Abstract
The kinetics and inherent chain transfer on a monomer in radically polymerizing methyl methacrylate (MMA) by cobaloxime (LCo) catalysis in the presence of chemical substance of various types are described. Nonpolar solvents at content up to 40% v/v do not influence kinetics and molecular-weight distribution (MWD) of polyMMA. The addition of 1–5% v/v of polar solvents in MMA, e.g., DMF and other amides, DMSO and pyridine enhances the rate of reduction of LCo(III) (inactivated state of catalyst) to LCo(II) (active state of catalyst) by radicalas at initial stage of polymerization but does not change the rate of chain transfer catalysis (CTC). The reduction in bulk MMA and MMA containing polar solvents is proved to be an autocatalytic process. Starting rate constants of LCo(III) reduction ranged from 200 to 3000 m−1s−1 depending on the substitute at glyoximato ligands. Benzoyl peroxide and cumyl hydroperoxide were found to oxidize LCo(II) to LCo(III) in polymerizing MMA medium at a rate constant ca. 10 M−1s−1 and thus peroxides decline titled catalytic activity of cobaloximes by discovered rules providing a new way of CTC control. In the case of styrene (St) the benzoyl peroxide causes irreversible poisoning of cobaloximes.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
N. S. Enicolopian, I. M. Belgovskii, A. A. Gridnev, A. P. Marchenko, and B. R. Smirnov, USSR Patent #940487 (1982).
A. F. Burzyk, K. F. O’Driscoll, and G. L. Rempel, J. Polym. Sci., Polym. Chem. Ed., 22, 3255 (1984).
A. A. Gridnev, Vysokomol. Soedin., Ser. A, 31, 2153 (1989).
N. S. Enikolopyan, B. R. Smirnov, G. V. Ponomarev, and I. M. Belgovskii, J. Polym. Sci., Polym. Chem. Ed., 19, 879 (1981).
A. P. Belokurova, R. A. Petrova, T. Yu. Kovrova, and O. I. Koifman, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 32, 90 (1989).
B. R. Smirnov, L. M. Puschaeva, and V. D. Plotnikov, Vysokomol. Soed., Ser. A, 31, 2378 (1989).
K. G. MkGardy and K. J. Laider, Can. J. Chem., 42, 818 (1964).
R. M. Joshi, J. Polym. Sci., 56, 313 (1962).
J. L. O’Brien and F. Gornick, J. Am. Chem. Soc., 77, 4757 (1955).
C. H. Bamford, W. G. Barb, A. J. Jenkins, and P. F. Onyon, “The Kinetics of Vinyl Polymerization by Radical Mechanism,” Butterworth, London, 1958.
L. I. Simandi, E. Budo-Zahonyi, Z. Szeverenyi, and S. Nemeth, J. Chem. Soc., Dalton Trans., 276 (1980).
A. A. Gridnev, I. M. Belgovskii, and N. S. Enicolopyan, Dokl. Akad. Nauk, SSSR, 289, 616 (1986).
A. A. Gridnev, I. M. Belgovskii, and N. S. Enicolopyan, Dokl. Akcad. Nauk SSSR, 289, 1408 (1986).
M. S. Kharasch, S. Pauson, and W. Nudenberg, J. Org. Chem., 18, 322 (1953).
G. Henrici-Olive and S. Olive, Makromol. Chem., 24, 64 (1957).
A. Bury, C. J. Cooksey, T. Funabiki, B. D. Gupta, and M. D. Johnson, J. Chem. Soc., Perkin Trans. 2, 1050 (1979).
J. P. Kitchin and D. A. Widdowson, J. Chem. Soc., Perkin Trans. 1, 1384 (1979).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Gridnev, A. Radical Polymerization of Methyl Methacrylate in the Presence of Cobaloximes and Benzoyl Peroxide. Polym J 24, 613–623 (1992). https://doi.org/10.1295/polymj.24.613
Issue date:
DOI: https://doi.org/10.1295/polymj.24.613
Keywords
This article is cited by
-
Novel polymerization of divinyl monomer to polyester catalyzed with organocobaloxime
Polymer Bulletin (1995)
