Controlled ROP of β-Butyrolactone Simply Mediated by Amidine, Guanidine, and Phosphazene Organocatalysts

Authors

  • Cédric G. Jaffredo,

    1. Institut des Sciences Chimiques de Rennes, Organometallics, Materials and Catalysis, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
    Search for more papers by this author
  • Jean-François Carpentier,

    Corresponding author
    1. Institut des Sciences Chimiques de Rennes, Organometallics, Materials and Catalysis, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
    • Institut des Sciences Chimiques de Rennes, Organometallics, Materials and Catalysis, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France.
    Search for more papers by this author
  • Sophie M. Guillaume

    Corresponding author
    1. Institut des Sciences Chimiques de Rennes, Organometallics, Materials and Catalysis, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
    • Institut des Sciences Chimiques de Rennes, Organometallics, Materials and Catalysis, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France.
    Search for more papers by this author

Abstract

Basic organocatalysts of the guanidine (1,5,7-triazabicyclo[4.4.0]dec-5-ene, TBD), amidine (1,8-diazabicyclo[5.4.0]-undec-7-ene, DBU), and phosphazene (2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2diazaphosphorine, BEMP) type do effectively polymerize β-butyrolactone (BL). Poly(3-hydroxybutyrate)s (PHBs) with controlled molecular features, that is, controlled molar masses, narrow molar mass distributions, and well-defined functional end groups are thus formed at 60 °C from bulk monomer, with equation image up to 21 500 g mol−1. The formation of α,ω-guanidine/amidine/phosphazene,crotonate functionalized PHBs, as demonstrated by NMR, SEC, and MALDI–ToF mass spectrometry analyses, mechanistically suggests the formation of N-acyl-α,β-unsaturated propagating species that originate from 1:1 guanidine/amidine/phosphazene:BL adducts.

Ancillary