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 donor molecules, making it difficult to identify specific binding motives. The surface sites with large ³⁵Cl NMR line widths can be observed using high radio frequency field strengths. For the 2,2-dimethyl-1,3-dimethoxypropane donor, we observe additional surface sites with intermediately high quadrupolar couplings, suggesting a different surface structure for this particular adduct compared to the other systems. For ²⁵Mg, pronounced effects of donor binding on the quadrupole interaction parameters are observed, both computationally and experimentally. Again the adduct with the 2,2-dimethyl-1,3-dimethoxypropane donor shows a different behavior of the surface sites compared to the other adducts, which display more asymmetric coordinations of the surface Mg sites. Identifying specific binding motives by comparing ²⁵Mg NMR results to DFT calculations also proves to be difficult, however. This is attributed to the existence of many defect structures caused by the ball-milling process. The existence of such defect structures both at the surface and in the interior of the MgCl₂ particles is corroborated by NMR relaxation studies. Finally, we performed heteronuclear correlation experiments, which reveal interactions between the support and Mg-OH surface groups, but do not provide indications for donor-surface interactions.