• Copolymerization of Ethylene and Cycloolefin with Metallocene Catalyst: Ⅰ. Effect of Catalyst
  • Lee DH, Jung HK, Kim WS, Min KE, Park LS, Seo KH, Kang IK, Noh SK
  • 메탈로센 촉매를 이용한 에틸렌과 시클로올레핀의 공중합: Ⅰ. 촉매의 영향
  • 이동호, 정희경, 김우식, 민경은, 박이순, 서관호, 강인규, 노석균
Abstract
The copolymerization to ethylene (E) and norbornene (N) was examined by using various metallocene catalysts and modified-MAO(MMAO) cocatalyst. For C2-symmetry catalysts such as rac-Et(Ind)2ZrCl2, Me2Si(Ind)2ZrCl2, Me2Si(Cp)2ZrCl2 and Cs-symmetrical iPr(FluCp)ZrCl2 as well as CGC and di-briged zirconocene, the effects of catalyst structure and [N]/[E] feed ratio on catalyst activity, thermal property and [N] content of copolymer (COC) was investigated. For rac-Et(Ind)2ZrCl2 catalyst of a constant [N]/[E] feed ratio, the appropriate conditions of [Al]/[Zr] mole ratio, polymerization temperature and cocatalyst structure were found to be 3000, 40℃, MMAO cocatalyst, respectively. As [N]/[E] feed ratio increased, the incorporation of norbornene to copolymer increased while the activity of catalyst decreased except fro iPr(FluCp)ZrCl2. With consideration of catalyst activity as well as N content, it was found that rac-Et(Ind)2ZrCl2/MMAO system exhibited relatively high activity and controllable Tg. Monomer reactivity ratio was determined by Kelen-00 method.

다양한 종류의 메탈로센 촉매와 공촉매인 개질-MAO(MMAO)을 이용한 에틸렌(E)과 노르보르넨(N)의 공중합에서 중합조건이 촉매 활성 및 공중합체의 구조와 성질 등에 미치는 영향을 조사하였다. 즉 C2-대칭구조를 가지는 rac-Et(Ind)2ZrCI2, M2Si(Ind)2ZrCl2, Me2Si-(Cp)2ZrCl2 및 CS-대칭구조를 가지는 iPr(FluCp)ZrCl2, 그리고 constrained geometry catalyst(CGC)와 이중다리(di-bridged) 지그코노센 등의 다양한 메탈로센 촉매를 사용하여 [N]/[E]공급비에 따른 촉매 활성, 공중합체(COC)의열적 성질 및 N 함량을 조사하였다. rac-Et(Ind)2ZrCI2를 촉매로 사용한 경우에 공촉매의 몰비, 중합 온도 및 공촉매 종류 등의 중합조건을 조사한 결과 [Al]/[Zr]=3000, 40℃, MMAO 공촉매 등이 적합하였다. [N]/[E]공급비가 증가됨에 따라 COC내의 N 함량이 증가하는 일반적인 경향을 보였으나, 촉매 활성은 감소하였으나 Cs-대칭구조의 경우에는 증가하였다 촉매활성과 N함량 등을 고려해 보면 rac-Et(Ind)2ZrCI2/MMAO계에서 비교적 높은 촉매 활성과 COC의 Tg제어가 용이한 결과를 얻을 수 있었다. 촉매종류에 따른 단랑체의 반응성비를 Kelen-Tudos방법으로 구하였다.

