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

Philipp Vana, Luca Albertin, Leonie Barner, Thomas P. Davis, Christopher Barner-Kowollik

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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.

Original languageEnglish
Pages (from-to)4032-4037
Number of pages6
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number22
Publication statusPublished - 15 Nov 2002
Externally publishedYes


  • Electrospray ionization (ESI)
  • Living polymerization
  • Mass spectrometry
  • Microstructure
  • Reversible addition-fragmentation chain transfer (RAFT)

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