水杨醛缩亚胺合钛的合成、表征及乙烯聚合  

Titanium Catalyst Based on Phenoxyimine Ligands:Synthesis,Characterization and Ethylene Polymerization

作　　者：韩书亮 金钊 方园园[1] 王路生[1] 宋文波[1] HAN Shuliang;JIN Zhao;FANG Yuanyuan;WANG Lusheng;SONG Wenbo(Sinopec Bejing Research Institute of Chemical Industry,Beijing 100013,China)

机构地区：[1]中国石油化工股份有限公司北京化工研究院,北京100013

出　　处：《塑料》2022年第3期98-103,114,共7页Plastics

摘　　要：采用多步偶联的方法合成了一种新型含有酯基的水杨醛缩亚胺配体及相应的非茂钛金属配合物,通过核磁共振谱、碳谱、质谱及元素分析对配体及其配合物进行详细的结构表征分析,保证新型催化剂结构的正确性。通过X射线衍射仪测定的晶体结构更明确地阐述了该配合物的立体构型以及活性中心周围位阻效应,结果表明,配合物中酯基位于钛金属中心的正上方,羰基氧原子朝向钛活性中心,其与2个可形成配位点的氯原子的距离分别为5.01?和5.49A。采用该配合物与甲基铝氧烷组成催化体系能有效催化乙烯均聚合和乙烯-1-己烯共聚合。当乙烯均聚时,聚合活性最高可达到1.43×10^(6) g/(mol·h),聚乙烯重均分子量可达到5.68×10^(5) g/mol,相对分子质量分布可在2.00以上,与未含有酯基的结构类似催化剂相比,重均分子量更高,相对分子质量分布更宽。当乙烯共聚时,聚合物中1-己烯摩尔比例可达到2.5%。A new phenoxyimine ligand containing ester group and its corresponding non metallocene titanium complex were synthesized by multi-step coupling method.The structures of the ligand and its complex were characterized by~1H NMR,^(13)C NMR,MS and elemental analysis to ensure the correctness of the structure of the new catalyst.The three-dimensional configuration of the complex and the steric effect around the active center were more clearly expounder by the crystal structure determined by X-ray diffractometer.The results showed that the ester group in the complex was directly above the titanium metal center,and the carbonyl oxygen atom was toward the titanium active center.The distances between the carbonyl oxygen atom and the two chlorine atoms which could form the coordination site were 5.01?and 5.49A,respectively.The homopolymerization of ethylene and copolymerization of ethylene-1-hexene were effectively carried out by the catalytic system composed of the complex and methylaluminoxane.When ethylene was polymerized,the highest activity was 1.43×10^(6) g/(mol·h),the weight average molecular weight could reach 5.68×10^(5) g/mol,and the distribution could be more than 2.00.Compared with the structurally similar catalyst without ester group,the weight average molecular weight was higher and the distribution was wider.As for the ethylene copolymerization,the molar ratio of 1-hexene in the polymer could reach 2.5%.

关 键 词：非茂金属配合物 水杨醛缩亚胺 乙烯聚合 协同作用 乙烯共聚物 

分 类 号：TQ426.61[化学工程] TQ325.1