茂金属催化剂催化1-癸烯齐聚研究（英文）  

The Study on the Oligomerization of 1-Decene with Metallocene Catalysts

作　　者：高针针[1] 王梦雪[1] 许胜[1] 米普科[1] 王斯晗[2] 王力搏[2] 

机构地区：[1]华东理工大学材料科学与工程学院,上海市先进聚合物材料重点实验室,超细材料制备与应用教育部重点实验室,上海200237 [2]中国石油天然气股份有限公司石油化工研究院大庆化工研究中心,黑龙江大庆163714

出　　处：《分子催化》2016年第3期214-225,共12页Journal of Molecular Catalysis(China)

基　　金：supported by the National Natural Science Foundation of China(No.U1162111 and U1362111)

摘　　要：考察了1-癸烯和不同结构的茂金属催化剂((η~5-C_5H_5)_2ZrC l_2,A;[μ,μ-(Me_2Si)_2(η~5-C_5H_3)_2][(η~5-C_5H_5)ZrC l_52)]2,B;[(C_6H_5)C(Me)_2(η~5-C_5H_4)]_2ZrC l_2,C;t BuN C(Me)_2(η-C_5H_4)ZrC l_2,D;(η-C_5H_4)C(C_5H_(10))(η~5-C_513H_8)ZrC l_2,E;(η~5-C_5H_4)C(Me)_2(η-C_(13)H_8)ZrC l_2,F;(η_5-C_5H_4)C(C_6H_5)_2(η~5-C_(13)H_8)ZrC l_2,G)/MAO的齐聚反应,并探讨了茂金属F的用量,聚合温度和Al/Zr比对聚合反应和齐聚物性能的影响.实验结果表明,由于其不同的位阻效应和电子效应,不同结构的茂金属对1-癸烯的催化活性和齐聚物组分分布影响显著.其中,Cp_2ZrCl_2,双核硅桥联的茂金属B和大位阻的茂金属C主要合成低粘度的齐聚物(100℃Kv:2~3 cS t,二聚体含量约为60%);限制构型的茂金属D因为有更加开放的配位结构呈现出高的催化活性,齐聚物的粘度也略高(100℃Kv:3~4 cS t);Cs-对称型茂金属E,F,G都有较高的催化活性,合成的齐聚物粘度也较高(100℃Kv>20cS t),主要归因于茂金属的特殊结构和聚合机理.GC-MS结果表明茂金属催化1-癸烯合成的齐聚物异构化较少,主要由二聚体到五聚体的混合物组成.茂金属F催化1-癸烯较优的齐聚条件是催化剂用量10μmol,聚合温度80℃,Al/Zr比300∶1.The oligomerizations of 1-decene have been carried out with zirconocene catalysts（（ η~5-C_5H_5）_2ZrC l_2,A; [μ,μ-（ Me_2Si）52（ η~5-C_5H_3）_2][（ η~5-C_5H_5） ZrCl_2） ]2,B; [（ C_6H_5） C（ Me）_2（ η^-C_5H_4） ]_2ZrC l_2,C; t BuN C（ Me）_2（ η-C_5H_4）ZrC l_2,D;（ η~5-C_5H_4） C（ C_5H_（10））（ η~5-C_（13）H_8） ZrC l_2,E;（ η~5-C_5H_4） C（ Me）2（ η~5-C_（13）H_8） ZrC l_2,F;（ η~5-C_5H_4） C（ C_6H_5）_2（ η~5-C_（13）H_8） ZrC l_2,G） in combination with MAO and the effects of the dosage of complex F,reaction temperature and Al/Zr ratio on oligomerization and properties of oligomers were also investigated. It was found that the structure of ligands with different steric effects and electronic effects affected the catalytic behavior greatly,and determined the oligomer＇s component and microstructure. Among them,Cp_2 ZrCl_2,silicon bridged binuclear zirconocene complex B and sterically hindered complex C mainly produced low viscosity oligomers（ 100 ℃ Kv： 2 ~ 3 cS t,dimer content about 60%）; As expected,constrained geometry configuration zirconocene complex D with more open coordination space displayed higher catalytic activity and the kinetics viscosity of oligomer was higher than that of Cp_2 ZrC l_2（ 100 ℃ Kv about 3 ~ 4 cS t）; It was interested to find that Cs symmetrical zirconocene complexes E,F,G showed higher activity and primarily produced medium-high viscosity oligomers（ 100 ℃ Kv20 cS t）,which was attributed to the special structure of the zirconocene catalysts and different polymerization mechanism. The GC-MS results demonstrated that the oligomer mixture was less isomerization and composed of dimer to pentamer. The optimum reaction conditions involved a dosage of complex F 10 μmol,a reaction temperature of 80 ℃,and an Al / Zr ratio of 300 ∶ 1.

关 键 词：茂金属 1-癸烯 齐聚 结构性能关系 性能与表征 

分 类 号：O632.12[理学—高分子化学]