Polymerization of liquid propylene with a fourth-generation Ziegler-Natta catalyst: Influence of temperature, hydrogen, monomer concentration, and prepolymerization method on powder morphology

Liquid propylene was polymerized in a 5-L autoclave batch reactor using a commercially available TiCl4/MgCl2/Al(ethyl)3/DCPDMS Ziegler-Natta catalyst, with a phthalate ester as internal electron donor. The powders from these polymerizations were characterized using laser diffraction particle size distribution (PSD) analysis, scanning electron microscopy (SEM), and bulk density measurements. These characteristics were analyzed as a function of the process conditions, including hydrogen and monomer concentration, polymerization temperature, and the prepolymerization method. It was shown that polymerization temperature influences the powder morphology to a large extent. At low temperatures, high-density particles were obtained, showing regular shaped particle surfaces and low porosities. With increasing temperature, the morphology gradually was transferred into a more open structure, with irregular surfaces and poor replication of the shape of the catalyst particle. When using a prepolymerization step at a relatively low temperature, the morphology obtained was determined by this prepolymerization step and was independent from conditions in main polymerization. The morphology obtained was the same as that observed after a full polymerization at temperature. Even when using a short polymerization at an increasing temperature, the morphology was strongly influenced by the initial conditions. The effect of variation in hydrogen concentration supported the conclusion that the initial polymerization rate determines the powder morphology. In the absence of hydrogen, high bulk densities, and regularly shaped particles were obtained, even at high temperatures. With increasing hydrogen concentration, the reaction rates increased rapidly, and with that changed the morphology.