Get access

Reversible addition–fragmentation chain-transfer polymerization: Unambiguous end-group assignment via electrospray ionization mass spectrometry

Authors

  • Philipp Vana,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
    Search for more papers by this author
  • Luca Albertin,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
    Search for more papers by this author
  • Leonie Barner,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
    Search for more papers by this author
  • Thomas P. Davis,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
    Search for more papers by this author
  • Christopher Barner-Kowollik

    Corresponding author
    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
    • Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
    Search for more papers by this author

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

Ancillary