Xanthate Mediated Living Polymerization of Vinyl Acetate: A Systematic Variation in MADIX/RAFT Agent Structure

Authors

  • Martina H. Stenzel,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
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  • Lyndal Cummins,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
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  • G. Evan Roberts,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
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  • 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
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  • 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
    2. Current address: Institut für Physikalische Chemie, Georg-August-Universität Göttingen, 37077 Göttingen, Germany.
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  • 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. Fax: +61 2 9385 6250
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Abstract

Eight xanthates were synthesized to induce living free radical polymerization of vinyl acetate. Four compounds, methyl (4-methoxyphenoxy)carbonothioylsulfanyl acetate, methyl (methoxycarbonothioyl)sulfanyl acetate, methyl (ethoxycarbonothioyl)sulfanyl acetate and methyl (isopropoxycarbonothioyl)sulfanyl acetate were identified as suitable MADIX/RAFT agents, yielding low polydispersity (PDI < 1.2) poly(vinyl acetate) of molecular weights exceeding 5 × 104 g · mol−1. All suitable MADIX/RAFT agents exhibited extended periods of inhibition (0.3 h < tinh < 10 h) and moderate rate retardation. The ability of these compounds to control vinyl acetate polymerization can be correlated with the electron density on the central carbon atom of the xanthate. Electrospray ionization mass spectrometric analysis was performed to complete the investigation on the new MADIX/RAFT agents.

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