芳氧亚胺锆络合物的合成及其催化乙烯聚合

以3-枯基-5-甲氧基水杨醛和2,6-二甲基环己胺为原料,经缩合反应合成了水杨醛亚胺配体(Ⅰ),利用四氯化锆-四氢呋喃络合物和配体反应制备了相应的芳氧基亚胺二氯化锆络合物(Ⅱ),用MS、~1HNMR和~(13)CNMR表征了配体及络合物的结构,并评价了络合物Ⅱ催化乙烯聚合的性能。在甲基铝氧烷(MAO)助催化下,Ⅱ成功地催化了乙烯聚合反应。在50℃、0.9MPa乙烯压力下,Ⅱ在甲苯中的催化活性为53.5kg聚乙烯(PE)/(mmol×Zr×h),所得聚合物为超高相对分子质量(简称分子量)聚乙烯,黏均分子量达3.3×10~6 g/mol。当以正己烷为溶剂时,聚乙烯黏均分子量提高至4.1×10~6 g/mol。

Synthesis of Bis(phenoxy-imine) Zirconium Complex and its Application in Ethylene Polymerization

Salicylaldehyde imine ligand (1) and bis(phenoxy-imine) zirconium dichloride complex (2) have been synthesized. Both ligand and complex were characterized by mass spectrum, 1H NMR and 13C NMR. In the presence of MAO as a cocatalyst, the complex 2 was capable to catalyze ethylene polymerization. 2 displayed ethylene polymerization activity of 53.5 kg of PE/mmol of Zr.h at 50 oC and 0.9 MPa pressure in toluene, resulting in ultra-high molecular weight polyethylene with a viscosity average molecular weight value of 3.3x106 g/mol. The introduction of n-hexane as reaction solvent could further increase the molecular weight of obtained polymer to 4.1x106 g/mol.