Synthesis, Characterization And Polyolefins Catalytic Performance Of Quinoline-8-olate Metal Complexes

This thesis focuses on designing and synthesis a series of half-titanocene complexesbearing5-t-butyl-2-(1-(arylimino)methyl)quinolin-8-olates as well as their correspondingvanadyl complexes, and apply it to the olefin polymerization. When activated with somealkyl aluminum reagent, all these complexes were investigated for the(co-)polymerization. From different substituent on the ligand, the influence of electroniceffect and space steric effect was studied on catalytic activities; From the usage of variouspolymerization reaction conditions such as co-catalyst, polymerization temperature,polymerization time, polymerization reaction pressure and so on to check the influence onthe catalysts performance and the properties of the obtained polymers, furthermore,studying from the related data and summarizing. This thesis mainly includes the follwingthree parts:The first part, the progress of polyethylene was summarized as well as thedevelopment of the catalyst. Some classical catalysts were introduced in detail. Thedevelopment advantages of some catalysts were suggested as well as the drawback.The second part, a series of new designed5-t-butyl-2-(1-(arylimino)methyl)-quinolin-8-ol ligands and their corresponding half-titanocene complexes were synthesizedand fully characterized by NMR analyses, elemental analyses, FTIR and single-crystalX-ray diffractions. When activated with MAO or MMAO, all the half-titanocenecomplexes exhibited good catalytic activity for ethylene polymerization. the obtainedpolyethylene showed ultrahigh molecular weight (up to1.18million) while the molecularweight distribution still keep narrow. In addition, the co-polymerization of ethylene with1-hexene or1-octene was efficient achieved.The third part, using the above ligands, a series of Di(5-t-butyl-2-((arylimino)methyl)quinolin-8-olate) vanadyl complexes was synthesized and fully characterized. Whenusing Et2AlCl as the c-ocatalyst and the ETA as the reactivate agent, this catalysts systemshowed high catalytic activities. Compared with the previous half-titanocene complexes,the activities of vanadyl complexes not only promote a lot, but also the good thermalstability. The resulting polymer also exist ultra high molecular weight and narrowmolecular weight distribution. The copolymerization of ethylene with norbornene or1-hexene also showed good activities and good insertions of co-monomer.