Kinetic investigation of the anionic polymerization of MMA using sparteine as σ-ligand

François Lavaud, Michel Fontanille*, Yves Gnanou

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

The kinetics of the anionic polymerization of methyl methacrylate using THF as solvent, 1,1-diphenylhexyllithium as initiator and sparteine as ligand has been investigated in a flow-tube reactor for initiator concentrations higher than 1 x 10-3 mol 1-1 and a temperature range between - 10 and 20 °C. Addition of sparteine induced a decrease in both the reactivity of the growing enolates and the extent of termination reactions. While a fractional kinetic order relative to the active centres was obtained in the presence of sparteine, this additive shifted the equilibrium between aggregated and unimeric species toward the formation of unimeric-ligated enolates as indicated by entropic and enthalpic parameters of the aggregation equilibrium. The rate constants of propagation and termination of these growing species were also determined.

Original languageEnglish (US)
Pages (from-to)7195-7205
Number of pages11
JournalPolymer
Volume43
Issue number25
DOIs
StatePublished - Oct 28 2002

Keywords

  • 1,1-Diphenylhexyllithium
  • Anionic polymerization
  • Sparteine

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

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