TY - JOUR
T1 - Remarkable solvent effects of oxygen- and sulfur-containing compounds on the propagation rate of methyl methacrylate
AU - Harrisson, Simon
AU - Barner-Kowollik, Christopher
AU - Davis, Thomas P.
AU - Evans, Richard
AU - Rizzardo, Ezio
AU - Stenzel, Martina
AU - Yin, Ming
PY - 2005/4/12
Y1 - 2005/4/12
N2 - 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, kp, of MMA was found to be 25% to 100% higher compared to bulk polymerisations under the same conditions. The significant increase of kp was explained by electron donation from the sulfur-containing solvents, which increased the reactivity of the macroradicals. MDOP had no observable effect on kp. 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.
AB - 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, kp, of MMA was found to be 25% to 100% higher compared to bulk polymerisations under the same conditions. The significant increase of kp was explained by electron donation from the sulfur-containing solvents, which increased the reactivity of the macroradicals. MDOP had no observable effect on kp. 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.
KW - Free Radical Polymerization
KW - Propagation Rate Coefficients
KW - Solvent Effects
UR - http://www.scopus.com/inward/record.url?scp=15944385248&partnerID=8YFLogxK
U2 - 10.1524/zpch.219.3.267.59184
DO - 10.1524/zpch.219.3.267.59184
M3 - Article
AN - SCOPUS:15944385248
VL - 219
SP - 267
EP - 281
JO - Zeitschrift fur Physikalische Chemie
JF - Zeitschrift fur Physikalische Chemie
SN - 0942-9352
IS - 3
ER -