铬系催化乙烯配位聚合/齐聚分子模拟研究进展  

Recent Progress on Molecular Modeling of Ethylene Polymerization/Oligomerization Catalyzed by Chromium-Based Catalysts

作　　者：刘振[1] 程瑞华[1] 何雪莲[1] 田洲[1] 刘柏平[1] 

机构地区：[1]华东理工大学化学工程联合国家重点实验室,上海200237

出　　处：《化学反应工程与工艺》2014年第3期218-228,共11页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金项目(21004020;21104019;21174037;21274040;51003027;21304033);国家863项目子课题(2012AA040306);中央高校基本科研业务费专项资金;111引智计划项目(B08021);博士后基金项目(2013M541482)

摘　　要：针对工业中广泛应用的Phillips铬系乙烯聚合催化剂和铬系乙烯选择性齐聚催化体系,从分子模拟角度对近期相关研究进展进行综述。主要介绍了分子模拟在Phillips铬系催化剂诱导期内乙烯聚合活性中心向乙烯易位活性中心转换机理、Ti改性Phillips铬系催化剂的乙烯聚合行为、Cr(III)2-EH/PIBAO/DME体系乙烯聚合和三聚转换机理以及Cr-SNS体系去质子化对乙烯三聚活性的影响等方面的研究进展。通过计算机分子模拟和实验手段相结合,可以获得对催化反应机理更为深刻的认识,从而为新型催化剂的设计与开发提供理论指导。Phillips chromium-based catalysts are widely used in industrial production of polyethylene andα-olefins through ethylene selective oligomerization. Recently, molecular modeling has been playing more and more important role in understanding the mechanism of ethylene polymerization and selective trimerization. From this point of view, the active site transformation from polymerization to metathesis during the induction period of the Phillips catalyst, the effect of Ti-modification on the Phillips catalyst, the transformation from ethylene polymerization to selective trimerization of the Cr（III） 2-EH/PIBAO/DME system, and the effect of deprotonation and Cr oxidation states in the Cr-SNS system on the ethylene selective trimerization were reviewed. A much profound mechanistic understanding has been achieved through combination of molecular modeling with experiments.

关 键 词：铬系催化剂 乙烯聚合 乙烯选择性齐聚 分子模拟 密度泛函理论 

分 类 号：O643.38[理学—物理化学] O6-39[理学—化学]