Cocatalytic Activities of Methylaluminoxane Prepared by Direct Water Addition Method in Ethylene Polymerization over Cp<sub>2</sub>ZrCl<sub>2</sub>

Han TK; Seo TS; Choi HK; Woo SI

Korean Journal of Chemical Engineering, Vol.16, No.2, 156-160, March, 1999

Cocatalytic Activities of Methylaluminoxane Prepared by Direct Water Addition Method in Ethylene Polymerization over Cp₂ZrCl₂

Han TK, Seo TS, Choi HK, Woo SI

The characterization of ethylene polymerization behaviors catalyzed over Cp₂ZrCl₂/MAO homogeneous system using methylaluminoxanes prepared by the direct hydrolysis of AlMe₃ (Me=methyl) were reported. The MAO was prepared at the ratio of [H₂O]/[Al]=1 and 0.5 and at three different temperatures, i.e., -40, -60 and -80℃. The polymerization rate was not decreased with polymerization time when the MAO prepared at the ratio of [H₂O]/[AlMe₃]=1 at -60℃ was used as a cocatalyst regardless of the ratio of Al/Zr and the polymerization temperature. The polymerization rate drastically decreased with polymerization time above 60℃ in case of using MAO prepared at the ratio of [H₂O]/[AlMe₃]=1 at -80℃. However, in case of the MAO prepared at the ratio of [H₂O]/[AlMe₃]=0.5 at -80℃, the rate continuously increased with polymerization time at the polymerization temperature of 70℃ and 80℃. The amount of MAO needed to activate Cp₂ZrC1₂ was larger than that of MAO prepared at the ratio of [H₂O]/[Al]=1. The viscosity molecular weight of polyethylene (PE) cocatalyzed with MAO prepared at the ratio of [H₂O]/[Al]=0.5 was lower than that of polyethylene obtained with MAO prepared at the ratio of [H₂O]/[Al]=1.

Keywords:MAO;Cp₂ZrC1₂;Metallocene;PE;Polymerization

[References]

Cam D, Albizzati E, Cinquina P, Makromol. Chem., 191, 1641 (1990)
Cam D, Giannini U, Makromol. Chem., 193, 1049 (1992)
Brintzinger HH, Fischer D, Mulhaupt R, Rieger B, Waymouth RM, Angew. Chem.-Int. Edit., 34, 1143 (1995)
Chiang R, J. Polym. Sci., 35, 235 (1958)
Elliott JH, Horowitz KH, Hoodock T, J. Appl. Polym. Sci., 19, 2947 (1970)
Kaminsky W, "Polymerization and Copolymerization with a Highly Active, Soluble Ziegler-Natta Catalyst," Transition Metal Catalyzed Polymerizations Alkenes and Diens, Quirk, R.P. ed., Harwood Academic Publishers, New York, 225 (1983)
Kaminsky W, Bark A, Steiger R, J. Mol. Catal., 74, 109 (1992)
Kissinger JB, Hughes RE, J. Phys. Chem., 63, 2002 (1959)
Pasynkiewicz S, Polyhedron, 9, 429 (1990)
Resconi L, Bossi S, Abis L, Macromolecules, 23, 4489 (1990)
Shugar GJ, "Chemical Techniques Ready Reference Handbook," MaGraw-Hill, Inc., 435 (1990)
Sinn H, Bliemeister J, Clausnitzer D, Tikwe L, Winter H, Zarncke O, "Some New Results on Methyl-Aluminoxane," Transition Metals and Organometallics as Catalyst for Olefin Polymerizations, Kaminsky, W. and Sinn, H. ed., Springer-Verlag, Berlin, 257 (1988)

[Referenced By]

[1] Cam D, Albizzati E, Cinquina P, Makromol. Chem., 191, 1641 (1990)

[2] Cam D, Giannini U, Makromol. Chem., 193, 1049 (1992)

[3] Brintzinger HH, Fischer D, Mulhaupt R, Rieger B, Waymouth RM, Angew. Chem.-Int. Edit., 34, 1143 (1995)

[4] Chiang R, J. Polym. Sci., 35, 235 (1958)

[5] Elliott JH, Horowitz KH, Hoodock T, J. Appl. Polym. Sci., 19, 2947 (1970)

[6] Kaminsky W, "Polymerization and Copolymerization with a Highly Active, Soluble Ziegler-Natta Catalyst," Transition Metal Catalyzed Polymerizations Alkenes and Diens, Quirk, R.P. ed., Harwood Academic Publishers, New York, 225 (1983)

[7] Kaminsky W, Bark A, Steiger R, J. Mol. Catal., 74, 109 (1992)

[8] Kissinger JB, Hughes RE, J. Phys. Chem., 63, 2002 (1959)

[9] Pasynkiewicz S, Polyhedron, 9, 429 (1990)

[10] Resconi L, Bossi S, Abis L, Macromolecules, 23, 4489 (1990)

[11] Shugar GJ, "Chemical Techniques Ready Reference Handbook," MaGraw-Hill, Inc., 435 (1990)

[12] Sinn H, Bliemeister J, Clausnitzer D, Tikwe L, Winter H, Zarncke O, "Some New Results on Methyl-Aluminoxane," Transition Metals and Organometallics as Catalyst for Olefin Polymerizations, Kaminsky, W. and Sinn, H. ed., Springer-Verlag, Berlin, 257 (1988)