화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.14, No.3, 338-342, June, 2006
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Kinetic Features of the Cobalt Dihalide/Methylaluminoxane Catalytic System in 1,3-Butadiene Polymerization
Dilip Chandra Deb Nath1, 2, Christopher M. Fellows3, †, and Takeshi Shiono1, 4
  • 1Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-Ku, Yokohama 226-8503, Japan
  • 2School of Biological, Biomedical and Molecular Sciences, University of New England, NSW 2351, Japan
  • 3School of Biological, Biomedical and Molecular Sciences, University of New England, NSW 2351, Australia
  • 4Now at Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan
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The kinetic features of polymerization with an active site comprising cobalt dihalides (CoX2, where X = Cl, Br, I) activated by methylaluminoxane (MAO) were investigated in 1,3-butadiene polymerization. The catalytic system exhibited the characteristic features of living polymerization. The initiation (ki) and propagation (kp) rate coefficients were estimated using the kinetic model for slow initiation previously reported by Shiono et al.1 The energy of activation for the propagation reaction was calculated to be 27-30 kJmol-1. The marked changes in reaction rate observed with different halides could be adequately described in terms of variations in the initiation process, with the same Arrhenius curve fitting propagation rate coefficients estimated from all three halides, suggesting that the halide does not participate in the growing chain end.
Keywords:1,3-butadiene;cobalt dihalide;methylaluminoxane;initiation rate coefficient;propagation rate coefficient
  1. Nath DCD, Shiono T, Ikeda T, Macromol. Chem. Phys., 203, 756 (2002) 
  2. Nath DCD, Shiono T, Ikeda T, J. Polym. Sci. A: Polym. Chem., 40(17), 3086 (2002) 
  3. Nath DCD, Shiono T, Ikeda T, Macromol. Chem. Phys., 203, 1171 (2002) 
  4. Nath DCD, Shiono T, Ikeda T, Macromol. Chem. Phys., 204, 2017 (2003) 
  5. Peluso A, Improta R, Zambelli A, Organometallics, 19, 411 (2000) 
  6. Improta R, Peluso A, Macromolecules, 32(20), 6852 (1999) 
  7. Cass P, Pratt K, Mann T, Laslett B, Rizzardo E, Burford R, J. Polym. Sci. A: Polym. Chem., 37(16), 3277 (1999) 
  8. Ban HT, Tsunogae Y, Shiono T, J. Polym. Sci. A: Polym. Chem., 42(11), 2698 (2004) 
  9. Nath DCD, Shiono T, Ikeda T, Appl. Catal. A: Gen., 238(2), 193 (2003) 
  10. Endo K, Hatakeyama N, Kobunshi Ronbunshu, 59, 309 (2002)
  11. Miyazawa A, Kase T, Soga K, Macromolecules, 33(8), 2796 (2000) 
  12. Miyazawa A, Kase T, Soga K, J. Polym. Sci. A: Polym. Chem., 37(6), 695 (1999) 
  13. Nakayama Y, Baba Y, Yasuda H, Kawakita K, Ueyama N, Macromolecules, 36(21), 7953 (2003) 
  14. Ricci G, Italia S, Macromol. Chem. Phys., 195, 1389 (1994) 
  15. Marechal JC, Dawans F, Teyssie PH, J. Polym. Sci. A-1, 8, 1993 (1970) 
  16. De Candia F, Maglio G, Musco A, Paiaro G, Inorg. Chim. Acta., 23, 233 (1968) 
  17. Vrieze K, in Fluxional Allyl Complexes, L. J. Jackman and F. A. Cotton, Eds., New York (1975)
  18. Endo K, Uchida Y, Matsuda Y, Macromol. Chem. Phys., 197, 3515 (1996) 
  19. Karl J, Dahlmann M, Erker G, Bergander K, J. Am. Chem. Soc., 120(23), 5643 (1998) 
  20. Seth M, Ziegler T, Macromolecules, 36(17), 6613 (2003) 
  21. Cass P, Pratt K, Fairhall K, Laslett B, Rizzardo E, J. Polym. Sci. A: Polym. Chem., 39(13), 2256 (2001)