Synthesis, characterization and ethylene oligomerization of MIL-125(Ti)-NH2 grafted salicylaldehyde nickel complexes

Abstract

Metal-organic framework MIL-125(Ti)-NH2 was prepared and coordinated with salicylaldehyde and NiCl2·6H2O to create a heterogeneous catalyst for ethylene polymerization. The structure of the products was characterized by a variety of physical methods, such as Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma mass spectrometry (ICP-MS), and nitrogen adsorption-desorption. The catalytic performance of MIL-125(Ti)-NH2-Sal-Ni was also investigated. The results showed that the reaction temperature, Al/Ni molar ratio, and ethylene pressure influenced on the catalytic activity and product selectivity. Under optimal reaction conditions, the catalytic activity of MIL-125(Ti)-NH2-Sal-Ni for ethylene oligomerization could reach 5.90 × 104 g·(mol Ni·h)−1 using cyclohexane as the solvent and MAO as the co-catalyst; the main products were C4 and C6. In addition, MIL-125(Ti)-NH2-Sal-Ni had good catalytic stability and recycling, which could be reused at least twice without significant loss of activity. Moreover, based on the evaluation of catalytic performance, the catalytic ethylene oligomerization mechanism of MIL-125(Ti)-NH2-Sal-Ni was also deduced.