• Polymerizaion of α-olefin Catalyzed by rac-(EBI)M(NMe2)2(M=Zr, Hf)/AIR3/[Ph3C][B(C6F5)4]
  • Kim I, Choi CS, Kim KT
  • rac-(EBI)M(NMe2)2(M=Zr, Hf)/AIR3/[Ph3C][B(C6F5)4] 촉매를 이용한 α-올레핀의 중합
  • 김일, 최창수, 김기태
Abstract
Polymerization of α-Olefin Catalyzed by rac-(EBI)M(NMe2)2 (EBI=1,2-ethylenebis-(1-indenyl); M=Zr(rac-1); M=Hf(rac2) in the presence of Al(i-Bu)3/[Ph3C][B(C6F5)4]. The polymerization of high α-olefin showed high activity and simialr polymerization behavior. The polymerization activity was affected by both monomer size and lateral size of polymer chain. The conversion of monomer to polymer decreases with the increased lacteral size in the order of 1-pentene>1-hexene>1-octene>1-decene. The same dependencesof melting behavior and intrinsic viscosity of polyolefin on lateral size were observed according to the results obrained by differential scanning calorimetry and intrinsic viscosity. All poly(α-olefin)s showed very high isotacticity(triad) and the isotacticity increases in the order of poly(1-pentene)1H NMR and Raman spectra analysis showed that chain transfer to cocatalyst, which generates saturated methyl groups, is a main chain termination. The β-hydride eliminations, which generate unsaturated vinylidene, tri-substituted, and vinylene end group. are found to be minor chain terminations

이소특이성 촉매인 rac-(EBI)M(NMe2)2 [EBI=1,2-ethylenebis-(1-indenyl); M=Zr(rac-1), M=Hf(rac-2)]와 공촉매계로서 Al(iBu3/[Ph3C][B(C6F5)4]를 이용하여 고차 α-올레핀의 중합특성을 조사하였다. 고차 α-올레핀의 중합은 높은 활성을 나타냈으며, rac-1과 rac-2의 두 촉매계는 유사한 중합거동을 나타냈다. 중합 활성은 단량체의 크기와 중합된 고분자 가지의 길이에 의해 영향을 받았다. 단량체의 전환율은 1-pentene>1-hexene>1-octene>1-decene의 순서로 감소하였다. 또한 합성된 폴리(α-올레핀)의 고유점도값과 시차주사열분석기에 의한 용융거동도 유사한 경향을 나타냈다. 폴리(α -올레핀)은 매우 높은 이소탁틱도 트리에드를 나타냈으며 poly(1-pentene)1H NMR과 Raman 스펙트럼을 이용한 고분자 사슬의 말단기 분석 결과로부터, 주로 일어나는 사슬정지반응은 말단에 포화된 메틸기를 생성하는 공촉매로부터 전이이며, 소수 반응으로 비닐리덴, 삼차치환 및 비닐렌 이중결합을 생성하는 β-수소제거 반응이 일어남을 알 수 있었다.

