Self-directed formation of uniform unsaturated macromolecules from acrylate monomers at high temperatures

Authors

  • Thomas Junkers,

    Corresponding author
    1. Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
    • Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
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  • Francesca Bennet,

    1. Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
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  • Sandy P. S. Koo,

    1. Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
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  • Christopher Barner-Kowollik

    Corresponding author
    1. Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
    • Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
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Abstract

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Structurally highly uniform poly(butyl acrylate) macromonomers are conveniently synthesized via autoinitiated free-radical polymerization at high temperatures in solution of butyl or hexyl acetate without the need to employ any mediating agent. ESI-MS analysis reveals that neither the primary initiating radical nor the empoyed solvent has a large impact on the product distribution. It is further demonstrated that the mechanism of their formation relies on complex addition-fragmentation equilibria not unlike the RAFT mechanism effectively resulting in a self-organization of the reaction. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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