Get access

Xanthates as Chain-Transfer Agents in Controlled Radical Polymerization (MADIX): Structural Effect of the O-Alkyl Group

Authors

  • Mathias Destarac,

    Corresponding author
    1. Rhodia Recherches, Centre de Recherches d'Aubervilliers, 52, rue de la Haie Coq, 93308 Aubervilliers Cedex, France
    • Rhodia Recherches, Centre de Recherches d'Aubervilliers, 52, rue de la Haie Coq, 93308 Aubervilliers Cedex, France.
    Search for more papers by this author
  • Wojciech Bzducha,

    1. Rhodia Recherches, Centre de Recherches d'Aubervilliers, 52, rue de la Haie Coq, 93308 Aubervilliers Cedex, France
    Search for more papers by this author
  • Daniel Taton,

    1. Rhodia Recherches, Centre de Recherches d'Aubervilliers, 52, rue de la Haie Coq, 93308 Aubervilliers Cedex, France
    2. Laboratoire de Chimie des Polymères Organiques, ENSCPB-CNRS-Université Bordeaux 1, 16, Avenue Pey Berland, 33 607 Pessac Cedex, France
    Search for more papers by this author
  • Isabelle Gauthier-Gillaizeau,

    1. Département de Synthèse Organique, Ecole Polytechnique, 91128 Palaiseau Cedex, France
    Search for more papers by this author
  • Samir Z. Zard

    Corresponding author
    1. Département de Synthèse Organique, Ecole Polytechnique, 91128 Palaiseau Cedex, France
    • Département de Synthèse Organique, Ecole Polytechnique, 91128 Palaiseau Cedex, France.
    Search for more papers by this author

  • Supporting information for this article is available on the journal's homepage under www.mrc-journal.de or from the author.

Abstract

The capability of three chain-transfer agents, O-alkyl-S-(1-ethoxycarbonyl)ethyl xanthates (CH3CHCO2C2H5)S(C[DOUBLE BOND]S)OZ′, to control the free-radical polymerization of styrene and ethyl acrylate by the MADIX process was examined. The reactivity of the xanthates varied according to the following trend: Z′ [DOUBLE BOND] CH2CH3 < CH2CF3 < CH[P(O)(OEt)2]CF3. This change in reactivity allowed a lowering of the polydispersity index from 2.0 for Z′ [DOUBLE BOND] CH2CH3 to 1.15 for Z′ [DOUBLE BOND] CH[P(O)(OEt)2]CF3 in the case of the polymerization of styrene.

original image

Evolution of Mw/Mn with conversion during the polymerization of ethyl acrylate in the presence of xanthates X1, X2 and X3. Reaction conditions: [EA]0 = 4.6 M, [X]0 = 5.75 × 10−2M, [AIBN]0 = 1.72 × 10−3M ; T = 80 °C ; solvent: toluene.

Ancillary