Probing Interactions between Electron Donors and the Support in MgCl2-Supported Ziegler-Natta Catalysts

Olefin polymerization using Ziegler–Natta catalysts (ZNCs) is an important industrial process. Despite this, fundamental insight into the inner working mechanisms of these catalysts remains scarce. Here, we focus on the low-γ nuclei 25Mg and 35Cl for an in-depth solid-state NMR and density functional theory (DFT) study of the catalyst’s MgCl2 support in binary adducts prepared by ball-milling. Besides the bare MgCl2 support and a MgCl2–TiCl4 adduct, samples containing donors that are part of the families of 2,2-dialkyl-1,3-dimethoxypropanes and phthalates used in fourth- and fifth-generation ZNCs are studied. DFT calculations indicate that the quadrupolar coupling parameters of the chlorines differ significantly between bulk and surface sites. As a result, the NMR visibility of the chlorine sites correlates with the particle size except for the adduct with 2,2-dimethyl-1,3-dimethoxypropane donor. The DFT calculations furthermore show that the surface sites are fairly insensitive to binding of different do...