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Radical entry mechanisms in redox-initiated emulsion polymerizations

David J Lamb, Christopher Fellows, Robert G Gilbert

Research output: Contribution to journalArticlepeer-review

31 Citations (Scopus)

Abstract

The mechanisms and kinetics of radical entry in emulsion polymerizations utilizing redox initiation are investigated using polymerization rate data obtained by reaction calorimetry and electrospray mass spectroscopy analysis of initiator-derived aqueous-phase products. These data have been used to evaluate an initiation scheme for redox-initiated emuslion polymerizations of common monomers such as styrene and methyl methacrylate based around the oxidant, 'tert'-butyl hydroperoxide. Redox initiators are broadly classed by the solubility of their radical products: Hydrophilic radicals enter by propagating to a critical degree of polymerization to become surface-active whilst more hydrophobic radicals may enter particles directly. When direct entry is applicable (the hydrophobic case), initiation efficiency will always be very high.
Original languageEnglish
Pages (from-to)469-481
JournalPolymer
Volume46
Issue number19
DOIs
Publication statusPublished - 2005

Keywords

  • Physical Chemistry of Materials
  • Chemical Thermodynamics and Energetics
  • Chemical Characterisation of Materials

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