BACKGROUND: Kinetic and morphological aspects of slurry propylene polymerization using a MgCl2‐supported Ziegler–Natta catalyst synthesized from a Mg(OEt)2 precursor are investigated in comparison with a ball‐milled Ziegler–Natta catalyst. RESULTS: The two types of catalyst show completely different polymerization profiles: mild activation and long‐standing activity with good replication of the catalyst particles for the Mg(OEt)2‐based catalyst, and rapid activation and deactivation with severe fragmentation of the catalyst particles for the ball‐milled catalyst. The observed differences are discussed in relation to spatial distribution of TiCl4 on the outermost part and inside of the catalyst particles. CONCLUSION: The Mg(OEt)2‐based Ziegler–Natta catalyst is believed to show highly stable polymerization activity and good replication because of the uniform titanium distribution all over the catalyst particles. Copyright © 2008 Society of Chemical Industry

Summary: Effects of external donor induced direct contact without alkylaluminum were studied for Ziegler-Natta catalysts containing monoester and diester as internal donors on the catalytic performances such as activity and stereoselectivity. Traditional slurry polymerizations were carried out for rather short period after direct contact for a variety of time. GC analysis was also performed to observe replacement phenomena of donors during direct contact. It was postulated that the different performances of the catalysts were greatly affected by the pair of internal and external donors.

Though preparation procedures of heterogeneous Ziegler‐Natta catalysts for propylene polymerization are sophisticated, it is uncertain whether the nature of the active sites is similar or different for different preparation procedures. In this study, the effects of preparation procedures on the nature of the active sites were investigated by stopped‐flow polymerization in combination with microstructure analysis of polymers. Both basic and advanced types of catalysts showed the same two kinds of isospecific active site, which indicated little influence of the preparation method on the active site structure. On the contrary, the ratios of the two kinds of isospecific sites were not the same, resulting in variation of average polymer properties.