Journal of Polymer Science Part A: Polymer Chemistry, Vol.35, No.10, 2063-2074, 1997
Kinetic-Study of Gas-Phase Olefin Polymerization with a Ticl4Mgcl2 Catalyst .1. Effect of Polymerization Conditions
This study focuses on the kinetics of ethylene/propylene (homo/co)polymerization reactions using a high activity TiCl4/MgCl2/AlEt3 catalyst. The reactor system is a gas phase reactor equipped with an on-line composition control scheme. As such, important kinetic data such as the instantaneous reaction rate of each monomer is readily obtained. In the investigation, experiments are performed to study the effects of comonomer composition variations, temperature variations, hydrogen concentration variations, and variations in the Al/Ti ratio. It is observed that the ethylene and propylene instantaneous reaction rates show a rather peculiar pattern with the appearance of a second peak. Our work linked the existence of this peak to the Al/Ti ratio used. A theory based on the oxidation state change is proposed. This theory is also used to explain the effects of temperature changes and hydrogen concentration changes on the system. A variety of analytical techniques are employed to study the polymer properties and evidence is provided to support the existence of polymer partial melting at relatively high reaction temperatures. The resulting diffusion limitation is believed to be partially responsible for the observed activity decrease at such elevated temperatures.