Abstract
Highly isotactic PMMAs with narrow molecular weight distribution (Mw/Mn<1.2) have been prepared by the polymerization of MMA in toluene at −78°C initiated by t-C4H9MgBr prepared in diethyl ether. The polymerization proceeded in a “living” manner, in which the initiation reaction was fast and quantitative whereas the propagation was slow. The ether solution of t-C4H9MgBr used as the initiator contained almost equal amounts of MgBr2 produced by an Wurtz type coupling during the preparation. It has been found from 1H NMR analyses that the excess amount of MgBr2 contributes to form the initiating species of homogeneous activity and stereospecificity. Polymerizations of MMA by n-, iso-, and s-C4H9MgBr were also investigated in toluene at −78°C. With an increase in the bulkiness of the alkyl group the isotacticity of the polymer increased and the molecular weight distribution became narrower. The addition of MgBr2 also increased the isotacticity of the polymer. The results of block copolymerizations of MMA and MMA-d8 or ethyl methacrylate are also described.
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B. O. Bateup and P. E. M. Allen, Eur. Polym. J., 13, 761 (1977).
P. E. M. Allen and B. O. Bateup, Eur. Polym. J., 14, 1001 (1978).
P. E. M. Allen, J. Makromol. Sci., Chem., A14, 11 (1980).
P. E. M. Allen, M. C. Fisher, C. Mair, and E. H. Williams, “Anionic Polymerization: Kinetics, Mechanisms, Synthesis,” ACS Symp. Ser., No. 166, 185 (1981).
P. E. M. Allen and C. Mair, Eur. Polym. J., 20, 697 (1984).
K. Matsuzaki, H. Tanaka, and T. Kanai, Makromol. Chem., 182, 2905 (1981).
K. Hatada, T. Kitayama, H. Sugino, M. Furomoto, and H. Yuki, “Preparation and Properties of Stereoregular Polymer,” R. W. Lenz and F. Chiardelli, Ed., D. Reidel Publishing Company, Dordrecht, Holland, 1979, p 185.
K. Hatada, T. Kitayama, K. Fujikawa, K. Ohta, and H. Yuki, ACS Symp. Ser., No. 166, 327 (1981).
T. Miyamoto and H. Inagaki, Polym. J., 1, 46 (1970).
K. Hatada, T. Kitayama, S. Okahata, and H. Yuki, Polym. J., 14, 971 (1982).
K. Hatada, K. Ute, and T. Kitayama, Polym. Prepr., Jpn., 33, 1391 (1984).
K. Ute and K. Hatada, Polym. J., to be submitted.
K. Hatada, K. Ute, K. Tanaka, T. Kitayama, and Y. Okamoto, Polym. J., 17, 977 (1985).
Y. Okamoto, K. Ohta, K. Hatada, and H. Yuki, ACS Symp. Ser., No. 166, 353 (1981).
M. A. Doherty and T. E. Hogen-Esch, Polym. Prepr., A.C.S., Div. Polym. Chem., 25(2), 5 (1984).
K. Hatada, K. Ute, and K. Tanaka, Polym. J., to be submitted.
K. Ute, T. Kitayama, and K. Hatada, Polym. J., 18, 249 (1986).
K. Hatada, T. Kitayama, S. Okahata, and H. Yuki, Polym. J., 13, 1045 (1981).
J. Salonen and G.-A. Holmberg, Acta Chem. Scand., B31, 719 (1977).
A. Soum, N. D’Accorso, and M. Fontanille, Makromol. Chem., Rapid Commun., 4, 471 (1983).
P. E. M. Allen and D. R. G. Williams, Ind. Eng. Chem. Prod. Res. Dev., 24, 334 (1985).
K. Ute and K. Hatada, Polym. J., to be submitted.
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Hatada, K., Ute, K., Tanaka, K. et al. Living and Highly Isotactic Polymerization of Methyl Methacrylate by t-C4H9MgBr in Toluene. Polym J 18, 1037–1047 (1986). https://doi.org/10.1295/polymj.18.1037
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DOI: https://doi.org/10.1295/polymj.18.1037
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