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Kinetic Features of Elementary Events in the Radical Polymerization of Methyl Methacrylate under Conditions of Nitroxide-Mediated Reversible Inhibition

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Abstract

The kinetic features of the elementary events of initiation, reinitiation, and reversible termination in the radical polymerization of methyl methacrylate mediated by piperidine and imidazoline nitroxides are studied. The rate constants of these reactions and the constant of equilibrium between the dormant and growing chains are determined. In all the systems studied, the reinitiation rate constant and the equilibrium constant decrease during polymerization. The activity of imidazoline nitroxides in the termination reaction turns out to be an order of magnitude lower than that of piperidine ones, and the constant of interaction of both types of nitroxides with methyl methacrylate growing radicals is two and a half orders of magnitude lower than that with their low molecular weight counterparts.

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Notes

  1. Note that the nitroxide SG-1, the termination constant of which is one order of magnitude lower and equal to 104 L/(mol s), does not suppress the quadratic termination of PMMA radicals.

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ACKNOWLEDGMENTS

We are grateful to E.S. Garina for the GPC analysis of the polymers and D.A. Parkhomenko for his help in determining the initiation constant.

Funding

This study was supported by the Russian Foundation for Basic Research (project no. 18-03-00707).

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Authors and Affiliations

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

    M. Yu. Zaremski & V. V. Odintsova

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  1. M. Yu. Zaremski
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  2. V. V. Odintsova
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Correspondence to V. V. Odintsova.

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Zaremski, M.Y., Odintsova, V.V. Kinetic Features of Elementary Events in the Radical Polymerization of Methyl Methacrylate under Conditions of Nitroxide-Mediated Reversible Inhibition. Polym. Sci. Ser. B 62, 1–13 (2020). https://doi.org/10.1134/S1560090420010121

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