화학공학소재연구정보센터
Macromolecular Research, Vol.18, No.7, 695-700, July, 2010
A New Method of Active Center Determination for Olefin Polymerization with Supported Ziegler-Natta Catalysts
E-mail:
A novel method based on a reaction between the growing polymer chain and cinnamoyl chloride (CC) was developed to determine the number of active centers (Cp) in olefin polymerization with supported Ziegler-Natta catalysts. The reaction of titanium-polymeryl bonds in the active centers of MgCl2/ID/TiCl4-AlR3 type catalysts with CC was very fast at 20~80 ℃. Cinnamoyl labeled polymer chains were formed, which were stable in the reaction system for at least 10 min when the CC/Al molar ratio was > 1. The number of active centers was determined by measuring the number of carbonyl groups in the polymer with the UV-vis method. The Cp values of the 1-hexene polymerization systems with the addition of hydrogen were also measured.
  1. Morini G, Albizzati E, Balbontin G, Mingozzi I, Sacchi MC, Forlini F, Tritto I, Macromolecules, 29(18), 5770 (1996)
  2. Kissin YV, Mink RI, Nowlin TE, J. Polym. Sci. A: Polym. Chem., 37(23), 4255 (1999)
  3. Nishiyama I, Liu BP, Matusoka H, Nakatani H, Terano M, Macromol. Symp., 193, 71 (2003)
  4. Liu BP, Nitta T, Nakatani H, Terano M, Macromol. Symp., 213, 7 (2004)
  5. Kissin YV, J. Polym. Sci. A: Polym. Chem., 41(12), 1745 (2003)
  6. Kissin YV, Mirabella FM, Meverden CC, J. Polym. Sci. A: Polym. Chem., 43(19), 4351 (2005)
  7. Kissin YV, Chadwick JC, Mingozzi I, Morini G, Macromol. Chem. Phys., 207, 1344 (2006)
  8. Ko YS, Jeon JK, Yim JH, Park YK, Macromol. Res., 17(5), 296 (2009)
  9. Fan ZQ, Feng LX, Yang SL, J. Polym. Sci. A: Polym. Chem., 34(16), 3329 (1996)
  10. Marques MM, Tait PJT, Mejzlik J, Dias AR, J. Polym. Sci. A: Polym. Chem., 36(4), 573 (1998)
  11. Yaluma AK, Tait PJT, Chadwick JC, J. Polym. Sci. A: Polym. Chem., 44(5), 1635 (2006)
  12. Bukatov GD, Zakharov VA, Yermakov YI, Makromol. Chem., 179, 2097 (1978)
  13. Mejzlik J, Lesna M, Makromol. Chem., 178, 261 (1977)
  14. Mejzlik J, Lesna M, Majer J, J. Makromol. Chem., 184, 1975 (1983)
  15. Burfield DR, Savariar CM, Macromolecules, 12, 243 (1979)
  16. Warzelhan V, Burger TF, Stein DJ, Makromol. Chem., 183, 489 (1982)
  17. Mejzlik J, Lesna M, Kratochvila J, J. Adv. Polym. Sci., 81, 83 (1986)
  18. Vozka AP, Mejzlik J, J. Makromol. Chem., 190, 1489 (1989)
  19. Vozka AP, Mejzlik J, J. Makromol. Chem., 191, 589 (1990)
  20. Vozka AP, Mejzlik J, J. Makromol. Chem., 191, 1519 (1990)
  21. Kissin YV, J. Catal., 200(2), 232 (2001)
  22. Bukatov GD, Goncharov VS, Zakharov VA, Makromol. Chem., 187, 1041 (1986)
  23. Liu BP, Matsuoka H, Terano M, Macromol. Rapid Commun., 22(1), 1 (2001)
  24. Mori H, Terano M, Trends Polym. Sci., 5, 314 (1997)
  25. Tritto I, Sacchi MC, Locatelli P, Makromol. Chem. Rapid Commun., 4, 623 (1983)
  26. Fan ZQ, Feng LX, Yang SL, Acta Polym. Sin., 4, 503 (1991)
  27. Fan ZQ, Feng LX, Yang SL, Chin. J. Polym. Sci., 9, 113 (1991)
  28. Zhang LT, Fan ZQ, Fu ZS, E-Polymers, 143, 1 (2008)
  29. Busico V, Cipullo R, Polzone C, Talarico G, Chadwick JC, Macromolecules, 36(8), 2616 (2003)
  30. Busico V, Chadwick JC, Cipullo R, Ronca S, Talarico G, Macromolecules, 37(20), 7437 (2004)
  31. Busico V, Cipullo R, Corradini P, Makromol. Chem., 194, 1079 (1993)
  32. Busico V, Cipullo R, Romanelli V, Ronca S, Togrou M, J. Am. Chem. Soc., 127(6), 1608 (2005)
  33. Mole T, Jeffery EA, in Organoaluminium Compounds, Elsevier Publishing Company, Amsterdam, 1972, pp 294-300.
  34. Soares JB, Hamielec AE, Polymer, 37(20), 4599 (1996)
  35. Guastalla G, Giannini U, Makromol. Chem. Rapid Commun., 4, 519 (1983)
  36. Bukatov GD, Goncharov VS, Zakharov VA, Macromol. Chem. Phys., 196, 1751 (1995)
  37. Parsons IW, Alturki TM, Polym. Commun., 30, 72 (1989)
  38. Kissin YV, Rishina LA, J. Polym. Sci. A: Polym. Chem., 40(9), 1353 (2002)