Termination kinetics of styrene free-radical polymerization studied by time-resolved pulsed laser experiments

Buback, M., Kowollik, C., Kurz, C., & Wahl, A. (2000) Termination kinetics of styrene free-radical polymerization studied by time-resolved pulsed laser experiments. Macromolecular Chemistry and Physics, 201(4).

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Abstract

The single pulse (SP)-pulsed-laser polymerization (PLP) technique has been applied to measure kt/kp, the ratio of termination to propagation rate coefficients, for the free-radical bulk polymerization of styrene at temperatures from 60 to 100°C and pressures from 1800 to 2650 bar. kt/kp is obtained by fitting monomer concentration vs. time traces that are determined via time-resolved (μs) near infrared monitoring of monomer conversion induced by single excimer laser pulses of about 20 ns width. Styrene is a difficult candidate for this kind of measurements as conversion per pulse is small for this low kp and high kt monomer. Thus between 160 to 300 SP signals were co-added to yield a concentration vs. time trace of sufficient quality for deducing kt/kp with an accuracy of better than ±20 per cent. With kp being known from PLP-SEC experiments, chain-length averaged kt values are immediately obtained from kt/kp. At given pressure and temperature, kt is independent of the degree of overall monomer conversion, which, within the present study, has been as high as 20 %. The kt value, however, is found to slightly increase with the amount of free radicals produced by a single pulse in laser-induced decomposition of the photoinitiator DMPA (2,2-dimethoxy-2-phenyl acetophenone). This remarkable observation is explained by DMPA decomposition resulting in the formation of two free radicals which significantly differ in reactivity. Extrapolation of SP-PLP kt data from experiments at rather different DMPA levels and laser pulse energies toward low primary free-radical concentration, yields very satisfactory agreement of the extrapolated kt values with recent literature data from chemically and photochemically induced styrene polymerizations. © Wiley-VCH Verlag GmbH, 2000.

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ID Code: 99040
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :62
Export Date: 20 September 2016
CODEN: MCHPE
Correspondence Address: Buback, M.; Institut für Physikalische Chemie, Universität Göttingen, Tammannstraße 6, D-37077 Göttingen, Germany
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ISSN: 10221352
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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