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In situ nitroxide-mediated polymerization of styrene promoted by the N-tert-butyl-α-isopropylnitrone/bpo pair: ESR investigations

Authors

  • Christophe Detrembleur,

    Corresponding author
    1. Department of Chemistry, University of Liege, Center for Education and Research on Macromolecules (CERM), Sart-Tilman, B6A, B-4000 Liège, Belgium
    • Department of Chemistry, University of Liege, Center for Education and Research on Macromolecules (CERM), Sart-Tilman, B6A, B-4000 Liège, Belgium
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  • Jean-Louis Clément,

    1. Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire UMR7273, Av. Esc. Normandie Niemen 13397 Marseille Cedex 20, France
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  • Valérie Sciannaméa,

    1. Chimie des Polymères, Institut Charles Sadron CNRS UPR22, 23 rue du Loess, BP 84037, 67034 Strasbourg Cedex, France
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  • Christine Jérôme,

    1. Department of Chemistry, University of Liege, Center for Education and Research on Macromolecules (CERM), Sart-Tilman, B6A, B-4000 Liège, Belgium
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  • Jean-Marie Catala,

    1. Chimie des Polymères, Institut Charles Sadron CNRS UPR22, 23 rue du Loess, BP 84037, 67034 Strasbourg Cedex, France
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  • Didier Gigmes,

    Corresponding author
    1. Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire UMR7273, Av. Esc. Normandie Niemen 13397 Marseille Cedex 20, France
    • Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire UMR7273, Av. Esc. Normandie Niemen 13397 Marseille Cedex 20, France
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  • Laurent Autissier,

    1. Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire UMR7273, Av. Esc. Normandie Niemen 13397 Marseille Cedex 20, France
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  • Edith Botek,

    1. Laboratoire de Chimie Théorique, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
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  • Natalia Zarycz,

    1. Laboratoire de Chimie Théorique, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
    2. Departamento de Fisica, Universidad Nacional del Nordeste, 3400 Corrientes, Argentina
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  • Benoît Champagne

    Corresponding author
    1. Laboratoire de Chimie Théorique, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
    • Laboratoire de Chimie Théorique, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
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Abstract

The styrene polymerization initiated by benzoyl peroxide (BPO) in the presence of N-tert-butyl-α-isopropylnitrone as nitroxide precursor is well-controlled provided that a prereaction between the nitrone and BPO is carried out in suitable conditions prior to polymerization at a higher temperature. Electron spin resonance (ESR) spectroscopy was implemented to probe the nitroxides formed during both steps, that is, the prereaction and polymerization, and to get crucial information regarding the structure of the nitroxides responsible for the polymerization control. ESR studies combined with first principles calculations have evidenced that nitroxides observed during the prereaction in the presence of styrene and during the polymerization steps consist of a mixture of two macronitroxides. One is formed by the addition of a growing polystyrene chain to the nitrone as would be expected. However, the second one results from the addition of a polystyrene chain to tert-butyl nitroso that is in situ formed presumably by decomposition of the first macronitroxide type. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

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