입체규칙성이 다른 Ziegler-Natta 촉매에 의한 올레핀의 삼원 공중합

이동호; 이동희; Soga K

Polymer(Korea), Vol.20, No.3, 427-430, May, 1996

Export Citation

입체규칙성이 다른 Ziegler-Natta 촉매에 의한 올레핀의 삼원 공중합

Olefins Terpolymerization with Ziegler-Natta Catalysts of Different Stereoregularity

이동호, 이동희, Soga K

초록

고입체규칙성 촉매와 비입체규칙성 촉매를 이용하여 프로필렌/1-헥센/1-헥사데센 삼원공중합을 행하였다. 고입체규칙성인 Solvay TiC1₃-Cp₂TiMe₂를 사용한 삼원공중합에서 1-헥센과 1-헥사데센의 단량체 공급비가 증가할 때 중합속도가 가속화되고 삼원공중합체 내의 1-헥~센 및 1-헥사데센의 함량이 증가하였다. 반면에 비입체규칙성 MgCl₂/TiCl₃-TEA 촉매계를 사용한 경우에는 공단량체가 첨가됨에 따라 촉매활성과 공~단량체의 함량이 감소하였다. 이러한 결과를 단량체 확산의 개념으로 설명하였다.

Terpolymerizations of propylene/1-hexene/1-hexadecene had been carried out with high-isospecific and nonisospecific catalysts. For high-isospecific Solvay TiCl₃-Cp₂TiMe₂ catalyst system, polymerization rate accelerated and incorporation of 1-hexone and 1-hexadecene in terpolymer increased when feed ratio of 1-hexone and/or1-hexadecene increased. In contrast, catalyst activity and comonomers content decreased with addition of comonomers for nonisospecific MgC1₂/TiCl₃-TEA catalyst system. These phenomena might be explained with the concept of monomer diffusion limitation.

Keywords:terpolymerization;Solvay TiCl₃-Cp₂TiMe₂;MgCl₂/TiCl₃ -TEA

[References]

Seppala JV, J. Appl. Polym. Sci., 31, 657 (1986)
Spitz R, Duranel L, Mason P, DarricadeaLlauro MF, Guyot A, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 719, Cambridge University Press, New York (1988)
Tait PJT, Downs GW, Akinbami AA, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 834, Cambridge University Press, New York (1988)
Fink G, Ojala TA, "Transition Metals and Organometallics as Catalysts for Olefin Polymerization," eds. by W. Kaminsky and H. Sinn, p. 169, Springer-Verlag, Berlin (1988)
Chien JCW, Nozaki T, J. Polym. Sci. A: Polym. Chem., 31, 227 (1993)
Nagel EJ, Kirillov VA, Ray WH, Ind. Eng. Chem. Prod. Res. Dev., 19, 372 (1980)
Soga K, Yanagihara H, Lee DH, Makromol. Chem., 190, 995 (1989)
Soga K, Ohgizawa M, Shiono T, Lee DH, Macromolecules, 24, 1699 (1991)
Soga K, Yanagihara H, Makromol. Chem. Rapid Commun., 9, 23 (1988)
Shiono T, Uchino H, Soga K, Polym. Bull., 21, 19 (1989)
Clauss K, Bestian H, Justus Liebigs Ann. Chem., 654, 8 (1962)
Kissin YV, "Isospecific Polymerization of Olefins with Heterogeneous Ziegler-Natta Catlaysts," p. 3, Springer Verlag, New York (1985)
Randall JC, Hsieh ET, "NMR and Macromolecules,", p. 131, American Chemical Society, Washington, D.C. (1984)

[Referenced By]

[1] Seppala JV, J. Appl. Polym. Sci., 31, 657 (1986)

[2] Spitz R, Duranel L, Mason P, DarricadeaLlauro MF, Guyot A, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 719, Cambridge University Press, New York (1988)

[3] Tait PJT, Downs GW, Akinbami AA, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 834, Cambridge University Press, New York (1988)

[4] Fink G, Ojala TA, "Transition Metals and Organometallics as Catalysts for Olefin Polymerization," eds. by W. Kaminsky and H. Sinn, p. 169, Springer-Verlag, Berlin (1988)

[5] Chien JCW, Nozaki T, J. Polym. Sci. A: Polym. Chem., 31, 227 (1993)

[6] Nagel EJ, Kirillov VA, Ray WH, Ind. Eng. Chem. Prod. Res. Dev., 19, 372 (1980)

[7] Soga K, Yanagihara H, Lee DH, Makromol. Chem., 190, 995 (1989)

[8] Soga K, Ohgizawa M, Shiono T, Lee DH, Macromolecules, 24, 1699 (1991)

[9] Soga K, Yanagihara H, Makromol. Chem. Rapid Commun., 9, 23 (1988)

[10] Shiono T, Uchino H, Soga K, Polym. Bull., 21, 19 (1989)

[11] Clauss K, Bestian H, Justus Liebigs Ann. Chem., 654, 8 (1962)

[12] Kissin YV, "Isospecific Polymerization of Olefins with Heterogeneous Ziegler-Natta Catlaysts," p. 3, Springer Verlag, New York (1985)

[13] Randall JC, Hsieh ET, "NMR and Macromolecules,", p. 131, American Chemical Society, Washington, D.C. (1984)