Abstract
The kinetics and mechanism of initiation and reinitiation reactions in the polymerization of methyl methacrylate mediated by the ammonia–tripropylborane–oxygen and 2-isopropyl-2-boraadamantane–oxygen systems are studied by ESR spectroscopy using C-phenyl-N-tert-butylnitrone and 2-methyl-2-nitrosopropane as spin traps. It is shown that alkyl and alkoxyl radicals are the main initiating radicals and the rate of initiation is directly proportional to the concentration of oxygen. Two mechanisms of radical formation are valid in the postpolymerization of methyl methacrylate at room temperature under vacuum. The first one (which is predominant) is the decomposition of poly(methyl methacrylate)–boroxyl macromolecules, i.e., the reinitiation of polymerization; the second one (additional during the first 30 min of the process) is the decomposition of borane peroxide compounds accumulated during the stage of oxidation.
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M. Yu. Zaremski, E. S. Garina, M. E. Gurskii, and M. E. Bubnov, Polym. Sci., Ser. B 55 (5–6), 304 (2013).
D. V. Ludin, Yu. L. Kuznetsova, and S. D. Zaitsev, Russ. J. Appl. Chem. 88 (2), 295 (2015).
D. V. Ludin, Yu. L. Kuznetsova, I. D. Grishin, V. A. Kuropatov, and S. D. Zaitsev, Russ. Chem. Bull. 65 (7), 1859 (2016).
V. A. Dodonov, R. V. Galkin, T. I. Starostina, Y. B. Malysheva, and V. A. Kuropatov, Dokl. Chem. 463 (1), 174 (2015).
T. C. M. Chung, W. Janvikul, and H. L. Lu, J. Am. Chem. Soc. 118 (3), 705 (1996).
A. C. Moran, N. V. Lebedeva, S. Richert, and M. D. E. Forbes, Appl. Magn. Reson. 41, 295 (2011).
C. Olliver and P. Renaud, Chem. Rev. 101 (11), 3415 (2001).
R. Rensch and H. Fribolin, Chem. Ber. 110, 2189 (1977).
R. Hunschens, R. Rensch, and H. Fribolin, Chem. Ber. 114, 3581 (1981).
N. L. Zutty and F. J. Welch, Org. Chem. 25, 861 (1960).
R. L. Hansen and R. R. Hamann, J. Phys. Chem. 67, 2868 (1963).
Z.-C. Zhang and T. C. M. Chung, Macromolecules 39 (16), 5187 (2006).
A. G. Davies, D. G. Hare, and F. M. White, J. Chem. Soc. 1960, 1040 (1960).
A. G. Davies, D. G. Hare, and F. M. White, J. Chem. Soc. 1961, 341 (1961).
S. B. Mirviss, J. Am. Chem. Soc. 83 (14), 3051 (1961).
D. Griller, K. U. Ingold, L. K. Patterson, J. C. Scaiano, and R. D. Small, J. Am. Chem. Soc. 101 (14), 3780 (1979).
T. Sato, K. Hibino, N. Fukumura, and T. Otsu, Chem. Ind. 4 (15), 745 (1973).
A. G. Davis, D. Griller, and B. P. Roberts, J. Chem. Soc. 1971, 1823 (1971).
P. J. Krusic and J. K. Kochi, J. Am. Chem. Soc. 91 (14), 3938 (1969).
M. Yu. Zaremski, D. V. Budanov, S. A. Romanov, A. V. Plutalova, E. S. Garina, V. B. Golubev, S. Yu. Erdyakov, M. E. Gurskii, and Yu. N. Bubnov, Polym. Sci., Ser. B 53 (1), 1 (2011).
D. E. Bergbreiter and G. F. Xu, Macromolecules 28, 4756 (1995).
S. Yu. Erdyakov, O. A. Melrnik, M. E. Gurskii, A. V. Ignatenko, and Ya. S. Vygodskii, Russ. Chem. Bull. 53, 2215 (2004).
M. E. Gurskii, A. S. Shashkov, and B. M. Michailov, Russ. Chem. Bull. 2, 341 (1981).
G. R. Buettner, Free Radical Biol. Med. 3, 259 (1987).
F. J. Welch, J. Polym. Sci. 61, 243 (1962).
T. C. Chung, US Patent No. 6515088 B2 (2003).
T. C. Chung, US Patent No. 6420502 B1 (2003).
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Original Russian Text © M.Yu. Zaremskii, V.V. Odintsova, A.V. Plutalova, M.E. Gurskii, Yu.N. Bubnov, 2018, published in Vysokomolekulyarnye Soedineniya, Seriya B, 2018, Vol. 60, No. 2, pp. 123–133.
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Zaremskii, M.Y., Odintsova, V.V., Plutalova, A.V. et al. Reactions of Initiation and Reinitiation in Polymerization Mediated by Organoborane–Oxygen Systems. Polym. Sci. Ser. B 60, 162–171 (2018). https://doi.org/10.1134/S1560090418020082
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DOI: https://doi.org/10.1134/S1560090418020082