Controlled/living heterogeneous radical polymerization in supercritical carbon dioxide

Authors

  • Per B. Zetterlund,

    Corresponding author
    1. Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe 657-8501, Japan
    • Centre of Advanced Macromolecular Design, School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, New South Wales 2052, Australia
    Search for more papers by this author
  • Fawaz Aldabbagh,

    Corresponding author
    1. School of Chemistry, National University of Ireland, Galway, Ireland
    • School of Chemistry, National University of Ireland, Galway, Ireland
    Search for more papers by this author
  • Masayoshi Okubo

    Corresponding author
    1. Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe 657-8501, Japan
    • Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe 657-8501, Japan
    Search for more papers by this author

Abstract

Supercritical carbon dioxide (scCO2) is an inexpensive and environmentally friendly medium for radical polymerizations. ScCO2 is suited for heterogeneous controlled/living radical polymerizations (CLRPs), since the monomer, initiator, and control reagents (nitroxide, etc.) are soluble, but the polymer formed is insoluble beyond a critical degree of polymerization (Jcrit). The precipitated polymer can continue growing in (only) the particle phase giving living polymer of controlled well-defined microstructure. The addition of a colloidal stabilizer gives a dispersion polymerization with well-defined colloidal particles being formed. In recent years, nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition fragmentation chain transfer (RAFT) polymerization have all been conducted as heterogeneous polymerizations in scCO2. This Highlight reviews this recent body of work, and describes the unique characteristics of scCO2 that allows composite particle formation of unique morphology to be achieved. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3711–3728, 2009

Ancillary