Keywords: metallocene; ethylene; morbornene; copolymer; cycloolefin

References
  • 1. Sinn H, Kaminsky W, Adv. Organomet. Chem., 18, 99 (1980)
  •  
  • 2. Kaminsky W, Spiedhl R, Makromol. Chem., 190, 515 (1989)
  •  
  • 3. Kaminsky W, Moller-Lindenhof N, Bull. Soc. Chem. Belg., 99, 103 (1990)
  •  
  • 4. Kaminsky W, Bark A, Arndt M, Makromol. Chem. Makromol. Symp., 47, 83 (1991)
  •  
  • 5. Kaminsky W, Noll A, Polym. Bull., 31, 175 (1993)
  •  
  • 6. Sekka MEur. Patent, 283,164 (1987)
  •  
  • 7. Hoechst AGEur. Patent, 304,671 (1987)
  •  
  • 8. Hoechst AGEur. Patent, 503,422 (1987)
  •  
  • 9. Hoechst AGU.S. Patent, 5,204,429 (1987)
  •  
  • 10. Hoechst AGGerman Patent, 3,835,044 (1988)
  •  
  • 11. Kaminsky W, Noll AZiegler Catalysts, eds. by G. Fink, R. Mulhaupt, and H.H. Brintzinger, p. 149, Springer Verlag, Berlin, 1995 (1995)
  •  
  • 12. Bergstrom CH, Starck PG, Seppala JV, J. Appl. Polym. Sci., 67(3), 385 (1998)
  •  
  • 13. Marathe S, Sivaram S, Macromolecules, 27(5), 1083 (1994)
  •  
  • 14. Lasarvov H, Pakkanen T, Macromol. Rapid Commun., 20, 356 (1999)
  •  
  • 15. Arndt M, Engehausen R, Kaminsky W, Zoumis K, J. Mol. Catal., 101, 171 (1995)
  •  
  • 16. Henshcke O, Koller F, Arnold M, Macromol. Rapid Commun., 18, 617 (1997)
  •  
  • 17. Hoechst/Mitsui extend COC deal, Asian Chemical News, January 30, 23 (1995)
  •  
  • 18. Arndt M, Beulich I, Kaminsky WProceedings of MetCon'96, Catalyst Consultant Inc., Houston, Tx, 1996 (1996)
  •  
  • 19. Weiss K, Neugebauer U, Blau S, Lang HJ, J. Org. Chem., 520, 171 (1996)
  •  
  • 20. Noh SK, Jung JH, Lee DH, Park SK, Kim HJ, J. Org. Chem., 592, 147 (2000)
  •  
  • 21. Dow, Eur. Patent, 0416815A2 (1990)
  •  
  • 22. Dow, Eur. Patent, 0514828A1 (1992)
  •  
  • 23. Devor DD, Timmers FJ, Hasha DL, Rosen RK, Marks TJ, Deck PA, Stern CL, Organometallics, 14, 3132 (1995)
  •  
  • 24. McKnight AL, Waymouth RM, Macromolecules, 32(9), 2816 (1999)
  •  
  • 25. Kaminsky W, Arndt M, Adv. Polym. Sci., 127, 177 (1997)
  •  
  • 26. Fineman M, Ross SD, J. Polym. Sci., 5, 259 (1950)
  •  
  • 27. Kelen T, Tudos F, React. Kinet. Catal. Lett., 1, 487 (1974)
  •  
  • 28. Bergstrom CH, Vaananen TL, Seppala JV, J. Appl. Polym. Sci., 63(8), 1071 (1997)
  •  
  • 29. Pietikainen P, Seppala JV, Macromolecules, 27(6), 1325 (1994)
  •  
  • 30. Herfert N, Montag P, Finck G, Macromol. Chem., 194, 3167 (1993)
  •  
  • 31. Sishta C, Hathoron R, Marks T, J. Am. Chem. Soc., 114, 122 (1992)
  •  
  • 32. Hedden D, Marks TJ, J. Am. Chem. Soc., 110, 1649 (1988)
  •  
  • 33. Jordan RF, La Pointe WE, Baenziger NC, Hinch GD, Organometallics, 8, 1539 (1990)
  •  
  • 34. Chien JCW, Song W, Rausch MD, Macromolecules, 26, 3239 (1993)
  •  
  • 35. Kaminsky W, Engehausen R, Zoumis K, Spaleck W, Rohrmann J, Makromol. Chem., 193, 1643 (1992)
  •  
  • 36. Dorer B, Prosenc MH, Rief U, Brintzinger HH, Organometallics, 13, 3868 (1994)
  •  
  • 37. Roth H, Meyer U, Koinzer JP, Wiegand G, Plast. Kautsch, 32, 291 (1985)
  •  
  • 38. Kaminsky W, Arndt M, Bark A, Polym. Prepr., 32, 467 (1990)
  •  
  • 39. Montag P, Ruchatz D, Fink G, Kautsch. Gummi Kunstst, 49, 582 (1996)
  •  
  • 40. Rische T, Waddon AJ, Dickinson LC, MacKnight WJ, Macromolecules, 31(6), 1871 (1998)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2024 Impact Factor : 0.6
  • Indexed in SCIE

This Article

  • 2000; 24(4): 445-452

    Published online Jul 25, 2000