A priori prediction of propagation rate coefficients in free-radical polymerizations: Propagation of ethylene

Heuts, J.P.A., Gilbert, R.G. and Radom, L. (1995) A priori prediction of propagation rate coefficients in free-radical polymerizations: Propagation of ethylene. Macromolecules, 28 26: 8771-8781. doi:10.1021/ma00130a009

Author Heuts, J.P.A.
Gilbert, R.G.
Radom, L.
Title A priori prediction of propagation rate coefficients in free-radical polymerizations: Propagation of ethylene
Journal name Macromolecules   Check publisher's open access policy
ISSN 0024-9297
Publication date 1995-12
Sub-type Article (original research)
DOI 10.1021/ma00130a009
Volume 28
Issue 26
Start page 8771
End page 8781
Total pages 11
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Abstract A method is derived for calculating Arrhenius parameters for propagation reactions in free-radical polymerizations from first principles. Ab initio molecular orbital calculations are carried out initially to determine the geometries, vibrational frequencies, and energies of the reactants and the transition state. Transition state theory then yields the Arrhenius parameters. The lowest frequencies are replaced by appropriate (hindered or unhindered) internal rotors, to better model these modes in the calculation of frequency factors. It is found that a high level of molecular orbital theory (e.g., QCISD-(T)/6-311G**) is required to produce reasonable activation energies, whereas satisfactory frequency factors can be obtained at a relatively simple level of theory (e.g., HF/3-21G), because the frequency factor is largely determined by molecular geometries which can be reliably predicted at such a level. Obtaining reliable frequency factors for quite large systems is thus possible. The overall procedure is illustrated by calculations on the propagation of ethylene, and the results are in accord with literature experimental data. Means are also derived for extending the results from propagation of monomeric radicals to propagation of polymeric radicals, without additional computational requirements. The method is expected to be generally applicable to those propagation reactions that are not significantly influenced by the presence of solvent (i.e., relatively nonpolar monomers in nonpolar solvents). The calculations show that the magnitude of the frequency factor is largely governed by the degree to which the internal rotations of the transition state are hindered. They also suggest that there can be a significant penultimate unit effect in free-radical copolymerization. Furthermore, the calculations explain the rate-enhancing effect found upon deuteration of the monomers and explain why the rate coefficient for the first propagation step is larger than that for the long-chain propagation step.
Keyword Transition-state Theory
Consistent Values
Rate Parameters
Rate Constants
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Chemistry and Molecular Biosciences
Centre for Nutrition and Food Sciences Publications
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Created: Mon, 07 Mar 2011, 15:47:37 EST