Synthesis Of The Late Trasition Metal Complexes Based On5,6,7-trihydroquionolin And Their Application In Ethlene Reaction

The catalyst of polyolefin has developed for nearly a century, andformed three catalytic system included Ziegler-Natta catalyst,metallocene catalyst and transition metal catalyst etc. The late transitionmetal catalyst system was developed in the mid of1990’s, due to thecharacteristics of low-cost, good catalytic performance and loweroxophilicity.etc, attracted people’s great interest.In this thesis,2-chloro-5,6,7,8-tetrahydroquinolin-8-ol was used asthe raw material, the hydroxyl of which was protected by TMS. Then2-alkyl-6,7-dihydro-5H-quinolin-8-one was synthesized after Kumadacoupling, deprotection and Anelli oxidation. And then one-pot process,involving2-alkyl-6,7-dihydro-5H-quinolin-8-one and the correspondinganilines together with NiCl₂·6H₂O in acetic acid, was undertaken tosynthesize a series of novel N, N bidentate （2-alkyl-6,7-dihydro-5H-quinolin-8-ylidene）arylamine nickel complexes. At last, we studied theirperformance in ethylene oligomerization scientifically, and investigatedthe influence of reaction conditions, such as the reaction temperature, the molar ratio of Al/Ni etc, and ligand environment. All the nickelcomplexes showed good catalytic activity (up to1.1×10⁶g mol^-1h^-1) andthe selectivity for a-olefins.Following closely, we selected PMB to protect the hydroxyl of2-chloro-5,6,7,8-tetrahydroquinolin-8-ol, then by Stille coupling,hydrolyzing, and oxidation by DDQ/TBN/O2system,2-acetyl-6,7-dihydro-5H-quinolin-8-one was synthetized, then reactedwith the anilines, corresponding diimine ligands were got. At lastcorresponding N, N, N trident2,8-bisimino-6,7-dihydro-5H-quinolin ironcomplexes were formed by reacting ligands with FeCl₂·4H₂O. Theircatalytic behaviors towards ethylene polymerization were researched, andthe influence of the catalytic activity and polymer molecular weight byreaction parameters, including Al/Ni molar ratio and reaction temperature,and ligand environment were investigated. All the iron complexesshowed very high catalytic activity (up to24.04×10⁶g mol^-1h^-1).