Study On The Catalytic Properties Of Heterocyclic Amine Complexes

α-Olefins are widely used in many areas as chemical intermediate for the production of lubricants, drilling fluids, plasticizers and other additives. Propylene carbonate is an excellent solvent with a high boiling point and low vapor pressure. In addition it also can be used as plasticizers for adhesives and sealants, phenolic resin curing accelerator and a water-soluble adhesive dispersing agent. This thesis reviews the current development and research of metal complexes and the progress of metal complexes in catalyzing the ethylene oligomerization(or polymerization) and the synthesis of propylene carbonate was also reviewed. Meanwhile the catalytic reaction mechanism of the metal complexes in catalyzing ethylene oligomerization/polymerization and the synthesis of cyclic carbonate with carbon dioxide was introduced.In this thesis, three kinds of ligands and eighteen metal complexes were synthesized, and the catalytic properties of the relevant metal complexes tested via the reaction of ethylene oligomerization and the synthesis of propylene carbonate with carbon dioxide. Meanwhile, mulliken charges and electron density with molecular energy of the involved ligands were calculated by Gaussian software at the level of RB3LYP/6-311+G, and the electrotic environment and the stability of the corresponding complexes investigated as well.Three kinds of bis(imino)pyridyl ligand(2,6-bis[1-(2,4-dimethylphenylimine)methyl] pyridine(L1), 2,6-bis [1-(4-methoxy-2-methylphenylimine)methyl]pyridine(L2), and 2-[1-(2,4-dimethylpheny imine)], 6-[1-(4-methoxy-2-methylphenylimine)methyl]pyridine(L3) were synthesized using a new synthetic method for the first time and three kinds of transition metal complexes 2-1, 2-2, 2-3 were synthesized exploring the ligand L2 with the corresponding metal chloride. Furthermore, the complexs were characterized by IR, UV-vis spectroscopy and TG-DSC. The catalytic properties of ethylene oligomerization were tested at 1 MPa, 50℃ and 1 h. The complexs showed high catalytic performance, reaching the highest catalytic activity of complexes 2-1, up to 2.2×108 g mol-1 h-1. For the first time the catalytic performance of the synthesis of propylene carbonate by carbon dioxide reactions was studied at the reaction conditions of 1.5 MPa and 100℃, the catalyst for long-term resistance up to 7 h, which exhibited high catalytic activity. Among these complexs, complex 2-1 shows the highest catalytic conversion of propylene carbonate by 90.84%.Through deprotonation of compound Hdpa, the corresponding post-transition metal complexes of cobalt and the rare earth metal erbium, neodymium and gadolinium metal complexes were synthesized. The complexes were characterized by infrared absorption, coordination was deduced through the comparision of ligand and complexes. The comlexes were found to have a very low ethylene oligomerization catalytic activity and high conversion rate of propylene carbonate, reaching 54.28 %.Using three kinds of heterocyclic amine compounds H2 dmpzda, H2 pdpzpz and H2 dpzda as ligands, nine corresponding metal complexes were synthesized. These complexes were characterized by infrared absorption and TG-DSC. Their catalytic performance were first studied, showing a very low ethylene oligomerization catalytic activity, complexes 4-1 has the highest conversion rate of propylene carbonate, reaching 88.68%.Two trimetal string complexes were synthesized with the ligand Hdpa, and the catalytic performance of them were first tested. The results show a very low catalytic activity in ethylene oligomerization, and a high activity in the synthesis of propylene carbonate. The highest conversion rate of propylene carbonate reaches 86.23%.