MgCl<sub>2</sub>/2-Ethyl-1-hexanol/TiCl<sub>4</sub>-Triethylaluminum 촉매계 의한 올레핀 중합. 1. 프로필렌의 중합

도재구; 정영태; 이동호

Polymer(Korea), Vol.14, No.3, 240-249, June, 1990

MgCl₂/2-Ethyl-1-hexanol/TiCl₄-Triethylaluminum 촉매계 의한 올레핀 중합. 1. 프로필렌의 중합

Olefins Polymerization with MgCl₂/2-Ethyl-1-Hexanol/TiCl₄-Triethylaluminum Catalyst System.1. Polymerization of Propylene

도재구, 정영태, 이동호

초록

염화마그네슘을 2-Ethyl-1-hexanol(EHA)에 녹인 용액으로부터 제조한 사염화티탄 지지촉매로 프로필렌을 중합할 때에 촉매의 제조조건 및 중합조건 등이 촉매의 활성과 입체규칙성에 미치는 영향을 조사하였다. 이 촉매계에서는 사염화티탄에 염화마그네슘-EHA-헥산 용액을 조금씩 넣어 제조한 촉매계가 높은 활성을 나타내었으며 염화마그네슘과 EHA의 몰비는 6부근에서 최적조건이 존재하였다. 염화마그네슘용액과 사염화티탄의 반응온도가 증가함에따라 Lewis염기가 존재하지 않는 촉매계에서는 촉매의 활성은 감소하였으나 입체규칙성은 증가하였다. 하지만 Lewis염기가 존재하는 촉매계에서는 반응온도가 증가함에 따라 촉매의 활성과 입체규칙성이 모두 증가하였다. 그리고 제조된 촉매를 사염화티탄으로 다시 반응시킬 때에 반응횟수가 증가함에 따라 촉매의 활성과 입체규칙성이 증가하였다. 프로필렌 중합시 촉매성분의 농도비는 [Al]/[Ti]의 비가 40부근에서, 중합온도는 40℃에서 최대활성을 나타내었으며, 중합시간이 길어짐에 따라 촉매의 활성, 즉 중합속도는 감소하지만 입체규칙성은 거의 일정한 값을 유지하였다. 또한 Lewis염기를 첨가함에 따라 촉매의 활성은 감소하지만 입체규칙성은 증가하였으며 내부 Lewis염기로 DIBP를 사용한 촉매가 ER를 사용한 경우보다 높은 입체규칙성을 나타내었다.

The polymerization of propylene with MgCl₂/EHA/TiCl₄ system in hexane has been studied in which MgCl₂ was dissolved in EHA and treated with TiCl₄. In this catalyst system, the catalyst obtained by adding the MgCl₂-EHA-hexane solution to TiC1₄ showed the higher activity than that of reverse addition order and the optimum condition was existed at [EHA]/[MgCl₂] ratio of about 6. With increasing the reaction temperature of MgCl₂ solution with TiCl₄, the activity of catalyst was decreased and the isotactic index was increased for the catalyst system without Lewis base, while the activity of catalyst and the isotactic index were increased for the presence of Lewis base. This catalyst system showed the maximum activity at [Al]/[Ti] ratio of about 40 and at the polymerization temperature of 40℃. With the Polymerization rate decreased but the stereospecificity remained almost constant after a slight increase. The addition of Lewis base caused the decrement of activity but increment of stereospecificity and the DIBP as an internal donor showed the higher stereospecificity compared to EB with some external Lewis base.

[References]

