predictable number-average molecular weights (1600–4400), narrow molecular weight distributions (1.09–1.31), and an initiator efficiency of 0.95. The polymerization process was monitored by gas chromatographic analysis. The tertiary amine-functionalized polymers were characterized by thin-layer chromatography, size exclusion chromatography, potentiometry, and spectroscopy. All experimental evidence was consistent with quantitative functionalization via the 1,1-diphenylethylene derivative. Polymerization kinetic measurements showed that the polymerization reaction followed first-order-rate kinetics with respect to monomer consumption and that the number-average molecular weight increased linearly with monomer conversion. © 2001 John Wiley & Sons, Inc. J Polym Sci A Part A: Polym Chem 39: 2058–2067, 2001