Abstract
Totally deuterated methyl methacrylate (MMA-d8) was polymerized by C4H9MgCl in toluene at −78°C, and the resulting polymer and oligomer were analyzed by 1H NMR spectroscopy. The polymer and oligomer was found to contain butyl pentadeuteroisopropenyl ketone (BIPK-d5) units. The ketone was formed by the addition of the initiator onto the carbonyl group of the monomer. The content of BIPK-d5 units in the polymer and oligomer was found to be 0.3 and 0.4 per chain, respectively. FD- and EI-mass spectra of the fractionated oligo(MMA)s indicated that most of the BIPK units were located at their terminating chain ends. Structures which were produced by intramolecular cyclization and by carbonyl addition of propagating anions onto MMA or BIPK were found at the end of the oligomer chain, but the amounts of these structures were at most 10% of the chain. The fate of the initiator during the polymerization was clarified for the most part. From the results, the mechanism of polymerization is discussed in some detail.
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W. E. Goode, F. H. Owens, R. P. Fellman, W. H. Snyder, and J. E. Moore, J. Polym. Sci., 46, 317 (1960).
A. Nishioka, H. Watanabe, K. Abe, and I. Sono, J. Polym. Sci., 48, 241 (1960).
P. Pino and U. W. Suter, Polymer, 17, 977 (1976).
H. Yuki and K. Hatada, Adv. Polym. Sci., 31, 1 (1979).
B. L. Erussalimsky, E. Yu. Melenevskaya, and V. N. Sgonnik, Acta Polymerica, 32, 183 (1981).
P. E. M. Allen and B. O. Bateup, Eur. Polym. J., 14, 1001 (1978).
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).
P. E. M. Allen, C. Mair, D. R. G. Williams, and E. H. Williams, Eur. Polym. J., 20, 119 (1984).
W. E. Goode, F. H. Owens, and W. L. Myers, J. Polym. Sci., 47, 75 (1960).
Y. Yasuda, N. Kawabata, and T. Tsuruta, J. Macromol. Sci., Chem., A1, 669 (1967).
B. O. Bateup and P. E. M. Allen, Eur. Polym. J., 13, 761 (1977).
K. Hatada, T. Kitayama, and H. Yuki, Makromol. Chem., Rapid Commun., 1, 51 (1980).
K. Hatada, T. Kitayama, and H. Yuki, Polym. Bull., 2, 15 (1980).
K. Hatada, T. Kitayama, K. Fujikawa, K. Ohta, and H. Yuki, ACS Symp. Ser., 166, 327 (1981).
K. Hatada, T. Kitayama, S. Okahata, and H. Yuki, Polym. J., 13, 1045 (1981).
K. Hatada, T. Kitayama, S. Okahata, and H. Yuki, Polym. J., 14, 971 (1982).
T. Kitayama, K. Ute, and K. Hatada, Polym. J., 16, 925 (1984).
S. C. Watson and J. F. Eastham, J, Organometal. Chem., 9, 165 (1967).
K. Hatada, Y. Terawaki, and H. Okuda, Org. Magn. Res., 9, 518 (1977).
D. M. Wiles and S. Bywater, Trans. Faraday Soc., 61, 150 (1965).
K. Hatada, T. Kitayama, H. Sugino, and Y. Umemura, Polym. J., 12, 535 (1980).
K. Hatada, K. Ute, K. Tanaka, T. Kitayama, and Y. Okamoto, Polym. J., 17, 977 (1985).
K. Ute and K. Hatada, Polym. J., to be submitted.
H. Schreiber, Makromol. Chem., 36, 86 (1960).
G. E. Ham, “Copolymerization,” John Wiley & Sons Inc., New York., N. Y., 1964, p. 845.
T. Miyamoto, and H. Inagaki, Polym. J., 1, 46 (1970).
K. Hatada, T. Kitayama, H. Sugino, M. Furomoto, and H. Yuki, “Preparation and Properties of Stereoregular Polymers,” R. W. Lenz and F. Ciardelli, Ed., D. Reidel Publishing Company, Dordrecht, Holland, 1979, p 185.
K. Hatada, K. Ute, and T. Kitayama, Polym. Prepr., Jpn., 32, 1459 (1983).
T. Miyamoto, S. Tomoshige, and H. Inagaki, Polym. J., 6, 564 (1974).
K. Hatada, K. Ute, T. Kitayama, and M. Kamachi, Polym. J., 15, 771 (1983).
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Ute, K., Kitayama, T. & Koichi, H. Studies on the Polymerization of Methyl Methacrylate with Butylmagnesium Chloride by the Aid of Totally Deuterated Monomer—Structures of Polymerization Products and Fate of Initiator. Polym J 18, 249–261 (1986). https://doi.org/10.1295/polymj.18.249
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DOI: https://doi.org/10.1295/polymj.18.249
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