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Tributylborane/p-quinone system: reversible and irreversible inhibition in the styrene polymerization

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Polymerization of styrene with tributylborane in the presence of various p-quinones (2,3-dimethyl-1,4-benzoquinone, 1,4-naphthoquinone, menadione, duroquinone, 2,5-di-tert-butyl-1,4-benzoquinone) has been investigated. It was found that in spite of dual nature of p-quinone and the presence of tributylborane in the initial mixture, the semi-quinone macroradical is capable to “chain regeneration”. Neither solvent introduction nor use of a more reactive triethylborane affects this process. The insensitivity of this reaction to external conditions may be caused by the cell effect. For some p-quinones in the presence of tributylborane, the realization of reversible-deactivation radical polymerization is observed. Mechanism of the chain termination reactions was established by the MALDI-TOF technique. It consists of reversible inhibition causing the formation of active macromolecules as well as irreversible inhibition causing the formation of “dead” macromolecules. The ratio of these directions depends on the relative reactivity of p-quinone (kz/kp). The higher is kz/kp, the lower is the probability of irreversible inhibition. Polymers obtained in the presence of the tributylborane/p-quinone system can re-initiate polymerization. Post-polymers with distinct molecular weight characteristics (Đ = 1.12 – 1.19) were obtained during this synthesis. Only polystyrene macro-radicals are formed during polymerization re-initiation. This fact has been proven by ESR spectroscopy. The macroinitiator polymers isolated at the initial conversions have the same reactivity regardless of the p-quinone nature. The linear dependence of Mn with conversion, the polydispersity lessening, and the constant concentration of macro-radicals indicate realization of reversible-deactivation radical polymerization.

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Information is available regarding the borane synthesis, hydroquinone oxidation, MNP synthesis, MNQ reactivity determination, GPC data, MALDI-TOF mass spectra, FT-IR spectra, data on chain extension, and block copolymerization. The materials are available via the Internet at http://www.springer.com/

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Acknowledgements

This work was supported by Ministry of Education of the Russian Federation (No. AAAA-A20-120092990108-5). "The work was carried out using the equipment of the center for collective use "Analytical Center of the IOMC RAS" with the financial support of the grant "Ensuring the development of the material and technical infrastructure of the centers for collective use of scientific equipment" (Agreement Number 13.CCU.21.0017) in the framework of the Russian state assignment"

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Ministry of Education of the Russian Federation, AAAA-A20-120092990108-5.

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Authors and Affiliations

  1. Research Educational Center “Chemistry of Molecules and Materials”, Minin University, 7 Minin and Pozharskii Square, Nizhny Novgorod, Russian Federation, 603005

    Dmitrii V. Ludin, Ekaterina V. Bobrina & Igor L. Fedushkin

  2. Chemistry department, Lobachevsky State University of Nizhny Novgorod, 23 Gagarin Avenue, Nizhny Novgorod, Russian Federation, 603950

    Nadezhda V. Illarionova, Ivan D. Grishin & Sergey D. Zaitsev

  3. G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Science (RAS), 49 Tropinina Street, Nizhny Novgorod, Russian Federation, 603137

    Konstantin A. Kozhanov & Igor L. Fedushkin

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  1. Dmitrii V. Ludin
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Ludin, D.V., Illarionova, N.V., Bobrina, E.V. et al. Tributylborane/p-quinone system: reversible and irreversible inhibition in the styrene polymerization. Macromol. Res. 31, 271–283 (2023). https://doi.org/10.1007/s13233-023-00136-7

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