Abstract
Catalytic activity of various Lewis acids in the group transfer polymerization (GTP) of 1-butadienyloxytrimethylsilane (BdTMS) initiated with benzaldehyde was investigated. Among the Lewis acids studied, three zinc halides (ZnBr2, ZnI2, ZnCl2) and HgBr2 gave soluble polymers with narrow molecular weight distributions in quantitative yields. The polymerizations proceeded apparently on the insoluble solid catalyst. The other soluble Lewis acid catalysts, including (C2H5)2AlCl, AlCl3, SnCl4, SnBr4, and TiBr4, gave polymers in moderate to poor yields and often gelled polymers. Through 1H NMR monitoring of the polymerization, time vs. monomer and initiator consumption curves were obtained, and then initiation and propagation rates were estimated from slopes of the curves. Both rates were enhanced in an order of ZnBr2>ZnI2>ZnCl2. This order is consistent with that of chemical shifts of formyl carbon of equimolar mixture of ZnX2 with benzaldehyde, as well as crotonaldehyde which is a model for a polymer end, in chloroform-d. This order was also compatible with the decreasing order in M̅w/M̅n values of the resulting polymers. Thus, use of ZnBr2 as the catalyst resulted in P(BdTMS) with the smallest M̅w/M̅n (1.26) which was determined by a GPC method.
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
M. Morton, “Anionic Polymerization: Principles and Practice,” Academic, New York, N. Y., 1983.
A. Hirao, K. Takenaka, S. Packirisamy, K. Yamagauchi, and S. Nakahama, Makromol. Chem., 186, 1157 (1985).
D. Y. Sogah and O. W. Webster, Macromolecules, 19, 1775 (1986).
F. P. Boettcher, Makromol. Chem., Makromol. Symp., 13/14, 193 (1988).
T. Hirabayashi, T. Ito, and K. Yokota, Polym. J., 20, 1041 (1988).
T. Hirabayashi, T. Kawasaki, and K. Yokota, Polym. J., 22, 287 (1990).
S. Danishefsky and T. Kitahara, J. Org. Chem., 40, 538 (1975).
G. A. Olah, “Friedel-Crafts and Related Reactions,” Vol. I, Interscience, New York, N. Y., 1963, p 860.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Sumi, H., Hirabayashi, T., Inai, Y. et al. Selection of Catalyst for Group Transfer Polymerization of 1-Butadienyloxytrimethylsilane. Polym J 24, 669–677 (1992). https://doi.org/10.1295/polymj.24.669
Issue date:
DOI: https://doi.org/10.1295/polymj.24.669
Keywords
This article is cited by
-
Group transfer polymerization of acrylonitrile in bulk at ambient temperature
Polymer Bulletin (2005)
