Abstract
The kinetics and mechanism of the pseudoliving free-radical polymerization of styrene are studied for the first time under the conditions of reversible inhibition by TEMPO nitroxides. An abnormal decline in the reduced rate of polymerization, which is inconsistent with a decrease in the concentration of the monomer, and an increase in the steady-state concentration of the free nitroxide are discovered. The main quantitative characteristics of the pseudoliving process are determined, namely, the rate constants of reinitiation and reversible recombination, and the constant of pseudoliving equilibrium between dormant and growing chains. It is shown that the polarity of a medium and the concentration of the monomer determine the character of polymerization in a solution: With an increase in the polarity of the solvent, the pseudoliving equilibrium constant increases, the reduced rate of styrene polymerization decreases, and the molecularmass-distribution of the polymer formed at initial conversions narrows. The smaller the concentration of styrene in the reaction system, the more pronounced the above differences associated with the solvent nature.
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Original Russian Text © M.Yu. Zaremski, Chen Xin, A.P. Orlova, V.B. Golubev, S.A. Kurochkin, V.P. Grachev, 2010, published in Russian in Vysokomolekulyarnye Soedineniya, Ser. B, 2010, Vol. 52, No. 9, pp. 1675–1688.
This work was supported by the Russian Foundation for Basic Research, project no. 08-03-00269a.
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Zaremski, M.Y., Xin, C., Orlova, A.P. et al. Effect of the nature of a solvent on pseudoliving free-radical polymerization of styrene mediated by TEMPO. Polym. Sci. Ser. B 52, 528–541 (2010). https://doi.org/10.1134/S1560090410090034
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DOI: https://doi.org/10.1134/S1560090410090034