Investigations on the Ethylene Polymerization with Bisarylimine Pyridine Iron (BIP) Catalysts

The kinetics and terminations of ethylene polymerization, mediated by five bisarylimine pyridine (BIP) iron dichloride precatalysts, and activated by large amounts of methyl aluminoxane (MAO) was studied. Narrow distributed paraffins from initially formed aluminum polymeryls and broader distributed 1-polyolefins and (bimodal) mixtures, thereof, were obtained after acidic workup. The main pathway of olefin formation is beta-hydrogen transfer to ethylene. The rate of polymerization in the initial phase is inversely proportional to the co-catalyst concentration for all pre-catalysts; a first-order dependence was found on ethylene and catalyst concentrations. The inhibition by aluminum alkyls is released to some extent in a second phase, which arises after the original methyl groups are transformed into n-alkyl entities and the aluminum polymeryls partly precipitate in the toluene medium. The catalysis is interpretable in a mechanism, wherein, the relative rate of chain shuttling, beta-hydrogen transfer and insertion of ethylene are determining the outcome. Beta-hydrogen transfer enables catalyst mobility, which leads to a (degenerate) chain growth of already precipitated aluminum alkyls. Stronger Lewis acidic centers of the single site catalysts, and those with smaller ligands, are more prone to yield 1-olefins and to undergo a faster reversible alkyl exchange between aluminum and iron.

Synthesis of Nickel(II) Complexes and its Application to Ethylene Oligomerization

A kind of N-((3-chloro-1H-indol-2-yl) methylene)-2,6-diisopropylbenzenamin Ni (II) complex has been synthesized. Ethylene oligomerizations were carried out by using those complexes in combination with methyl aluminoxane (MAO) and produced olefin. The effects of important parameters such as temperature and MAO concentration. on the catalytic activity and the distribution of resulting oligomer were investigated.

Boryl-substituted Zirconocene Dichloride Complexes as Catalyst Precursors for Homogeneous Ethylene Polymerization

The synthesis and characterization of 16 new boryl-substituted zirconocene dichloride complexes are reported. After activation with methyl aluminoxane (MAO) these complexes are catalysts for homogeneous ethylene polymerization. The combination of these complexes with nickel catalysts containing Lewis basic substituents produces polymers with bimodal molecular weight distributions.