Living Polymerization of 1,3-Butadiene Catalyzed by Half-titanocene Complex Bearing Dibenzhydryl-substituted Aryloxide Ligand  

作　　者：Bo Dong Rui Zhuang Chun-yu Zhang Wen-jie Zheng He-xin Zhang Yan-ming Hu 孙广平 张学全 

机构地区：[1]College of Materials Science and Engineering, Jilin University [2]Key Laboratory of Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

出　　处：《Chinese Journal of Polymer Science》2017年第6期721-727,共7页高分子科学（英文版）

基　　金：financially supported by the National Basic Research Program of China(No.2015CB654700);the National Natural Science Foundation of China(No.U1462124);the National Key Technology R&D Program(No.2014BAE14B00)

摘　　要：Half-titanocene complexes bearing dibenzhydryl-substituted aryloxide ligands （2a-2d） were prepared. Among them, 2e adopted a three-legged distorted tetrahedral geometry evidenced by X-ray crystallography. The poly-1,3-butadiene with high molecular weight and narrow molecular weight distribution was obtained by using these complexes as the catalysts activated with methylaluminoxane （MAO）. The catalytic activities of the complexes depended on their structures. The Ti-- O--C bond in the complexes with large angle afforded them with higher activity, while Cp＊-based complexes exhibited lower activities than the Cp-based analogues. The activity of complex increased with increasing the polymerization temperature while the selectivity remained no change, indicating the high thermal stability. Furthermore, the polymerization of 1,3-butadiene catalyzed by 2a/MAO at 0 ℃ has been found in a living fashion.Half-titanocene complexes bearing dibenzhydryl-substituted aryloxide ligands （2a-2d） were prepared. Among them, 2e adopted a three-legged distorted tetrahedral geometry evidenced by X-ray crystallography. The poly-1,3-butadiene with high molecular weight and narrow molecular weight distribution was obtained by using these complexes as the catalysts activated with methylaluminoxane （MAO）. The catalytic activities of the complexes depended on their structures. The Ti-- O--C bond in the complexes with large angle afforded them with higher activity, while Cp＊-based complexes exhibited lower activities than the Cp-based analogues. The activity of complex increased with increasing the polymerization temperature while the selectivity remained no change, indicating the high thermal stability. Furthermore, the polymerization of 1,3-butadiene catalyzed by 2a/MAO at 0 ℃ has been found in a living fashion.

关 键 词：Half-titanocene complexes 1 3-BUTADIENE Thermal stability Living polymerization 

分 类 号：O643.3[理学—物理化学] O631.5[理学—化学]