A discussion on the kinetic behavior of Ziegler-Natta ethylene polymerization at early moments of the reaction via modeling

The gas-phase ethylene polymerizations with SiO2-supported Ziegler-Natta (ZN) catalyst at early moments of reaction is modeled. The experimental data used in this work show that at initial stages of the polymerization there is a sharp reduction in the reaction rate and a sharp rise in molecular weight. In the modeling, multi-active sites assumption and diffusion limitations inside the particle are studied. Energy balance to calculate the temperature at early moment is applied. Kinetic model including initiation, propagation, chain transfers and active site deactivation steps are used to predict the reaction rate and molecular weights. Polymeric flow model (PFM) is applied for single particle model (SPM). The results show two distinct regions. First region with sharp gradient for reaction rate and molecular weights and then, shortly there is a smooth region in which the changes in rate and molecular weights are slow. To fit this sharp gradient followed by a nearly steady state behavior two types of active sites are necessary. A group of highly active sites which deactivated soon and the active sites with lower activity and relatively long-lasting.