高针针,王梦雪,许胜,米普科,王斯晗,王力搏.茂金属催化剂催化1-癸烯齐聚研究[J].分子催化,2016,30(3):214-225
茂金属催化剂催化1-癸烯齐聚研究
The Study on the Oligomerization of 1-Decene with Metallocene Catalysts
投稿时间:2016-03-21  修订日期:2016-04-19
DOI:
中文关键词:  茂金属,1-癸烯 ,齐聚,结构性能关系, 性能与表征
英文关键词:Metallocene , 1-decene ,oligomerization, structure-property relations, properties and characterization
基金项目:国家自然科学基金
作者单位E-mail
高针针 华东理工大学 gaozhenzhen0301@163.com 
王梦雪 华东理工大学 wmx19910825@163.com 
许胜 华东理工大学 xusheng@ecust.edu.cn 
米普科* 华东理工大学 mpk869@163.com 
王斯晗 中国石油天然气股份有限公司 919939435@qq.com 
王力搏 石油化工研究院 495704080@qq.com 
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中文摘要:
      本文考察了1-癸烯和不同结构的茂金属催化剂((η5-C5H5)2ZrCl2,A;[μ,μ-(Me2Si)2(η5-C5H3)2][(η5-C5H5)ZrCl2)]2,B;[(C6H5)C(Me)2(η5-C5H4)]2ZrCl2,C; tBuNC(Me)2(η5-C5H4)ZrCl2,D;(η5-C5H4)C(C5H10)(η5-C13H8)ZrCl2,E;(η5-C5H4)C(Me)2(η5-C13H8)ZrCl2,F;(η5-C5H4)C(C6H5)2(η5-C13H8)ZrCl2,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, Cp2ZrCl2 ,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°C Kv:2-3cSt,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°C Kv:3-4cSt); 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°C Kv>20cSt),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°C, Al/Zr 比 300:1。 关键词:茂金属,1-癸烯,齐聚,结构性能关系,性能与表征
英文摘要:
      Abstract: In this article, the oligomerizations of 1-decene have been carried out with zirconocene catalysts ((η5-C5H5)2ZrCl2,A; [μ,μ-(Me2Si)2(η5-C5H3)2][(η5-C5H5)ZrCl2)]2,B; [(C6H5)C(Me)2(η5-C5H4)]2ZrCl2,C; tBuNC(Me)2(η5-C5H4)ZrCl2,D; (η5-C5H4)C(C5H10)(η5-C13H8)ZrCl2,E; (η5-C5H4)C(Me)2(η5-C13H8)ZrCl2, F; (η5-C5H4)C(C6H5)2(η5-C13H8)ZrCl2,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, Cp2ZrCl2, silicon bridged binuclear zirconocene complex B and sterically hindered complex C mainly produced low viscosity oligomers (100°C Kv:2-3cSt, 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 Cp2ZrCl2 (100°CKv about 3-4cSt); It was interested to find that Cs symmetrical zirconocene complexes E , F, G showed higher activity and primarily produced medium-high viscosity oligomers (100°C Kv>20cSt), 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 10μmol, a reaction temperature of 80°C, and an Al/Zr ratio of 300:1. Key words: Metallocene, 1-decene, oligomerization, structure-property relations, properties and characterization
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