N-金刚烷基芳氧亚胺锆配合物的合成及其催化乙烯聚合  

Synthesis of N-adamantyl bis(phenoxy-imine) zirconium(Ⅳ)dichloride complexes and application for ethylene polymerization

作　　者：王原 郑浩 刘婷婷 叶晓峰 罗勇 WANG Yuan;ZHENG Hao;LIU Ting-ting;YE Xiao-feng;LUO Yong(Shanghai Research Institute of Chemical Industry Co.,Ltd.,State Key Laboratory of Polyolefins and Catalysis,Shanghai 200062,China)

机构地区：[1]上海化工研究院有限公司聚烯烃催化技术与高性能材料国家重点实验室,上海200062

出　　处：《应用化工》2018年第9期1939-1943,共5页Applied Chemical Industry

基　　金：上海市浦江人才计划(17PJ1432700)

摘　　要：以3-叔丁基-5-甲氧基水杨醛和金刚烷胺为原料,合成了两个水杨醛亚胺配体(1,2)及相应的锆络合物(3,4),并用MS、1H NMR和13C NMR等方法表征了配体及络合物。在甲基铝氧烷(MAO)助催化下,研究了络合物催化乙烯聚合性能。(3)在70℃时催化乙烯聚合活性为18. 1 kg PE/mmol·Zr·h,而(4)在30℃时催化乙烯聚合活性达到23. 8 kg PE/mmol·Zr·h,络合物催化所得聚乙烯的粘均分子量在3. 8×104%18. 9×104g/mol之间。红外谱图结果表明,聚合物以乙烯基封端,DSC测试表明聚乙烯的熔点分别为130℃和133℃,GPC测试聚乙烯的分子量分布为7. 6。Salicylaldehyde imine ligands(1,2)and corresponding bis(phenoxy-imine)zirconium complexes(3,4)have been synthesized by using 3-tert-butyl-5-methoxy salicylaldehyde and adamantyl amine as the starting material.Both ligands and complexes were characterized by mass spectrum,1H NMR and 13 C NMR spectroscopy.In the presence of MAO as a cocatalyst,the catalytic performances of ethylene polymerization catalyzed by complexes were studied.Complex(3)exhibited ethylene polymerization activity of 18.1 kg of PE/mmol of Zr·h at 70℃,while complex(4)displayed good activity of 23.8 kg of PE/mmol of Zr·h at 30℃,affording the polyethylene with a viscosity average molecular weight between 3.8×10 4~18.9×10 4 g/mol.The infrared spectra indicated that the polymer was terminated with vinyl group.DSC curves suggested that the melting point of polyethylene were 130℃and 133℃respectively.The GPC measurement showed that the molecular weight distribution of polyethylene was 7.6.

关 键 词：芳氧亚胺 金刚烷基 锆配合物 乙烯聚合 

分 类 号：TQ032.42[化学工程] TQ316.31