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The ethylene polymerization by Cp2ZrCl2/MAO (Cp = η5: cyclopentadienyl; MAO = methyl aluminoxane) and CpZrCl3/MAO have been studied. The MW and PD (= Mw/Mw) of polymers obtained after 2.5‐60 min are the same, which indicate short chain lifetime. The values of rate constants for Cp2ZrCl2 at 70°C are: kp = 168−1670 (M s)−1 and ktrA1 = 0.012‐0.81 s−1 depending upon [Zr] and [MAO,] ktrβ = 0.28 s−1, and ktrH = 0.2 M−1 torr−1/2 s−1. These chain transfer rate constant values are two to three orders of magnitude greater than the corresponding values found for MgCl2 supported titanium catalysts. One significant difference between the heterogeneous and homogeneous catalysts is that the former decays according to an apparent second order kinetics, whereas the latter decay is simple first order at 0°C and biphasic first order at higher temperatures. The productivity of the catalysts depends weekly on temperature while the MW decreases strongly with increase of temperature above 30°C. All the active species were formed upon mixing Cp2ZrCl2 with MAO while it took up to 20 min for the CpZnCl3/MAO system. The productivity of the former increase more strongly with the decrease of [Zr] than the latter. Otherwise, the two catalyst systems have all their kinetic parameters differing less than a factor of two.

Homopolymerization of ethylene and 1‐hexene and their copolymerizations were compared to investigate the influence of α‐olefin on the enhancement of ethylene polymerization rate (Rp), which is often referred to as the “comonomer” effect. With the two homogeneous Ziegler–Natta catalysts, Et[Ind]2ZrCl2/MAO and (π‐C5H5)2ZrCl2/MAO (MAO = methylaluminoxane), hexene causes reduction of Rp—in other words a negative “comonomer” effect. In the case of the high activity MgCl2 supported TiCl3 catalysts there is a slight positive “comonomer” effect; the Rp increases by 25 to 70% with the addition of 15 mol % of hexene. The “comonomer” effects in there catalyst systems are much smaller than that observed for the classical TiCl3 catalyst. © 1993 John Wiley & Sons, Inc.

Supported catalyst for fluidized bed polymerization processes has been prepared by reacting macroporous SiO2 first with MAO (methylaluminoxane) and then with Et [Ind]2ZrCl2. It contains 0.60 wt % of Zr and an [Al]/[Zr] ratio of 50. This catalyst produces homogeneous E/P (ethylene/propylene) copolymers with truly random copolymerization behaviors and required to achieve the same copolymerization activity for the Et[Ind]2ZrCl2/MAO would be required a total [Al]/[Zr] of only 670. Several time larger amount of MAO would be required to achieve the same copolymerization activity for the Et [Ind]2ZrCl2/MAO catalyst in solution. This random copolymerization is independent of catalyst concentration and composition. Activation of the supported catalyst with i‐butylaluminoxane, tri‐i‐butylaluminum, or trimethylaluminum resulted in lower activity and copolymers having high ethylene content and crystallinity.