Silica-magnesium-titanium Ziegler–Natta catalysts. Part II. Properties of the active sites and fragmentation behaviour

• Published in: Journal of catalysis 2023-07, Vol.423, p.10-18
• Main Authors: Zarupski, Jelena, Piovano, Alessandro, Werny, Maximilian J., Martini, Andrea, Braglia, Luca, Torelli, Piero, Hendriksen, Coen, Friederichs, Nicolaas H., Meirer, Florian, Weckhuysen, Bert M., Groppo, Elena
• Format: Article
• Language: English
• Subjects: Olefin polymerization kinetics; Particle fragmentation; Spectroscopic methods; Ti-alkyl; Ziegler–Natta catalysts
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2023.04.015

[Display omitted] •a multi-scale, multi-technique approach, is used to investigate the electronic properties and the accessibility of the Ti active sites in a highly active silica-supported Ziegler–Natta catalyst.•several titanium phases co-exist, whose relative amount depends on the concentration of the alkyl aluminum activator.•Two families of alkylated Ti(III) sites are detected by IR spectroscopy of adsorbed CO.•Two types of Ti-acyl species are formed upon CO insertion into the Ti-alkyl bond, characterized by a different extent of η2-coordination.•TiCl3 clusters are preferentially formed at the exterior of the catalyst particles, while only monomeric Ti(III) sites are formed at the interior of the catalyst particles. In this work, which follows Part I that is dedicated to the precatalyst, we investigate the electronic properties and the accessibility of the Ti active sites in a highly active silica-supported Ziegler–Natta catalyst for industrial polyethylene production, applying a multi-scale, multi-technique approach. Complementary electronic spectroscopies (i.e. Ti K-edge XANES, Ti L2,3-edge NEXAFS and DR UV–Vis-NIR) reveal the coexistence of several titanium phases, whose relative amount depends on the concentration of the alkyl aluminum activator. In addition to β-TiCl3-like clusters and monomeric Ti(IV) sites, which are already present in the precatalyst, isolated Ti(III) sites and α-TiCl3-like clusters are formed in the presence of the activator. Two families of alkylated Ti(III) sites characterized by a different electron density are detected by IR spectroscopy of adsorbed CO, and two types of Ti-acyl species are formed upon CO insertion into the Ti-alkyl bond, characterized by a different extent of η2-coordination. The whole set of data suggests that TiCl3 clusters are preferentially formed at the exterior of the catalyst particles, likely as a consequence of Ti(III) mobility in the presence of strong Lewis acids, in most cases hampering the spectroscopic detection of isolated Ti(III) sites. In contrast, only monomeric Ti(III) sites are formed at the interior of the catalyst particles, characterized by a high electron density evocative of the presence of electron donors in the close proximity (e.g. aluminum alkoxide by-products). These sites are less accessible because of diffusion limitations, and only become visible by surface-sensitive spectroscopic methods (such as Ti L2,3-edge TEY-NEXAFS) upon the fragmentation of the catalyst particles.