Abstract
A study has been made of the electrochemical reductive breakdown (ECRB) of solid-phase chlorinated butyl rubber (CBR). It has been established that CBR does not accept electrons under conditions of fast sweep of electrode potential; however, with prolonged cathodic polarization of the substrate at the polymer/cathode/solution three-phase boundary, it undergoes reduction and subsequent chemical conversion, including intermolecular cross-linking and breakdown of the macromolecules. The rate of ECRB of the CBR depends on the potential and materials of the cathode, and also on the nature of the solvent. In a aprotic medium, the process of CBR breakdown leads to the formation of long polyconjugated structures that color its surface black in the vicinity of the three-phase boundary. In an aqueous medium, no such color is observed, but the products of ECRB are found to contain conjugated double bonds with a shorter conjugation chain than in the case of the aprotic medium. It has been established that he starting reaction in ECRB of CBR is reduction of the C-Cl bond and subsequent elimination of Cl−.
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B. L. Funt and P. M. Hoang, “The voltammetric response of solutions of electroactive polymers,” J. Electrochem. Soc., 131, No. 10, 2295–2298 (1984).
R. U. Bruners, G. Ya. Litsitis, and A. V. Vosekalis, “Investigation of electrically conductive polymeric coatings on electrodes. 1. Electrochemical properties of films of polyaniline in solutions of acids,” Izv. Akad. Nauk Latv. SSR, Ser. Khim., No. 4, 450–454 (1986).
A. A. Pud, G. S. Shapoval, A. P. Tomilova, and T. S. Yatsimirskaya, Teor. Éksp. Khim., 20, No. 5, 584–589 (1984).
G. S. Shapoval, A. V. Gorodyskii, A. P. Tomilova, and A. A. Pud, “Electrochemical reductive breakdown of polymers,” Dokl. Akad. Nauk SSSR, 263, No. 5, 1179–1182 (1982).
G. S. Shapoval, B. A. Sternik, A. P. Tomilov, and A. A. Pud, “Investigation of process of electrochemical reductive breakdown of polyvinyl chloride,” Élektrokhimiya, 18, No. 8, 1028–1032 (1982).
G. S. Shapoval, A. A. Pud, P. V. Zamotaev, and A. A. Kachan, “Electrochemical reductive breakdown of certain carbochain polymers,” Vysokomol. Soedin., Ser. A, 27, No. 10, 2161–2164 (1985).
G. S. Shapoval, A. P. Tomilov, A. A. Pud, and V. A. Vonsyatskii, “Electrochemical reductive breakdown of polytetrafluoroethylene,” Teor. Éksp. Khim., 20, No. 2, 247–249 (1984).
G. S. Shapoval, A. A. Pud, and A. P. Tomilov, “Electrochemical reductive breakdown of certain polymeric dielectrics,” Dokl. Akad. Nauk SSSR, 283, No. 2, 434–437 (1985).
A. A. Dontsov, G. Ya. Lozovik, and S. P. Novitskaya, Chlorinated Polymers [in Russian], Khimiya, Moscow, (1979).
V. A. Vonsyatskii, E. A. Roter, V. A. Teterskii, and A. N. Tynnyi, Fiz.-Khim. Mekh. Mater., No. 5, 64–70 (1982).
V. S. Shmarlin, V. P. Bugrov, L. S. Timofeeva, and Ya. N. Prokof'ev, Synthesis, Properties, and Application of Modified Butyl Rubbers [in Russian], Thematic Review, TsNIITÉneftekhim, Synthetic Rubber Industry Series, Moscow (1973).
L. J. Bellamy, The Infra-red Spectra of Complex Molecules, 2nd edn., Methuen, London (1958).
S. G. Mairanovskii, Ya. P. Stradyn', and V. D. Bezuglyi, Polarography in Organic Chemistry [in Russian], Khimiya, Leningrad (1975).
K. S. Minsker, R. F. Gataullin, V. V. Lisitskii, et al., “Change in molecular characteristics of butyl rubbers in the course of chlorination,” Vysokomol. Soedin., Ser. A, 25, No. 8, 1686–1690 (1983).
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 6, pp. 710–715, November–December, 1989.
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Pud, A.A., Shapoval, G.S., Skubin, V.K. et al. Electrochemical reductive breakdown of solid-phase chlorinated rubber in aprotic and aqueous media. Theor Exp Chem 25, 653–658 (1989). https://doi.org/10.1007/BF00534447
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DOI: https://doi.org/10.1007/BF00534447