Dependence of the kinetics of the anionic polymerization of methyl methacrylate on the concentration in active centers

François Lavaud, Michel Fontanille, Yves Gnanou*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


Studies on the anionic polymerization of methyl methacrylate in tetrahydrofuran and in the presence of sparteine have revealed a beneficial effect due to this additive, resulting in a decrease in the extent of termination. Better control of the definition of the polymers formed can thus be achieved in the presence of this additive. On the other hand, macromolecular engineering requires a range of active species concentrations lower than 10 -3 mol L-1 and particularly the synthesis of polymers of high molar masses. For a better understanding of the mechanism of chain growth under such concentration conditions, the kinetics of polymerization have been investigated with a technique based on adiabatic calorimetry. Sparteine has been found to lack sufficient cation-binding power to prevent the propagating enolate ion pairs from aggregating. The rate constant of propagation of nonaggregated species has been estimated, as well as the aggregation constant of equilibrium. For very low initiator concentrations, termination reactions have been shown to profoundly alter the control of the polymerization and to prevent a quantitative monomer conversion. Theoretical maximal conversions have been calculated from kinetic data and compare well with the experimental values.

Original languageEnglish (US)
Pages (from-to)4964-4975
Number of pages12
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number19
StatePublished - Oct 1 2004
Externally publishedYes


  • Adiabatic calorimetry
  • Aggregation constant
  • Anionic polymerization
  • Kinetic studies
  • Methyl methacrylate
  • Sparteine

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry


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