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General features and specifics of the kinetics of the pseudoliving radical polymerization of 4-vinylpyridine and styrene mediated by TEMPO

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Abstract

The kinetics of the pseudoliving radical polymerization of 4-vinylpyridine mediated by TEMPO is studied for the first time, and quantitative parameters characterizing the pseudoliving mechanism of the reaction, namely, the rate constant of reinitiation and the product of the equilibrium constant and the propagation-rate constant, are estimated. It is shown that the general kinetic features of the TEMPO-mediated polymerizations of 4-vinylpyridine and styrene (the pattern of kinetic curves and the zero reaction order with respect to the concentration of alkoxyamine) and the distinctive features of the polymerization of 4-vinylpyridine (an abnormally low rate and a high steady-state concentration of free TEMPO) are determined by three main factors: the rate of spontaneous initiation, the rate of self-termination of macroradicals, and the constant of equilibrium between active and dormant chains.

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Authors and Affiliations

  1. Faculty of Chemistry, Moscow State University, Moscow, 119991, Russia

    M. Yu. Zaremski, Chen Xin & A. P. Orlova

  2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991, Russia

    I. V. Blagodatskikh

Authors
  1. M. Yu. Zaremski
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  2. Chen Xin
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  3. A. P. Orlova
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  4. I. V. Blagodatskikh
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  5. V. B. Golubev
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Corresponding author

Correspondence to M. Yu. Zaremski.

Additional information

Original Russian Text © M.Yu. Zaremski, Chen Xin, A.P. Orlova, I.V. Blagodatskikh, V.B. Golubev, 2011, published in Russian in Vysokomolekulyarnye Soedineniya, Ser. B, 2011, Vol. 53, No. 8, pp. 1474–1482.

This work was supported by the Russian Foundation for Basic Research, project no. 11-03-00640.

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Zaremski, M.Y., Xin, C., Orlova, A.P. et al. General features and specifics of the kinetics of the pseudoliving radical polymerization of 4-vinylpyridine and styrene mediated by TEMPO. Polym. Sci. Ser. B 53, 476 (2011). https://doi.org/10.1134/S1560090411080069

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