Hydroxy-indane Imine Ligand Complexes Synthesis And Catalytic Activity For Olefin Polymerization

In this dissertation,a series of complexes with hydroxyindanone-imine ligands have been synthesized and characterized,which included early transition metal complexes based on titanium and late transition metal complexes based on nickel and copper.And catalytic behavior of these complexes as catalysts for polymerization of olefins and polar monomers was investigated.The full dissertation was summarized as follows:1.A series of new hydroxyindanone-imine ligands were synthesized by the condensation reaction of hydroxyindanone and corresponding aniline under acidic condition.2.A series of Ni(â…¡) complexes beating hydroxyindanone-imine ligands had been synthesized and characterized.The X-ray structure analyses clearly indicate that Ni(â…¡) complexes bearing ligand without substituted groups on aniline are octahedral and trimeric,while Ni(â…¡) complexes bearing ligand containing more bulkly N-2,6-diisopropylphenyl moiety are mononuclear with a square planar N₂O₂ coordination geometry.Activated with methylaluminoxane(MAO),these Ni(â…¡) complexes can promote the addition polymerization of norbornene(NB) with very high activities(up to 10⁷ gPNBmol^-1Nih^-1) to obtain the polynorbornene(PNB) with high molecular weights (10⁶ gmol^-1),low stereoregularity and high heat stability.The effects of catalyst structures, polymerization conditions such as Al/Ni molar ratio,reaction temperature,and the concentration of catalyst and monomer on norbornene polymerization behavior had been discussed in detail.3.Activated with MAO,these Ni(â…¡) complexes we firstly prepared can also polymerize methyl methacrylate(MMA) containing polar ester group,producing syndiotactic-rich poly(methyl methacrylate)(PMMA)(rr up to 80%) with relatively wide molecular weight distribution(M_w/M_n=4-7).And the influence of catalyst structures and polymerization conditions on catalytic activities of Ni(â…¡) complexes and the microstructure of PMMA had been discussed in detail.4.After activation with MAO,these Ni(â…¡) complexes are also capable of catalyzing the polymerization of styrene to obtain isotactic-rich polystyrene(PS)(mm up to 60%). The molecular weight distributions of polymer are around 2 which indicated the presence of single active site during the polymerization reaction.And the effects of catalyst structures and polymerization conditions on catalytic activities of Ni(â…¡) complexes and the microstructure of PS had been discussed in detail.According to the analysis of ¹³C NMR spectra of obtained polymer,the polymerization proceeds through a coordination mechanism,which was supported by the structure of dimmer of styrene obtained in the low Al/Ni ratio.5.A series of Cu(â…¡) complexes beating hydroxyindanone-imine ligands had been synthesized and characterized.X-ray structures reveal that Cu(â…¡) complexes adopt a square planar or distorted square planar N₂O₂ coordination geometry.The moderate catalytic activities(up to 10⁵ gPNBmol^-1Cuh^-1) for the addition polymerization of norbornene have been provided by them at the activation of MAO.The polymers with high molecular weights(10⁶ gmol^-1),low stereoregularity and high heat stability were obtained.At the similar reaction condition,the catalytic activities change in descending order R=Me＞H＞Cl.The effects of polymerization conditions such as Al/Cu molar ratio and reaction temperature on norbornene polymerization behavior had been discussed in detail.6.A trinuclear titanium complex beating hydroxyindanone-imine and cyclopentadienyl ligand had been synthesized and characterized.After activation with MAO, the complex can polymerize polymerization of ethylene with moderate catalytic activities (up to 10⁵ gPEmol^-1Tih^-1).The molecular weights of polyethylene(PE) ranged from 35×10⁴ gmol^-1 to 186×10⁴ gmol^-1,which suggests the production of high to ultrahigh molecular weight polyethylene.The effects of polymerization conditions such as Al/Ti molar ratio and reaction temperature on catalytic activities of complex and the molecular weights of PE had been discussed in detail.