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A quantitative study was carried out on the homogeneous zirconocene dichloride/methylalumoxane/trimethylaluminum (Cp 2 ZrCl 2 /MAO/TMA) catalyst system in ethylene polymerization. The effects of variation of the Al MAO /Zr ratio, absolute Zr concentration, and addition of TMA on ethylene polymerization activity and polymer properties were investigated. The polymerization profiles for small Al MAO /Zr ratios and the changes with the Zr concentration are explained with a complexation equilibrium for the active homogeneous complex and with the change to a heterogeneous catalyst upon polymer precipitation. Good polymer productivities can be achieved at Al MAO /Zr < 1000 when working at Zr concentrations between 10 −4 and 10 −5 mol/l with addition of TMA (Al MAO /Al TMA ≈ 1.4).
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Rieger et al. (1994) studied this question.
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