화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Korea Polymer Journal, Vol.8, No.5, 238-242, October, 2000
Export Citation
Polymerization of Ethylene Initiated with Trisiloxane-bridged Heterometallic Dinuclear Metallocene
Dong Ho Lee†, hun Bong Lee, Woo Sik Kim, Kyung Eun Min, Lee Soon Park, Kwan Ho Seo, Inn Kyu Kang, Seok Kyun Noh1, Chang Keun Song1, Sang Sun Woo2, and Hyun joon Kim2
  • Department of Polymer Science, Kyungpook National University, Taegu 702-701, Korea
  • 1School of Chemical Engineering and Technology, Yeungnam University, Kyungsan 712-749, Korea
  • 2R&D Center, Sansung General Chemicals, Ltd., Taejon 305-714, Korea
E-mail:
The new trisiloxane-bridged heterometallic dinuclear metallocenes, hexamethyltrisiloxanediy-1(cyclopentadienyltitanium trichloride) (cyclopentadienylidenyl zirconium dichloride), Cl2Ti-Cp(CH3)2Si-O-Si(CH3) 2-O-Si(CH3)2-Cp-ZrIndCl2 (1) and hexamethyltrisiloxanediyl(cyclopentadienylindenylhafnium dichloride) (cyclopentadienylindenyl zirconium dichloride), Cl2lndHf-Cp(CH32Si-O-Si(CH3) 2-O-Si(CH3)2-Cp-ZrlndCl2 (2) connecting two dissinilar metallocenes were synthesized and used for ethylene polymerization in the presence of modified methylaluminoxane (MMAO) cocatalyst. The catalytic activity of heterometallic dinuclear metallocenes, 1 and 2 was lower than that of corresponding mononuclear metallocene as well as two physically mixed catalysts. CpTiCl3/Cp2ZrCl2 and Cp2HfCl2ZrCl2. On the ofther hand, MWDof PE obtained with 1 and 2 remarkably broader (Mw/Mn became up to 9.4)than those of PEs prepared with the corresponding mononuclear metallocenes and mixed catalysts. With analysis by GPC and CFC, it was found that PE produced by the heterometallic dinuclear metallocenes exhibited the definite bimodal GPC curves that should cause the brodening of MWD.
  1. Scheirs J, Kaminsky W, Metallocenebased Polyolefins, Vol. 1 & 2, John Wiley & Sons, Chichester, 2000 (2000)
  2. Ciruelos S, Cuenca T, Gomez-Sal P, Mamazanero A, Royo P, Organometallics, 14, 177 (1995) 
  3. Lee DH, Yoon KB, Lee EH, Noh SK, Lee CS, Huh WS, Macromol. Rapid Commun., 17, 325 (1996) 
  4. Liang B, Li Y, Xie G, Macromol. Rapid Commun., 17, 193 (1996) 
  5. Lee DH, Noh SK, Macromol. Rapid Commun., 16, 265 (1995) 
  6. Lee DH, Noh SK, Macromol. Rapid Commun., 17, 325 (1996) 
  7. Lee DH, Noh SK, J. Org. Chem., 518, 1 (1996) 
  8. Lee DH, Noh SK, J. Org. Chem., 580, 90 (1997)
  9. Lee DH, Noh SK, J. Org. Chem., 595, 147 (2000)
  10. Lee DH, Yoon KB, Lee HB, Noh SK, Shim JY, Korea Polym. J., 4(2), 107 (1996)
  11. Lee DH, Noh SK, Bull. Korean Chem. Soc., 18, 618 (1997)
  12. Lee DH, Yoon KB, Noh SK, Woo SS, Polymer, 38(6), 1481 (1997) 
  13. Lee DH, Noh SK, Macromol. Symp., 118, 129 (1997)
  14. Lee DH, Lee HB, Noh SK, Kim JH, Yoon KB, Kim HJ, Woo SS, Korea Polym. J., 5(4), 234 (1997)
  15. Lee DH, Yoon KB, Kim HJ, Woo SS, Noh SK, J. Appl. Polym. Sci., 67(13), 2187 (1998) 
  16. Lee DH, Noh SK, Polym. Preprints, 40(2), 835 (1999)
  17. Tae W, Kim S, Noh SK, Kim T, Lee DH, Polym.(Korea), 24(2), 159 (2000)
  18. Noh SK, Kim S, Kim J, Lee DH, Yoon KB, J. Polym. Sci. A: Polym. Chem., 35(17), 3717 (1997) 
  19. Morris RJ, J. Org. Chem., 489, C4 (1995) 
  20. Ewen JA, Catalytic Polymerization of Olefins, T. Keii and K. Soga, Eds., Kodansha, Tokyo, 1986, pp 271 (1986)
  21. Lee DH, Yoon KB, Noh SK, Kim SC, Macromol. Rapid Commun., 17, 639 (1996) 
  22. Ahn TO, Hong SC, Kim IH, Lee DH, J. Appl. Polym. Sci., 67(13), 2213 (1998) 
  23. Ahn TO, Hong SC, Huh WS, Lee YC, Lee DH, Polym. Eng. Sci., 39(7), 1257 (1999) 
  24. Sugano T, Gotoh Y, Fujita T, Uozumi T, Soga K, Makromol. Chem., 193, 43 (1992)