Kinetic modeling of controlled living microemulsion polymerizations that use reversible addition-fragmentation chain transfer

Kevin D. Hermanson, Liu Shiyonc, Eric W. Kaler

Research output: Contribution to journalArticle

30 Scopus citations

Abstract

Reversible addition-fragmentation chain transfer (RAFT) polymerization is a useful technique for the formation of polymers with controlled architectures and molecular weights. However, when used in the polymerization of microemulsions, RAFT agents are only able to control the polymer molecular weight only at high RAFT concentrations. Here, a kinetic model describing RAFT microemulsion polymerizations is derived that predicts the reaction rates, molecular weight polydispersities, and particle size. The model predicts that at low RAFT concentrations, the RAFT agent will be consumed early in the reaction and that this will result in uncontrolled polymerization in particles nucleated late in the reaction. The higher molecular weight polydispersity that is observed in RAFT microemulsion polymerizations is the result of this uncontrolled polymerization. The model also predicts a shift in the conversion at which the maximum reaction rate occurs and a decrease in the particle size with increasing RAFT concentration. Both of these trends are also consistent with those observed experimentally.

Original languageEnglish (US)
Pages (from-to)6055-6070
Number of pages16
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume44
Issue number20
DOIs
StatePublished - Oct 15 2006

Keywords

  • Controlled living polymerization
  • Emulsion polymerization
  • Kinetics (polym.)
  • Microemulsion polymerization
  • Reversible addition fragmentation chain transfer (RAFT)

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