Article
  • Production of Polyethylene Wax via Metallocene Catalysts [(TMDS)Cp2]ZrCl2 and [(n-Bu)2Cp2]ZrCl2 in the Presence of Hydrogen Gas as a Chain Transfer Reagent
  • Kim JY, Yoon SY, Yang YD, Noh SK
  • 메탈로센 화합물인 [(TMDS)Cp2]ZrCl2 촉매와 [(n-Bu)2Cp2]ZrCl2 촉매를 이용한 고품질의 폴리에틸렌 왁스 제조
  • 김지윤, 윤석영, 양영도, 노석균
Abstract
Polyethylene has been prepared via metallocene catalysts [(TMDS)Cp2]ZrCl2, 1, and [(n- Bu)2Cp2]ZrCl2, 2, in the presence of hydrogen as a chain transfer reagent. Increase of hydrogen flow to the polymerization reactor resulted in the drop of catalytic activity, reduction of molecular weight of polyethylene, getting narrow of molecular weight distribution of polyethylene, and melting point of the polyethylene wax. It should be noticed that it was possible to control molecular weight down to 1500 and melting temperature to 60 ℃ of polyethylene wax using the catalyst 1 that has been developed by authors as well as the catalyst 2 from Exxon.

메탈로센 [(TMDS)Cp2]ZrCl2, 촉매 1과 Exxon 촉매인 [(n-Bu)2Cp2]ZrCl2, 촉매 2를 사용하여 폴리에틸렌 왁스를 제조하였다. 분자량을 조절하기 위하여 수소를 연쇄이동제로 사용하였다. 실험결과 수소의 주입량이 증가할수록 중합활성의 감소, 생성된 폴리에틸렌 왁스의 분자량과 분자량 분포의 감소, 그리고 폴리에틸렌 왁스의 융점저하가 관찰되었다. 수소의 주입으로 폴리에틸렌의 분자량은 1500, 융점은 60 ℃까지 조절이 가능하였다. 수소의양을 조절함으로써 메탈로센을 통해 분자량분포가 좁고 융점이 낮은 고품질의 폴리에틸렌 왁스의 제조가 가능하였다. 본 연구실에서 개발된 촉매 1은 알려진 가장 우수한 메탈로센인 촉매 2와 폴리에틸렌 왁스 제조에서 경쟁이 가능한 유사한 특성을 보였다.

Keywords: metallocene; polyethylene wax; hydrogen as a chain transfer reagent; molecular weight control

References
  • 1. Choi KH, HWAHAK KONGHAK, 39(6), 667 (2001)
  •  
  • 2. Ryu SH, Song JC, Lee WY, HWAHAK KONGHAK, 27(4), 489 (1989)
  •  
  • 3. Choi KH, Kor. Pat. 0000286 (2001)
  •  
  • 4. Vandenberg EI, US Patent 3051690, to Hercules Powder Co., C. A. No. 53:13660g (1962)
  •  
  • 5. Natta G, Cheim. Ind., 41, 519 (1959)
  •  
  • 6. Kaminsky W, Luker H, Makromol. Chem., Rapid Commun., 5, 225 (1984)
  •  
  • 7. Dutschke J, Kaminsky W, Luker H, Polymer Reaction Engineering, Reichert KH, Geiseler W, Eds., Hanser Publishers, Munich, p. 209 (1983)
  •  
  • 8. Chien JCW, Wang BP, J. Polym. Sci. Part A: Polym. Chem., 28, 15 (1990)
  •  
  • 9. Reddy SS, Sivram S, Prog. Polym. Sci., 20, 309 (1995)
  •  
  • 10. Randall JC, Rucker SP, Macromolecules, 27(8), 2120 (1994)
  •  
  • 11. Michelotti M, Altomare A, Ciardelli F, Ferrarini P, Polymer, 37(22), 5011 (1996)
  •  
  • 12. Chang M, U.S. Patent 4914253 (1990)
  •  
  • 13. Gibson VC, Spitzmesser SK, Chem. Rev., 103(1), 283 (2003)
  •  
  • 14. Ittel SD, Johnson LK, Brookhart M, Chem. Rev., 100(4), 1169 (2000)
  •  
  • 15. Al-Hymydi A, Garrison JC, Mohammed M, Youngs WJ, Collins S, Polyhedron, 24, 1234 (2005)
  •  
  • 16. Cuenca T, Pascal A, Royo P, Parra-Hake M, Organometallics, 14, 848 (1995)
  •  
  • 17. Noh SK, Byun GG, Lee CS, Lee DH, Yoon KB, Kang KS, J. Organomet. Chem., 518, 1 (1996)
  •  
  • 18. Rieger R, Jany G, Fawzi R, Steimann, Organometallics, 13, 647 (1994)
  •  
  • 19. BUSICO V, CIPULLO R, BORRIELLO A, Macromol. Rapid Commun., 16(4), 269 (1995)
  •  
  • 20. Noh SK, Kim S, Kim J, Lee DH, Yoon KB, J. Polym. Sci. A: Polym. Chem., 35(17), 3717 (1997)
  •  
  • 21. Schubbe R, Angermund K, Fink G, Goddard R, Macromol. Chem. Phys., 96, 467 (1990)
  •  
  • 22. Jung J, Noh SK, Lee H, Park SK, Lee DH, Kang KS, Polym.(Korea), 23(2), 189 (1999)
  •  
  • 23. Sawaguchi T, Ikemura T, Seno M, Macromolecules, 28(24), 7973 (1995)
  •  
  • 24. Shin DK, Kor. Pat. 0067267 (2000)
  •  
  • 25. Ratio of formation of Unsaturated end group(%)=[(A1/2)×100]/(A1/2)+{(A2/3)-(A1/2)/2}]. A1=Area of unsaturated bond between 4.6-5.4 ppm, A2=Area of methyl group at 0.9ppm
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2022 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2008; 32(6): 566-572

    Published online Nov 25, 2008

  • Received on Jul 3, 2008
  • Accepted on Aug 25, 2008