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Cobalt-Mediated Radical Polymerization of Acrylonitrile: Kinetics Investigations and DFT Calculations

  1. Antoine Debuigne Dr.1,
  2. Catherine Michaux Dr.2,
  3. Christine Jérôme Prof.1,
  4. Robert Jérôme Prof.1,
  5. Rinaldo Poli Prof.3,
  6. Christophe Detrembleur Dr.1

Article first published online: 15 JUL 2008

DOI: 10.1002/chem.200800371

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 14, Issue 25, pages 7623–7637, August 28, 2008

Additional Information

How to Cite

Debuigne, A., Michaux, C., Jérôme, C., Jérôme, R., Poli, R. and Detrembleur, C. (2008), Cobalt-Mediated Radical Polymerization of Acrylonitrile: Kinetics Investigations and DFT Calculations . Chem. Eur. J., 14: 7623–7637. doi: 10.1002/chem.200800371

Author Information

  1. 1

    Center for Education and Research on Macromolecules, University of Liège, Sart-Tilman, B6a, 4000 Liège (Belgium), Fax: (+32) 4-366-3497

  2. 2

    Chimie Biologique Structurale lab, CPTS group Facultés Universitaires Notre-Dame de la Paix (FUNDP), 61 rue de Bruxelles, 5000, Namur (Belgium)

  3. 3

    Laboratoire de Chimie de Coordination, UPR CNRS 8241 liée par convention à l'Université Paul Sabatier et à l'Institut National Polytechnique de Toulouse, 205 Route de Narbonne, 31077 Toulouse, (France), Fax: (+33) 561-553-003

Publication History

  1. Issue published online: 25 AUG 2008
  2. Article first published online: 15 JUL 2008
  3. Manuscript Received: 2 MAR 2008

Funded by

  • “Interuniversity Attraction Poles Programme (PAI VI/27) - Functional Supramolecular Systems”
  • “Fonds National de la Recherche Scientifique”
  • “Agence National de la Recherche”. Grant Number: NT05–2 42140

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Keywords:

  • acrylonitrile;
  • cobalt;
  • density functional calculations;
  • polymerization;
  • radical reactions

Abstract

The successful controlled homopolymerization of acrylonitrile (AN) by cobalt-mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried out starting from a conventional azo-initiator (V-70) in the presence of bis(acetylacetonato)cobalt(II) ([Co(acac)2]) but also by using organocobalt(III) adducts. Molar concentration ratios of the reactants, the temperature, and the solvent were tuned, and the effect of these parameters on the course of the polymerization is discussed in detail. The best level of control was observed when the AN polymerization was initiated by an organocobalt(III) adduct at 0 °C in dimethyl sulfoxide. Under these conditions, poly(acrylonitrile) with a predictable molar mass and molar mass distribution as low as 1.1 was prepared. A combination of kinetic data, X-ray analyses, and DFT calculations were used to rationalize the results and to draw conclusions on the key role played by the solvent molecules in the process. These important mechanistic insights also permit an explanation of the unexpected “solvent effect” that allows the preparation of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) by CMRP.

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