Abstract
Anionic polymerization of methyltrivinylsilane was conducted in the presence and absence of N,N,N′,N′-tetramethylethylenediamine (TMEDA). In the polymerization, cyclopolymerization always took place similarly to the polymerization of dimethyldivinylsilane. In the absence of TMEDA at −10°C, the polymerization proceeded extremely slowly and only 5% polymer was obtained even after 168 h. In the presence of TMEDA, on the other hand, the remarkable acceleration of the polymerization and the suppression of gelation were observed. The fraction of the remaining second and third vinyl groups in the polymer was much higher for the polymer obtained in the presence of TMEDA. These effects of TMEDA were explained by the change in the reactivity of the propagating ends, that is, the increase in the selectivity in the addition of propagating ends to vinyl groups.
Similar content being viewed by others
Article PDF
References
R. Asami, J. Oku, M. Takeuchi, K. Nakamura, and M. Takaki, Polym. J., 20, 699 (1988).
J. Oku, T. Hasegawa, K. Nakamura, M. Takeuchi, M. Takaki, and R. Asami, Polym. J., 23, 195 (1991).
J. Oku, T. Hasegawa, T. Takeuchi, and M. Takaki, Polym. J., 23, 1377 (1991).
J. Oku, T. Hasegawa, Y. Kubota, M. Takaki, and R. Asami, Polym. Bull., 28, 505 (1992).
J. Oku, T. Hasegawa, T. Kawakita, Y. Kondo, and M. Takaki, Macromolecules, 24, 1253 (1991).
S. G. Durgar’yan, V. S. Khotimskii, Yu. V. Barskov, and I. B. Shevaldina, U.S.S.R. SU 1460063, 1989.
J. Oku, M. Takeuchi, A. Saito, and R. Asami, Polym. J., 24, 1409 (1992).
J. Oku, T. Hasegawa, and M. Takaki, “Chemistry and Technology of Silicon and Tin,” V. G. Kumar Das, S. W. Ng, and M. Gielen, Ed., Oxford University Press, Oxford, 1992, p 440. Since there are many serious misprints, the erratum slip that was issued afterward should be referred to. For example, the title of the paper “Copolymerization of dimethyldivinylsilane” should be corrected to “Cyclopolymerization of dimethyldivinylsilane”.
J. V. Swisher and H.-H. Chen, J. Organometal. Chem., 69, 83 (1974).
B. T. Nguyen and F. K. Cartledge, J. Org. Chem., 51, 2206 (1986).
In the polymerization of DMDVS under similar conditions ([DMDVS] ∼ 0.3 mol l−1, [s-BuLi] ∼ 6 mmol l−1, [TMEDA] ∼ 0 or 6 mmol l−1, at −10°C, in hexane), the fraction of the remaining second vinyl groups was around 30% regardless of the TMEDA addition.7 Though the present results cannot be compared directly with the data on DMDVS, they indicate that the addition of TMEDA hinders especially the reaction of the third vinyl group in MTVS.
D. J. Worsfold and S. Bywater, Can. J. Chem., 38, 1891 (1960).
M. Morton, E. E. Bostick, R. A. Livigni, and L. J. Fetters, J. Polym. Sci., A, 1, 1735 (1963).
G. G. Eberhardt and W. A. Butte, J. Org. Chem., 29, 2928 (1964).
S. Dumas, J. Sledz, and F. Schué, ACS Symp. Ser., 166, 463 (1981).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Oku, Ji., Takahashi, M., Itoh, Y. et al. Anionic Polymerization of Vinylsilanes VI. Effects of N,N,N′,N′-Tetramethylethylenediamine on the Polymerization of Methyltrivinylsilane. Polym J 26, 79–84 (1994). https://doi.org/10.1295/polymj.26.79
Issue Date:
DOI: https://doi.org/10.1295/polymj.26.79
Keywords
This article is cited by
-
Anionic polymerization of vinylsilanes VII
Polymer Bulletin (1997)