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以价廉的水杨醛和Ti Cl4为主要原料,合成了四种水杨醛亚胺配体(5-8)及含(双苯氧基亚胺)配体的钛配合物[O-C6H4-ortho-CH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(13),[O-(5-NO2)-C6H3-ortho-CH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(14),[O-(3,5-di-Br)-C6H2-orthoCH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(15)和[O-(3,5-di-C(CH3)3)-C6H2-ortho-CH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(16)。用MS、1H-NMR和元素分析等手段表征了配体5-8分子结构,用1H-NMR和元素分析表征了配合物13-16的分子结构。经MAO(甲基铝氧烷)活化后,钛配合物(13-16)在甲苯溶剂中能有效催化乙烯聚合。在60℃,2.0 MPa及助催化剂与主催化剂摩尔比n(MAO)/n(cat)=1500∶1条件下钛配合物(14-16)催化乙烯聚合活性为1022.73-1302.27 g·PE/(mmol·Ti·h·MPa)),远高于无取代水杨醛亚胺钛配合物(13)。所得聚乙烯粘均分子量(粘度法)为19266-44754,GPC测定分子量分布Mw/Mn为1.88-2.12。具有最高活性的催化剂15催化乙烯聚合得到的聚合物样品,经13C-NMR和DSC的表征,结果表明为线型结晶聚乙烯。
The salicylaldimine ligands (5-8) and the titanium complexes containing (bisphenoxyimine) ligands [O-C6H4-ortho (I-Pr) 2-C6H3] 2TiCl2 (13), [O- (5-NO2) -C6H3-ortho-CH = N-2,6- (i-Pr) 2-C6H3] 2TiCl2 (14), [O- (3,5-di-Br) -C6H2-orthoCH = N-2,6- (i-Pr) - (3,5-di-C (CH3) 3) -C6H2-ortho-CH = N-2,6- (i-Pr) 2-C6H3] 2TiCl2 (16). The structure of ligand 5-8 was characterized by MS, 1H-NMR and elemental analysis. The molecular structure of complex 13-16 was characterized by 1H-NMR and elemental analysis. After MAO (methylaluminoxane) activation, the titanium complex (13-16) can effectively catalyze ethylene polymerization in toluene solvent. The ethylene polymerization activity of titanium complex (14-16) was 1022.73-1302.27 g · PE / (mol / L) at 60 ℃, 2.0 MPa and the molar ratio of cocatalyst to main catalyst of n (MAO) / n mmol · Ti · h · MPa), which is much higher than that of the non-substituted salicylaldiminato titanium complex (13). The obtained polyethylene had a viscosity average molecular weight (viscosity method) of 19266 to 44754 and a molecular weight distribution Mw / Mn of 1.88 to 2.12 as determined by GPC. The most active catalyst 15 catalyzed polymerization of ethylene polymer samples, characterized by 13C-NMR and DSC, the results showed that linear crystalline polyethylene.