Studies on Ziegler‐Natta catalysts. Part IV. Chemical nature of the active site

Abstract

AbstractThe determination of the number of sites active in the polymerization of ethylene on the surface of α‐TiCl3–Al(CH3)3 dry catalysts leads to the conclusion that this number is small in comparison to the total surface of the catalyst. Qualitatively this conclusion is also reached by two other independent methods. Infrared spectra of the catalyst before and after polymerization do not show a change in the type of bonds present in the surface. Electron microscopy proves that no active sites are formed on the basal plane of the α‐TiCl3 which constitutes 95% of the total surface. The results strongly favor the lateral faces of α‐TiCl3 as the preferred location of active centers. The lateral faces contain chlorine vacancies and incompletely coordinated titanium atoms. This must then be the essential conditions for the formation of active centers. The propagation of the polymer chain has been repeatedly shown to follow an insertion mechanism. The active site, therefore, necessarily contains a metal–carbon bond. The study of catalysts derived from TiCl3CH3 leads to the conclusion that a TiC bond on titanium of incomplete coordination is the active species in these cases. The alkylation of surface titanium atoms was proven to be an intermediate step in the catalyst formation from TiCl3 and AlR3. Survival of titanium–alkyl bonds on the lateral faces, where titanium atoms are incompletely coordinated explains best, in the light of our data, the activity of Ziegler‐Natta catalysts. Coordination of aluminum alkyl compounds in or around the active center probably complicates the structure of the active centers.