Kinetic study of 1,5-hydrogen transfer reactions of methyl acrylate and butyl acrylate using quantum chemistry

Xinrui Yu, Linda J. Broadbelt*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

1,5-Hydrogen transfer reactions in methyl acrylate and butyl acrylate free-radical polymerization are studied using quantum chemistry and transition state theory to estimate the kinetic parameters (k tr, E a, and A) with tetrameric radicals, requiring a number of atoms that ranks among the largest polymeric mimics to date. A two-step transformation accounted for the overall reaction: rotation from an extended conformation to a coiled conformation and abstraction of the fifth hydrogen atom by the end-chain radical. UB3LYP/6-31G(d) was used for geometry optimization, validation of the transition states, and calculation of frequencies that were used to obtain thermodynamic properties. The more computationally demanding level of theory, MPWB1K/6-31G(d,p), was used for calculation of the electronic energy.

Original languageEnglish (US)
Pages (from-to)461-469
Number of pages9
JournalMacromolecular Theory and Simulations
Volume21
Issue number7
DOIs
StatePublished - Aug 1 2012

Keywords

  • acrylates
  • free radical polymerization
  • hydrogen transfer
  • kinetics (polym.)
  • polymerization (general)

ASJC Scopus subject areas

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

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