Jump to main content
Jump to site search


Ab initio based kinetic Monte Carlo analysis to unravel the propagation kinetics in vinyl acetate pulsed laser polymerization

Author affiliations

Abstract

The radical propagation kinetics of vinyl acetate (VAc) in pulsed laser polymerization (PLP) is studied by combining ab initio calculated rate coefficients for propagation of head, tail and mid-chain radicals, and backbiting reactions with kinetic Monte Carlo modeling of PLP spectra. The intriguing laser pulse frequency dependency of the propagation kinetics is shown to be mainly caused by the formation of stabilized mid-chain radicals via backbiting of tail radicals, originating from head-to-head propagation. These mid-chain radicals are approximately 35 times less reactive towards propagation at 323 K which, in agreement with experimental observations, results in a 15% increase of the observed propagation rate coefficient if the laser pulse frequency is increased from low (25–100 s−1) to high (300–500 s−1) values. Under typical PLP conditions, only tail radicals are reactive towards backbiting while this reaction is energetically unfavorable for head radicals. Tail-to-tail propagation of the radicals formed by head-to-head propagation is not sufficiently slow to fully explain the observed frequency dependence. The effect of chain length dependent propagation remains limited but can no longer be neglected at frequencies above 500 s−1.

Graphical abstract: Ab initio based kinetic Monte Carlo analysis to unravel the propagation kinetics in vinyl acetate pulsed laser polymerization

Back to tab navigation

Supplementary files

Publication details

The article was received on 16 Jun 2017, accepted on 29 Oct 2017 and first published on 30 Oct 2017


Article type: Paper
DOI: 10.1039/C7PY01008G
Citation: Polym. Chem., 2017, Advance Article
  •   Request permissions

    Ab initio based kinetic Monte Carlo analysis to unravel the propagation kinetics in vinyl acetate pulsed laser polymerization

    G. B. Desmet, Y. W. Marien, P. H. M. Van Steenberge, D. R. D'hooge, M. Reyniers and G. B. Marin, Polym. Chem., 2017, Advance Article , DOI: 10.1039/C7PY01008G

Search articles by author

Spotlight

Advertisements