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Block copolymers via macromercaptan initiated ring opening polymerization

Authors

  • Catherine Lefay,

    Corresponding author
    1. UMR 6264 Laboratoire Chimie Provence, Université de Provence, Avenue Escadrille Normandie-Niémen, Case 542, Marseille 13397, Cedex 20, France
    • UMR 6264 Laboratoire Chimie Provence, Université de Provence, Avenue Escadrille Normandie-Niémen, Case 542, Marseille 13397, Cedex 20, France
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  • David Glé,

    1. UMR 6264 Laboratoire Chimie Provence, Université de Provence, Avenue Escadrille Normandie-Niémen, Case 542, Marseille 13397, Cedex 20, France
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  • Marion Rollet,

    1. UMR 6264 Laboratoire Chimie Provence, Université de Provence, Avenue Escadrille Normandie-Niémen, Case 542, Marseille 13397, Cedex 20, France
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  • Jérôme Mazzolini,

    1. Université de Lyon, Univ. Lyon 1, CPE Lyon, CNRS UMR5265, Laboratoire de Chimie, Catalyse, Polymères et Procédés (C2P2), Equipe LCPP, 43 Bd du 11 Novembre 1918, F-69616, Villeurbanne, France
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  • Denis Bertin,

    1. UMR 6264 Laboratoire Chimie Provence, Université de Provence, Avenue Escadrille Normandie-Niémen, Case 542, Marseille 13397, Cedex 20, France
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  • Stéphane Viel,

    1. UMR 6264 Laboratoire Chimie Provence, Equipe SACS, Université de Provence, Avenue Escadrille Normandie-Niémen, Case 512, Marseille 13397, Cedex 20, France
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  • Christina Schmid,

    1. Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany
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  • Christophe Boisson,

    1. Université de Lyon, Univ. Lyon 1, CPE Lyon, CNRS UMR5265, Laboratoire de Chimie, Catalyse, Polymères et Procédés (C2P2), Equipe LCPP, 43 Bd du 11 Novembre 1918, F-69616, Villeurbanne, France
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  • Franck D'Agosto,

    1. Université de Lyon, Univ. Lyon 1, CPE Lyon, CNRS UMR5265, Laboratoire de Chimie, Catalyse, Polymères et Procédés (C2P2), Equipe LCPP, 43 Bd du 11 Novembre 1918, F-69616, Villeurbanne, France
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  • Didier Gigmes,

    Corresponding author
    1. UMR 6264 Laboratoire Chimie Provence, Université de Provence, Avenue Escadrille Normandie-Niémen, Case 542, Marseille 13397, Cedex 20, France
    • UMR 6264 Laboratoire Chimie Provence, Université de Provence, Avenue Escadrille Normandie-Niémen, Case 542, Marseille 13397, Cedex 20, France
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  • Christopher Barner-Kowollik

    Corresponding author
    1. Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany
    • Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany
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Abstract

Poly(styrene) macromercaptanes (Mn = 1900, 3600, and 6100 g mol−1, PDI ≈ 1.2) derived from thiocarbonyl thio capped polymers prepared via reversible addition fragmentation chain transfer polymerization were employed to initiate the ring opening polymerization (ROP) of D,L-lactide under conditions of organo-catalyis employing 4,4-dimethylaminopyridine. Poly(styrene)-block-poly(lactide) polymers of number average molecular weights up to 25,000 g mol−1 (PDI ≈ 1.2 to 1.6) were obtained and characterized via multiple detection size exclusion chromatography (SEC) using refractive index as well as UV detection. In addition, diffusion ordered nuclear magnetic resonance and liquid chromatography at critical conditions (of both polystyrene as well as poly(lactide) were employed to assess the copolymers' structure. Furthermore, it was demonstrated that polyethylenes capped with a thiol moiety can also be readily chain extended in a ROP employing D,L-lactide, evidenced via NMR and high temperature SEC. This study indicates that the direct use of macromercaptantes is indeed a methodology to switch from a radical to a ROP process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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