Comparative Study on Kinetics of Ethylene and Propylene Polymerizations with Supported Ziegler⁻Natta Catalyst: Catalyst Fragmentation Promoted by Polymer Crystalline Lamellae.

The kinetic behaviors of ethylene and propylene polymerizations with the same MgCl₂-supported Ziegler⁻Natta (Z⁻N) catalyst containing an internal electron donor were compared. Changes of polymerization activity and active center concentration ([C*]) with time in the first 10 min were determined. Activity of ethylene polymerization was only 25% of that of propylene, and the polymerization rate () quickly decayed with time () in the former system, in contrast to stable in the latter. The ethylene system showed a very low [C*]/[Ti] ratio (<0.6%), in contrast to a much higher [C*]/[Ti] ratio (1.5%⁻4.9%) in propylene polymerization. The two systems showed noticeably different morphologies of the nascent polymer/catalyst particles, with the PP/catalyst particles being more compact and homogeneous than the PE/catalyst particles. The different kinetic behaviors of the two systems were explained by faster and more sufficient catalyst fragmentation in propylene polymerization than the ethylene system. The smaller lamellar thickness (<20 nm) in nascent polypropylene compared with the size of nanopores (15⁻25 nm) in the catalyst was considered the key factor for efficient catalyst fragmentation in propylene polymerization, as the PP lamellae may grow inside the nanopores and break up the catalyst particles.