Keywords: isopecific; metallocene; catalysts high α-olefin; polymerizaion

References
  • 1. Wang JS, Porter RS, Knox JR, Polym. J., 10, 619 (1978)
  •  
  • 2. Aubrey DW, Barnatt A, J. Polym. Sci. A: Polym. Chem., 6, 241 (1968)
  •  
  • 3. Chien JCW, Kuo CI, Ang T, J. Polym. Sci. A: Polym. Chem., 23, 723 (1985)
  •  
  • 4. Soga K, Lee DH, Shiono T, Kashiwa N, Makromol. Chem., 190, 2683 (1989)
  •  
  • 5. Kaminsky W, Macromol. Chem. Phys., 197, 3907 (1996)
  •  
  • 6. Olagoke O, Muhammad A, Kaminsky W, J. Macromol. Sci.-Rev. Macromol. Chem. Phys., C37(3), 519 (1997)
  •  
  • 7. Ribeiro MR, Deffieux A, Portela MF, Ind. Eng. Chem. Res., 36(4), 1224 (1997)
  •  
  • 8. Thayer AM, Chem. Eng. News, 73(37), 15 (1995)
  •  
  • 9. Brintzinger HH, Fischer D, Mulhaupt R, Rieger B, Waymouth RM, Angew. Chem.-Int. Edit., 34, 1143 (1995)
  •  
  • 10. Sinclair KB, Wilson RB, Chem. Ind., 857 (1994)
  •  
  • 11. Hring PCM, Coville NJ, J. Org. Chem., 479, 1 (1994)
  •  
  • 12. Stehling U, Diebold J, Kirsten R, Roll W, Brintzinger HH, Jungling S, Lhaupt RM, Langhauser F, Organometallics, 13, 964 (1994)
  •  
  • 13. Spaleck W, Kuber F, Winter A, Rohrmann J, Bachmann B, Antberg M, Dolle V, Paulus EF, Organometallics, 13, 954 (1994)
  •  
  • 14. Horton AD, Trends Polym. Sci., 2, 158 (1994)
  •  
  • 15. Farina M, Trends Polym. Sci., 2, 80 (1994)
  •  
  • 16. Kaminsky WMethoden der Organischen Chemie, J. Galbe and G. Thieme-Verlag, Eds., p. 894 Houben-Weyl, Stuttgart, 1986 (1986)
  •  
  • 17. Fries A, Mise T, Matsumoto A, Ohmori H, Wakatsuki R, Chem. Commun., 783 (1996)
  •  
  • 18. Sinn H, Kaminsky W, Adv. Organomet. Chem., 18, 99 (1980)
  •  
  • 19. Pino P, Mulhaupt R, Angew. Chem.-Int. Edit., 19, 857 (1980)
  •  
  • 20. Asakuua T, Omaki K, Zhu SN, Chujo R, Polym. J., 16, 717 (1984)
  •  
  • 21. Pena B, Delgado JA, Bello A, Perez E, Macromol. Chem. Rapid Commun., 12, 353 (1991)
  •  
  • 22. Wild FRWP, Wasiucionek M, Hutter G, Brintzinger HH, J. Org. Chem., 288, 63 (1985)
  •  
  • 23. Collins S, Kuntz BA, Taylor NJ, Ward DG, J. Org. Chem., 342, 21 (1988)
  •  
  • 24. Collins S, Kuntz BA, Hong Y, J. Org. Chem., 54, 4154 (1989)
  •  
  • 25. Grossman RB, Doyle RA, Buchwald SL, Organometallics, 10, 1501 (1991)
  •  
  • 26. Jordan RF, Diamond GMWO 9523979, 1995 (1995)
  •  
  • 27. Diamond GM, Rodewald S, Jordan RF, Organometallics, 14, 5 (1995)
  •  
  • 28. Diamond GM, Jordan RF, Petersen JL, J. Am. Chem. Soc., 118(34), 8024 (1996)
  •  
  • 29. Christopher JN, Jordan RF, Petersen L, Young VG, Organometallics, 16, 3044 (1997)
  •  
  • 30. Diamond GM, Jordan RF, Petersen JL, Organometallics, 15, 4030 (1996)
  •  
  • 31. Diamond GM, Jordan RF, Petersen JL, Organometallics, 15, 4045 (1996)
  •  
  • 32. Christopher JN, Diamond GM, Jordan RF, Petersen JL, Organometallics, 15, 4038 (1996)
  •  
  • 33. Kim I, Jordan RF, Macromolecules, 29(1), 489 (1996)
  •  
  • 34. Jordan RF, Diamond GM, Christopher JN, Kim I, Polym. Prepr., 37, 256 (1996)
  •  
  • 35. Kim I, Jordan RF, Polym. Bull., 39(3), 325 (1997)
  •  
  • 36. Kim I, J. Macromol. Sci.-Pure Appl. Chem., A34(2), 293 (1998)
  •  
  • 37. Kim I, Shin YS, Choi CS, Polym. Sci. Technol., 9(1), 24 (1998)
  •  
  • 38. Hwang GN, Kim I, J. Macromol. Sci.-Pure Appl. Chem., A35(12), 1987 (1998)
  •  
  • 39. Zhou JM, Kim I, J. Appl. Polym. Sci., 71, 2973 (1999)
  •  
  • 40. Ewen JA, Elder MJ, Makromol. Chem. Macromol. Symp., 66, 179 (1993)
  •  
  • 41. Chien JCW, Tsai WM, Makromol. Chem. Macromol. Symp., 66, 141 (1993)
  •  
  • 42. Chien JCW, Xu B, Makromol. Chem. Rapid Commun., 14, 109 (1993)
  •  
  • 43. Kim I, Jordan RFProceedings of 4th International Congress on Metallocene Polymers (Metallocenes Asia 97), Schotland Business Research, p. 253, 1997 (1997)
  •  
  • 44. Kim I, J. Appl. Polym. Sci., 71(6), 875 (1999)
  •  
  • 45. Kim IL, Zhou JM, J. Polym. Sci. A: Polym. Chem., 37(8), 1071 (1999)
  •  
  • 46. Kim I, J. Macromol. Sci.-Pure Appl. Chem., A35(2), 293 (1998)
  •  
  • 47. Koivumaki J, Fink G, Seppala JV, Macromolecules, 27(22), 6254 (1994)
  •  
  • 48. Herfert N, Montag P, Fink G, Macromol. Chem., 194, 3167 (1993)
  •  
  • 49. Plate NA, Shibaev UPComb-shaped Polymers and Liquid Crystals, Plenum Press, New York, 1987 (1987)
  •  
  • 50. Segre AL, Andruzzi F, Lupinacci D, Magagnini PL, Macromolecules, 14, 1845 (1981)
  •  
  • 51. Trafara G, Koch R, Blum K, Hummel D, Macromol. Chem., 177, 1089 (1976)
  •  
  • 52. Randall JCPolymer Characterization by ESR and NMR, ACS Symp. Ser. No. 142, A.E. Woodward and F.A. Bovey, Eds., American Chemical Society, Washington, 1980 (1980)
  •  
  • 53. Lindeman LP, Adams JQ, Anal. Chem., 43, 1245 (1971)
  •  
  • 54. Asakura T, Doi Y, Macromolecules, 16, 786 (1983)
  •  
  • 55. Suter UW, Flory PJ, Macromolecules, 8, 765 (1975)
  •  
  • 56. Rossi A, Odian G, Zhang JB, Macromolecules, 28(6), 1739 (1995)
  •  
  • 57. Silverstein RM, Bassler GC, Morrill TCSpectrometric Identification of Organic Compounds, 5th Ed., p. 215, Wiley, New York, 1991 (1991)
  •  
  • 58. Busico V, Cipullo R, Chadwick JC, Modder JF, Sudmeijer O, Macromolecules, 27(26), 7538 (1994)
  •  
  • 59. Stehling U, Diebold J, Kirsten R, Roll W, Brintzinger HH, Jungling S, Mulhaupt R, Langhauser F, Organometallics, 13, 964 (1994)
  •  
  • 60. Tsutsui T, Mizuno A, Kashiwa N, Polymer, 30, 428 (1989)
  •  
  • 61. Edwards HGM, Johnson AF, Lewis IR, J. Raman Spectrosc., 24, 435 (1993)
  •  
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This Article

  • 2000; 24(5): 646-655

    Published online Sep 25, 2000