Ab initio study of acrylate polymerization reactions: Methyl methacrylate and methyl acrylate propagation

Xinrui Yu, Jim Pfaendtner, Linda J Broadbelt

Research output: Contribution to journalArticle

65 Scopus citations

Abstract

The kinetic parameters of the free radical propagation of methyl methacrylate and methyl acrylate have been calculated using quantum chemistry and transition state theory. Multiple density functional theory (DFT) methods were used to calculate the activation energy, and it was found that MPWB1K76-31G(d,p) yields results that are in very good agreement with experimental data. To obtain values of the kinetic parameters that were in the best agreement with experimental data, low frequencies were treated using a one-dimensional internal rotor model. Chain length effects were also explored by examining addition reactions of monomelic, dimeric, and trimeric radicals to monomer for both methyl methacrylate and methyl acrylate. The results show that the values for the addition of the trimeric radical to monomer are closest to experimental data. The kinetic parameters that were calculated using a continuum description of the monomer as a solvent were not significantly different from the vacuum results.

Original languageEnglish (US)
Pages (from-to)6772-6782
Number of pages11
JournalJournal of Physical Chemistry A
Volume112
Issue number29
DOIs
StatePublished - Jul 24 2008

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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