Chain-length dependence of free-radical termination rate deduced from laser single-pulse experiments

Buback, M., Busch, M., & Kowollik, C. (2000) Chain-length dependence of free-radical termination rate deduced from laser single-pulse experiments. Macromolecular Theory and Simulations, 9(8).

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Abstract

Termination rate coefficients of free-radical polymerization are accessible from SP-PLP studies where monomer conversion induced by a laser single pulse is measured with a time resolution of microseconds. Previous experiments with 2,2-dimethoxy-2-phenylacetophenone (DMPA) acting as the initiator revealed that upon variation of the DMPA concentration, the resulting monomer conversion vs. time traces intersect. A detailed kinetic analysis of this unexpected type of behavior is presented. It turns out that such crossings occur in situations Where k(t) is chain-length dependent and, at the same time. the primary initiator-derived free-radical species differ in reactivity toward the monomer. As is known from the literature, this difference in radical reactivity is particularly pronounced with DMPA, which photo-decomposes to a propagating and to a non-propagating free radical. Modeling of the crossing behavior opens a novel route for determining chain-length dependent k(t). Results for methyl acrylate (MA) and styrene homopolymerizations at low degrees of monomer conversion, to a maximum of are presented. The decrease of k(t) with chain length is modeled via an exponential function. The dependence is significantly larger for styrene. The exponents derived from simulation studies via PREDICI® are in excellent agreement with corresponding data reported by Olaj et al. for styrene and by de Kock for methyl acrylate.

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ID Code: 99039
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :59
Export Date: 20 September 2016
CODEN: MTHSE
Correspondence Address: Buback, M.; Institut fur Physikalische Chemie, Universitat Gottingen, Tammannstrasse 6, D-37077 Gottingen, Germany
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Keywords: acetophenone derivative, acrylic acid methyl ester, free radical, monomer, styrene, article, chemical modification, chemical reaction, chemical reaction kinetics, laser, molecular model, photodegradation, polymerization, simulation
DOI: 10.1002/1521-3919(20001101)9:8<442::AID-MATS442>3.0.CO;2-I
ISSN: 10221344
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 22 Sep 2016 04:50

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