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Simon Harrisson, Christopher Barner-Kowollik, Thomas P. Davis, Richard Evans, Ezio Rizzardo, Martina Stenzel, Ming Yin

Remarkable Solvent Effects of Oxygen- and Sulfur-Containing Compounds on the Propagation Rate of Methyl Methacrylate

The propagation kinetics of methyl methacrylate (MMA) in the presence of a number of oxygen- and sulfur-containing compounds have been investigated. Solvents used were 2-methyl-1,3-dioxepane (MDOP), 2,6-dithiaheptane (DTHP) and 1,5-dithiacyclooctane (DTCO). In the presence of DTHP and DTCO, the propagation rate coefficient, k_p, of MMA was found to be 25% to 100% higher compared to bulk polymerisations under the same conditions. The significant increase of k_p was explained by electron donation from the sulfur-containing solvents, which increased the reactivity of the macroradicals. MDOP had no observable effect on k_p. The solvent influence on polymer tacticity was also studied using both ¹H and ¹³C NMR spectroscopy. No significant influence of the solvent on polymer tacticity was found.

Zeitschrift für Physikalische Chemie, Oldenbourg Wissenschaftsverlag

Print ISSN: 0942-9352
Volume: 219, 03/2005
Pages: 267 - 281

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