Abstract
Group transfer polymerization (GTP) of methyl crotonate was examined by using a ketene silyl acetal with tert-butyldimethylsilyl group in the presence of HgI2 and tert-butyldimethylsilyl iodide as a catalyst and a co-catalyst, respectively. Under optimized conditions, the GTP produced disyndiotactic polymers with narrow molecular weight distribution in quantitative yields. The trialkylsilyl group in the initiator components was found to exert control over the stereochemical process of the GTP; the bulky tert-butyldimethylsilyl group leads to the highest disyndiotacticity. The results provide a direct evidence for the transferring silyl group to be involved in the propagation steps in the GTP.
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O. W. Webster, W. R. Hertler, D. Y. Sogah, W. B. Farnham, and T. V. Rajanbabu, J. Am. Chem. Soc., 105, 5706 (1983).
W. B. Farnham and D. Y. Sogah, Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem., 27, 167 (1986).
D. Y. Sogah and W. B. Farnham in “Organosilicon and Bioorganosilicon Chemistry,” H. Sakurai, Ed., Wiley, New York, N.Y., 1986, p 219.
R. P. Quirk and G. P. Bidinger, Polym. Bull., 22, 63 (1989).
R. P. Quirk and J. Ren, Macromolecules, 25, 6612 (1992).
A. H. E. Müller, L. Lochman, and J. Trekoval, Macromol. Chem., 187, 1473 (1986).
M. A. Müller and M. Stickler, Makromol. Chem., Rapid Commun., 7, 575 (1986).
T. Nakano and D. Y. Sogah, J. Am. Chem. Soc., 117, 534 (1995).
K. G. Bannerjee and T. E. Hogen-Esch, Macromolecules, 26, 926 (1993).
H. Yuki, K. Hatada, T. Ninomi, and Y. Kikuchi, Polym. J., 1, 36 (1970).
K. Ute, T. Tarao, and K. Hatada, Polym. J., 29, 957 (1997).
K. Ute, T. Tarao, S. Nakao, and T. Kitayama, Polymer, 44, 7869 (2003).
R. Zhuang and A. H. E. Müller, Macromolecules, 28, 8035 (1995).
R. Zhuang and A. H. E. Müller, Macromolecules, 28, 8043 (1995).
K. Ute, T. Tarao, S. Hongo, H. Ohnuma, K. Hatada, and T. Kitayama, Polym. J., 31, 177 (1999).
1-Methoxy-1-(tert-butyldimethylsiloxy)-2-methyl-1-propene, the ketene silyl acetal with the same parent group as (1) and (2), was found far less reactive in the GTP. Thus the acetal (3) (R1=H) was used in the present work.
H. Vorbrügen, K. Krolikiewicz, and B. Bennua, Chem. Ber, 114, 1234 (1981).
H. C. Marsmann and H. G. Horn, Z. Naturforsch. B, 27, 1448 (1972).
M. Schmeißer, P. Sartori, and B. Lippsmeier, Chem. Ber, 103, 868 (1970).
H. W. Roesky and H. H. Giere, Z. Naturforsch. B, 25, 773 (1970).
G. Simchen and W. Kober, Synthesis, 259 (1976).
H. Emde and G. Simchen, Synthesis, 867 (1977).
M. R. Detty and M. D. Seidler, J. Org. Chem., 46, 1283 (1981).
R. J. Ogg, P. B. Kingsley, and J. S. Taylor, J. Magn. Reson., Ser. B, 104, 1 (1994).
W. J. Brittain and I. B. Dicker, Polym. Int., 30, 101 (1993).
W. J. Brittain and I. B. Dicker, Makromol. Chem., Macromol. Symp., 67, 373 (1993).
In the previous work, we found that, in the polymerizations of methyl crotonate by ketene silyl acetal 2, type of cocatalyst, (CH3)3SiI or (C2H5)3SiI, did not affect the stereostructure of the polymers obtained, suggesting the silyl group in the ketene silyl acetal has the prime importance in the stereoregulation.
K. Ute, T. Asada, Y. Nabeshima, and K. Hatada, Macromolecules, 26, 7086 (1993).
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Ute, K., Tarao, T. & Kitayama, T. Enhanced Stereocontrol in Disyndiotactic-specific Group Transfer Polymerization of Methyl Crotonate—Stereochemical Evidence of Group Transfer. Polym J 37, 578–583 (2005). https://doi.org/10.1295/polymj.37.578
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DOI: https://doi.org/10.1295/polymj.37.578