Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

Daria E. Lonsdale, Geoffrey Johnston-Hall, Amanda Fawcett, Craig A. Bell, Carl N. Urbani, Michael R. Whittaker, Michael J. Monteiro

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5 Citations (Scopus)


In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (Ctrs) determined using the Mayo method is equal to 3.8 × 10-3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10-3). Simulations, including chain-length-dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion-time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the Mn data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism.

Original languageEnglish
Pages (from-to)3620-3625
Number of pages6
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number16
Publication statusPublished - 15 Aug 2007
Externally publishedYes


  • Kinetics (polym.)
  • Modeling
  • Radical polymerization
  • Retardation time

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