Kashiwa N, Yoshitake J, "Transition Metal Catalyzed Polymerizations: Ziegler-Natta and Metathesis Polymerizations," R.P. Quirk. Ed., Cambridge University Press, New York, p. 240 (1988)
Tang S, "Catalytic Polymerization of Olefins," T. Keii and K. Soga eds., Kodansha, Tokyo, p. 165 (1986)
Hu Y, Chien JCW, J. Polym. Sci. A: Polym. Chem., 26, 2003 (1988)
Lee DH, Min KE, Ha KR, Jo WH, Polym.(Korea), 11(3), 278 (1987)
Lee DH, Min KE, Jo WH, Jeong YT, Polym.(Korea), 13(1), 68 (1989)
Ittel SD, Mulhaupt R, Klabunde U, J. Polym. Sci. A: Polym. Chem., 24, 3447 (1986)
Yano T, Ikai S, Shimizu M, J. Polym. Sci. A: Polym. Chem., 23, 1455 (1985)
Dumas C, Hsu CC, Rev. Macromol. Chem. Phys., C(3), 255 (1984)
Garoff T, Iiskola E, Sormunen P, "Transition Metals and Organometallics as Catalysts for Olefin Polymerization," W. Kaminsky and H. Sinn eds., Springer-Verlag, Berlin, p. 200 (1988)
Japanese Kokai 82,170,907 (1982)
Chem. Abs., 98, 126, 816n (1983)
Japanese Kokai 82,158,204 (1982)
Chem. Abs., 98, 107, 954q (1983)
Hogan JP, J. Polym. Sci. A: Polym. Chem., 8, 2637 (1970)
Korol FJ, Karapinka GL, J. Polym. Sci. A: Polym. Chem., 10, 2621 (1972)
Kakugo M, Miyatake T, Mizunuman K, Kawai Y, Macromolecules, 21, 2309 (1988)
Kashiwa N, Yoshitake J, "Catalytic Polymerization of Olefins," T. Keii and K. Soga, Eds., Kodansha, Tokyo, p. 43 (1986)
Tait PJT, "Transition Metal Catalyzed Polymerizations: Alkenes and Dienes, Part A," R.P. Quirk, H.L. Hsieh and P.J.T. Tait Eds., Harwood Academic Publishers, New York, p. 115 (1983)
Soga K, Shiono T, Doi Y, Makormol. Chem., 189, 1531 (1988)
Keii T, Suzuki E, Tamura M, Doi Y, "Transition Metal Catalyzed Polymerizations: Alkenes and Dienes, Part A," R.P. Quirk, H.L. Hsieh and P.J.T. Tait eds., Harwood Academic Publishers, New York, p. 97 (1983)

[Referenced By]

[1] Kashiwa N, Yoshitake J, "Transition Metal Catalyzed Polymerizations: Ziegler-Natta and Metathesis Polymerizations," R.P. Quirk. Ed., Cambridge University Press, New York, p. 240 (1988)

[2] Tang S, "Catalytic Polymerization of Olefins," T. Keii and K. Soga eds., Kodansha, Tokyo, p. 165 (1986)

[3] Hu Y, Chien JCW, J. Polym. Sci. A: Polym. Chem., 26, 2003 (1988)

[4] Lee DH, Min KE, Ha KR, Jo WH, Polym.(Korea), 11(3), 278 (1987)

[5] Lee DH, Min KE, Jo WH, Jeong YT, Polym.(Korea), 13(1), 68 (1989)

[6] Ittel SD, Mulhaupt R, Klabunde U, J. Polym. Sci. A: Polym. Chem., 24, 3447 (1986)

[7] Yano T, Ikai S, Shimizu M, J. Polym. Sci. A: Polym. Chem., 23, 1455 (1985)

[8] Dumas C, Hsu CC, Rev. Macromol. Chem. Phys., C(3), 255 (1984)

[9] Garoff T, Iiskola E, Sormunen P, "Transition Metals and Organometallics as Catalysts for Olefin Polymerization," W. Kaminsky and H. Sinn eds., Springer-Verlag, Berlin, p. 200 (1988)

[10] Japanese Kokai 82,170,907 (1982)

[11] Chem. Abs., 98, 126, 816n (1983)

[12] Japanese Kokai 82,158,204 (1982)

[13] Chem. Abs., 98, 107, 954q (1983)

[14] Hogan JP, J. Polym. Sci. A: Polym. Chem., 8, 2637 (1970)

[15] Korol FJ, Karapinka GL, J. Polym. Sci. A: Polym. Chem., 10, 2621 (1972)

[16] Kakugo M, Miyatake T, Mizunuman K, Kawai Y, Macromolecules, 21, 2309 (1988)

[17] Kashiwa N, Yoshitake J, "Catalytic Polymerization of Olefins," T. Keii and K. Soga, Eds., Kodansha, Tokyo, p. 43 (1986)

[18] Tait PJT, "Transition Metal Catalyzed Polymerizations: Alkenes and Dienes, Part A," R.P. Quirk, H.L. Hsieh and P.J.T. Tait Eds., Harwood Academic Publishers, New York, p. 115 (1983)

[19] Soga K, Shiono T, Doi Y, Makormol. Chem., 189, 1531 (1988)

[20] Keii T, Suzuki E, Tamura M, Doi Y, "Transition Metal Catalyzed Polymerizations: Alkenes and Dienes, Part A," R.P. Quirk, H.L. Hsieh and P.J.T. Tait eds., Harwood Academic Publishers, New York, p. 97 (1983)