Thioketone-mediated polymerization of butyl acrylate: Controlling free-radical polymerization via a dormant radical species

Thomas Junkers, Martina H. Stenzel, Thomas P. Davis, Christopher Barner-Kowollik

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35 Citations (Scopus)


It is demonstrated by experiment and simulation that the commercially available thioketone 4,4-bis(dimethylamino)thiobenzophenone is capable of controlling AIBN-initiated bulk butyl acrylate polymerization at 80°C. On the basis of molecular weight data and from monomer onversion versus time curves, the associated rate parameters are estimated. The addition rate coefficient, kad, for the reaction of a propagating chain with the thioketone is close to 106 L · mol-1 · s-1 -1 and the fragmentation rate coefficient, kfrag, is around 10-2 s-1 giving rise to large equilibrium constants in the order of 108 L · mol-1. Furthermore, cross-and self-termination of the dormant radical species are identified to be operational.

Original languageEnglish
Pages (from-to)746-753
Number of pages8
JournalMacromolecular Rapid Communications
Issue number6
Publication statusPublished - 16 Mar 2007
Externally publishedYes


  • Kinetics (polym.)
  • Living/controlled free radical polymerization
  • Molecular weight distribution
  • Thioketone mediated polymerization (TKMP)

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