Estimation of free radical polymerization rate coefficients using computational chemistry

Siziwe Bebe, Xinrui Yu, Robin A. Hutchinson*, Linda J. Broadbelt

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

13 Scopus citations


This study explores the application of computational chemistry to estimate free radical polymerization rate coefficients. The Evans-Polanyi relationship is combined with computed heats of polymerization to estimate copolymerization reactivity ratios for many vinyl monomer pairs, focusing on acrylates, methacrylates and styrene, with accuracy assessed by comparison to experimental values. The effect of different optimization approaches on the values of thermodynamic properties is explored, and it is concluded that a combination of conventional optimization and relaxed potential energy scans was most effective at identifying global minima. The difference between thermodynamic properties calculated using the harmonic oscillator treatment and a hindered rotor model is evaluated for methyl methacrylate polymerization.

Original languageEnglish (US)
Pages (from-to)179-189
Number of pages11
JournalMacromolecular Symposia
StatePublished - 2006


  • Conformation optimization
  • Hindered rotor model
  • Kinetics (polym.)
  • Quantum chemistry
  • Radical polymerization
  • Reactivity ratios

ASJC Scopus subject areas

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


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