Low conversion 4-acetoxystyrene free-radical polymerization kinetics determined by pulsed-laser and thermal polymerization

Ning Li, Andrew S. Cho, Linda J Broadbelt*, Robin A. Hutchinson

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The free-radical polymerization kinetics of 4-acetoxystyrene (4-AcOS) is studied over a wide temperature range. Pulsed-laser polymerization, in combination with dual detector size-exclusion chromatography, is used to measure kp, the propagation rate coefficient, between 20 and 110°C. Values are roughly 50% higher than those of styrene, while the activation energy of 28.7 kJ · mol-1 is lower than that of styrene by 3-4 kJ · mol-1. With known kp, conversion and molecular weight data from 4-AcOS thermal polymerizations conducted at 100, 140, and 170°C are used to estimate termination and thermal initiation kinetics. The behavior is similar to that previously observed for styrene, with an activation energy of 90.4 kJ · mol-1 estimated for the third-order thermal initiation mechanism.

Original languageEnglish (US)
Pages (from-to)1429-1438
Number of pages10
JournalMacromolecular Chemistry and Physics
Volume207
Issue number16
DOIs
StatePublished - Aug 23 2006

Keywords

  • 4-acetoxystyrene
  • Free-radical polymerization
  • Kinetics (polym.)
  • Pulsed-laser polymerization
  • Thermal polymerization

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

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