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Keywords:

  • living polymerization;
  • mass spectrometry;
  • electrospray ionization (ESI);
  • reversible addition–fragmentation chain transfer (RAFT);
  • microstructure

Abstract

Electrospray ionization mass spectrometry was performed to identify the structure of polymeric methyl acrylates generated via the cumyl dithiobenzoate (CDB), cumyl p-fluorodithiobenzoate (CPFDB), and 1-phenylethyl dithiobenzoate (PEDB) mediated reversible addition–fragmentation chain-transfer (RAFT) polymerizations. The relatively simple spectra clearly demonstrate the end groups of this living free-radical polymerization technique. Only polymeric chains carrying one leaving group of the RAFT agent and the dithiobenzoate end group as the active RAFT center were discovered. Multiple-stage mass spectrometric experiments and oxidation of the dithioester end group confirmed the structure of the generated polymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4032–4037, 2002