Metallocene–methylaluminoxane catalyst for olefin polymerization. II. Bis-η5-(neomenthyl cyclopentadienyl)zirconium dichloride

Bis(neomenthyl cyclopentadienyl)zirconium dichloride/methyl aluminoxane (η⁵-(NMCp)₂ZrCl₂/MAO) catalyst has been investigated for ethylene polymerization. About 51% of the Zr forms active sites more or less instantaneously according to quenching with tritiated methanol. There is an initial drop of rate of polymerization, R_p, of about 30% which remains constant thereafter. The catalytic activity increases monotonically with temperature; it is proportional to [MAO]^1.75 at a constant [Zr] = 1.5 μM and proportional to [Zr]^?1.2 at a constant [MAO] = 64.5 mM. At very large [MAO]/[Zr], the catalyst has extremely high activity; κ_p = 5 × 10³ (Ms)^?1 at 50°C. There is also facile chain transfer to aluminum, κ = 0.14 s^?1 at 50°C. Both κ_p and κ are about 30 times greater than the corresponding rate constants for MgCl₂ supported TiCl₃ catalysts. The TiCl₃/MgCl₂ and (NMCp)₂/MAO catalysts have nearly the same activation energy for propagation (ca. 7 kcal/mol^?1). The higher activity of the latter is due to its larger preexponential factor in κ_p. The dependence of catalytic activity on the [MAO]/[Zr] ratio may be explained by rapid association-dissociation equilibria of MAO involving acid-base and/or electron deficient bridge complexation.