Kinetic study of the copolymerization of methyl methacrylate and methyl acrylate using quantum chemistry

Xinrui Yu, Seth E. Levine, Linda J Broadbelt

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37 Scopus citations


Copolymerization of methyl methacrylate and methyl acrylate was studied using quantum chemistry and transition state theory to estimate the kinetic parameters for propagation (kp, A, Ea). A terminal model and penultimate effect models were studied explicitly by examining 28 different addition reactions involving monomelic, dimeric, and trimeric radicals and monomers for both self- and cross-propagation. Reactant and product conformations were optimized using a combination of a conventional optimization algorithm and relaxed potential energy scans for individual single-bond rotors using unrestricted B3LYP/6-31G(d). The electronic energy was then calculated using MPWB1K/6-31G(d,p). Low frequencies were treated using a one-dimensional internal rotor model. A and Ea were regressed based on a plot of In kp vs MT over a temperature range of 296.15-800 K. Reactivity ratios (r) characterizing the terminal model were calculated based on the monomelic, dimeric, and trimeric radical addition reactions, and ratios for the explicit penultimate model (r and s) were calculated based on the dimeric and trimeric radical addition reactions and compared to experimental values. The overall propagation rate constant (kp,copo) and composition of the copolymer (F) were calculated at different monomer fractions (J). The results based on radical addition of trimeric radicals showed very good agreement with those fitted based on experimental data. Finally, correlation of the activation energies (Ea) with the heats of reactions (ΔHr) was examined, and the classic Evans - Polanyi relationship was shown to hold well for self- and cross-propagation of methyl acrylates.

Original languageEnglish (US)
Pages (from-to)8242-8251
Number of pages10
Issue number21
StatePublished - Nov 11 2008

ASJC Scopus subject areas

  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry


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