Abstract
The reactions of methyl methacrylate (MMA) or I2 with the living zirconium-polyolefin bond (Zr-PO) using zirconocene catalyst system were examined. Although the reaction of MMA with the living Zr-PP does not proceed, I2 readily reacts with the living Zr-PO, such as atactic polypropylene (ataPP), iso poly(1-hexene) and syndiotactic poly(propylene) (synPP), quantitatively to give the terminal iodized polyolefins (PO-I). Moreover, PO-poly(methyl methacrylate) (PMMA) block copolymers could be obtained by the reaction of MMA with living Sm-PO, which was formerly prepared by the transformation of PO-I by Cp*2Sm.
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Y. Doi, T. Koyama, and K. Soga, Makromol. Chem., 186, 11 (1985).
Y. Doi, M. Nunomura, N. Ohgizawa, and K. Soga, Makromol. Chem. Rapid Commun., 12, 245 (1991).
H. Yasuda, M. Furo, and H. Yamamoto, Macromolecules, 25, 5115 (1992).
G. Desurmont, T. Tokumitsu, and H. Yasuda, Macromolecules, 33, 7679 (2000).
R. Nomura, M. Narita, and T. Endo, Macromolecules, 27, 4853 (1994).
R. Nomura, M. Narita, and T. Endo, Macromolecules, 27, 7011 (1994).
R. Nomura, Y. Shibasaki, and T. Endo, J. Polym. Sci., PartA: Polym. Chem., 36, 2209 (1998).
S. Collins and D. G. Ward, J. Am. Chem. Soc., 114, 5460 (1992).
S. Collins, D. G. Ward, and K. H. Suddaby, Macromolecules, 27, 7222 (1994).
Y. Li, D. G. Ward, S. S. Reddy, and S. Collins, Macromolecules, 30, 1875 (1997).
H. Nguyen, A. P. Jarvis, M. J. G. Lesley, W. M. Kelly, S. S. Reddy, N. J. Taylor, and S. Collins, Macromolecules, 33, 1508 (2000).
H. Deng, T. Yano, T. Shiono, and K. Soga, Macromolecules, 27, 7938 (1994).
H. Deng, T. Shiono, and K. Soga, Macromolecules, 28, 3067 (1995).
H. Deng and T. Shiono, Macromol. Chem. Phys., 196, 1971 (1995).
H. Deng and K. Soga, Macromolecules, 29, 1847 (1996).
T. Shiono, T. Saito, N. Saegusa, H. Hagihara, T. Ikeda, H. Deng, and K. Soga, Macromol. Chem. Phys., 199, 1573 (1998).
P. A. Cameron, V. C. Gibson, and A. J. Graham, Macromolecules, 33, 4329 (2000).
T. Stuhldreier, H. Keul, and H. Höcker, Macromol. Rapid Commun., 21, 1093 (2000).
H. Frauenrath, H. Keul, and H. Höcker, Macromolecules, 34, 14 (2001).
Y. Fukui, M. Murata, and K. Soga, Macromol. Rapid Commun., 20, 637 (1999).
Y. Fukui and M. Murata, Macromol. Chem. Phys., (accepted).
Y. Fukui and M. Murata, Macromol. Chem. Phys., (submitted).
The ataPP-I (M n = 14000/5500, MWD = 1.09/1.12) were also obtained.
P. C. Wailes, H. Weigold, and A. P. Bell, J. Organomet. Chem., 34, 155 (1972).
E. Samuel and M. D. Rausch, J. Am. Chem. Soc., 95, 6263 (1973).
S. Collins, B. A. Kuntz, N. J. Taylor, and D. G. Ward, J. Organomet. Chem., 342, 21 (1988).
F. R. W. P. Wild, M. Wasiucionek, G. Huttner, and H. H. Brintzinger, J. Organomet. Chem., 288, 63 (1985).
J. C. W. Chien, W.-M. Tsai, and M. D. Raush, J. Am. Chem. Soc., 113, 8570 (1991).
Y. Doi, Y. Watanabe, S. Ueki, and K. Soga, Makromol. Chem. Rapid Commun., 4, 533 (1983).
Reaction of living poly(1-hexene) with MMA (8 mmol) for 13 h was also conducted (M n = 6700, MWD = 1.04). 1H NMR spectrum was poly(1-hexene) homopolymer.
Polymerization of 1-hexene for 65 h was also conducted (M n = 12100, MWD = 1.06). The M n of the PHx increased with increasing polymerization time and MWD was narrow. Therefore, the living nature of poly(1-hexene) was kept at longer polymerization time.
The ataPP-I (M n = 14000, MWD = 1.09) and ataPP- block-synPMMA (M n = 20000, MWD = 1.16) were also obtained.
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Fukui, Y., Murata, M. Synthesis of Polyolefin/Poly(methyl methacrylate) Block Copolymer Using Zirconocene Catalyst System. Polym J 33, 528–533 (2001). https://doi.org/10.1295/polymj.33.528
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DOI: https://doi.org/10.1295/polymj.33.528