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• W3118451372 endingPage "972" @default.
• W3118451372 startingPage "966" @default.
• W3118451372 abstract "The effect of viscosity on the radical termination reaction between a transient radical and a persistent radical undergoing a coupling reaction (Coup) or hydrogen abstraction (Abst) was examined. In a non-viscous solvent, such as benzene (bulk viscosity ηbulk < 1 mPa s), all the transient radicals studied exclusively coupled with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) with >99% Coup/Abst selectivity, but Coup/Abst decreased as the viscosity increased (89/11 in PEG400 at 25 °C [ηbulk = 84 mPa s]). While bulk viscosity is a good parameter to predict the Coup/Abst selectivity in each solvent, microviscosity is the more general parameter. Poly(methyl methacrylate) (PMMA)-end radicals had a more significant viscosity effect than polystyrene (PSt)-end radicals, and the Coup/Abst ratio of the former dropped to 50/50 in highly viscous media (ηbulk = 3980 mPa s), while the latter maintained high Coup/Abst selectivity (84/16). These results, together with the low thermal stability of dormant PMMA-TEMPO species compared with that of PSt-TEMPO species, are attributed to the limitation of the nitroxide-mediated radical polymerization of MMA. While both organotellurium and bromine compounds were used as precursors of radicals, the former was superior to the latter for the clean generation of radical species. Considerable viscosity effect was observed on the radical termination reaction between a transient radical and a persistent radical, and a coupling reaction (Coup) decreased and hydrogen abstraction (Abst) increased as the increase of viscosity. While the same viscosity effect has been already reported in the self-termination reaction of transient radicals, this is the first example for the termination involving a persistent radical." @default.
• W3118451372 created "2021-01-18" @default.
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• W3118451372 date "2021-03-15" @default.
• W3118451372 modified "2023-09-23" @default.
• W3118451372 title "The Effect of Viscosity on the Coupling and Hydrogen-Abstraction Reaction between Transient and Persistent Radicals" @default.
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• W3118451372 doi "https://doi.org/10.1246/bcsj.20200398" @default.
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