Journal
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
Volume 48, Issue 7, Pages 1493-1501Publisher
WILEY
DOI: 10.1002/pola.23907
Keywords
acrylate; atom transfer radical polymerization (ATRP); ESR/EPR; continuous wave; Cu(II) species; kinetics (polym.)
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Funding
- Spanish Foundation for Science and Technology (FECYT)
- State secretariat of Universities and Research (Ministry of Science and Education)
- The FWO (Fund for Scientific Research Flanders, Belgium) [G.0312.05N]
- Belgian State, Prime Minister's office [P6/27]
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Identification of the paramagnetic species present in the Cu(I)Br-catalyzed atom transfer radical polymerization (ATRP) of a model monomer (isobornyl acrylate) has been carried out by electron paramagnetic resonance (EPR) in the continuous wave mode at 90 K. Up to five different species-four copper-based species and one organic radical-were detected with this technique. The EPR parameters of the copper-based species are found to differ strongly, and originate from diverse isolated Cu(II) complexes, as well as dipolarly interacting and even exchange-coupled Cu(II) species. The work highlights the complexity of the copper-based EPR signal observed in copper-mediated ATRP reactions. Analysis of the time evolution of the individual EPR contributions reveals the disadvantages of quantitative kinetics studies based on the summed EPR intensity of all copper-based species, as is commonly used in literature for this type of reactions. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1493-1501, 2010
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