Abstract
Polymerizations of various methacrylates and α-(p-substituted phenyl)acrylates were studied in toluene and tetrahydrofuran by several anionic initiators. The polymerization with octylpotassium in tetrahydrofuran was found to be the most suitable for the formation of the heterotactic polymer, defined as the polymer containing more than 50% heterotactic triads. Methacrylic acid esters of the primary alcohol gave the heterotactic polymers, whose heterotactic contents increased with an increase in the bulkiness of the ester group. Methacrylic esters of secondary alcohol generally gave heterotactic polymers with octylpotassium in tetrahydrofuran. In the polymerizations of methacrylic acid esters of tertiary alcohol, the heterotactic contents decreased with an increase in the bulkiness of the ester group. A perfectly atactic polymer was obtained in the polymerization of methyl α-phenylacrylate with butyllithium in tetrahydrofuran, but it gave the heterotactic polymer when initiated with octylpotassium in tetrahydrofuran. Methyl α-p-chlorophenylacrylate produced the heterotactic polymer in tetrahydrofuran with butyllithium as well as with octylpotassium. In the case of methyl α-p-bromophenylacrylate, the heterotactic polymer was obtained even in the polymerization in toluene with butyllithium. These results indicate that the acrylic acid ester having the bulkier substituent tends to give the heterotactic polymer more easily by anionic initiator.
Similar content being viewed by others
Article PDF
References
S. Nozakura, T. Okamoto, K. Toyora, and S. Murahashi, J. Polym. Sci., Polym. Chem. Ed., 11, 1043 (1973).
S. Nozakura, S. Ishihara, Y. Inaba, K. Matsumura, and S. Murahashi, J. Polym. Sci., Polym. Chem. Ed., 11, 1053 (1973).
E. G. Brame, Jr. and O. Vogl., J. Macromol. Sci., Chem. A1, 277 (1967).
M. Goodman and J. Brandrup, J. Polym. Sci., A, 3, 327 (1965).
K. Hatada, Y. Okamoto, H. Ise, S. Yamaguchi, and H. Yuki, J. Polym. Sci., Polym. Lett. Ed., 13, 731 (1975).
N. A. Adrova and L. K. Prokhorova, Vysokomol. Soedin., 3, 1509 (1961).
G. R. Ames and W. Davey, J. Chem. Soc., 1794 (1958).
E. J. Skerrett and D. Woodcock, J. Chem. Soc., 2804 (1952).
A. F. Halasa, private communication.
W. Fowells, C. Schuerch, F. A. Bovey, F. P. Hood, J. Am. Chem. Soc., 89, 1396 (1967).
G. W. H. Schere, R. K. Brown, Can. J. Chem., 38, 2450 (1960).
S. Murahashi, T. Niki, T. Obokata, H. Yuki, and K. Hatada, Kobunshi Kagaku, 24, 198 (1967).
K. Hatada, K. Ohta, Y. Okamoto, T. Kitayama, Y. Umemura, and H. Yuki, J. Polym. Sci., Polym. Lett. Ed., 14, 531 (1976).
H. J. Harwood, Angew. Makromol. Chem., 4/5, 279 (1968).
H. Yuki, K. Hatada, T. Niinomi, M. Hashimoto, and J. Ohshima, Polym. J., 2, 629 (1971).
D. Brau, M. Herner, U. Johnsen, and W. Kern, Makromol. Chem., 51, 15 (1962).
R. W. Lenz, K. Saunders, T. Balakrishnan, and K. Hatada, Macromolecules, 12, 392 (1979).
J. Junquera, N. Cardona, and J. E. Figueruelo, Makromol. Chem., 160, 159 (1972).
J. P. Pascault, J. Kawak, J. Golé, and Q. T. Pham, Eur. Polym. J., 10, 1107 (1974).
M. Tomoi, K. Sekiya, H. Kakiuchi, Polym. J., 6, 438 (1974).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Hatada, K., Sugino, H., Ise, H. et al. Heterotactic Polymers of α-Substituted Acrylic Acid Esters. Polym J 12, 55–62 (1980). https://doi.org/10.1295/polymj.12.55
Issue Date:
DOI: https://doi.org/10.1295/polymj.12.55
Keywords
This article is cited by
-
Preparation of heterotactic-rich poly(methyl methacrylate) with narrow molecular weight distribution bytert-butyllithium/bis(2,6-di-tert-butylphenoxy)methylaluminum
Polymer Bulletin (1994)
-
Dependence of the glass transition temperature of poly (methyl methacrylates) on their tacticity
Colloid and Polymer Science (1982)