中国科学院机构知识库网格
Chinese Academy of Sciences Institutional Repositories Grid
Differences between insertions of ethylene into metallocene and non-metallocene ethylene polymerization catalysts

文献类型:期刊论文

作者Zhang, Cheng-Gen1; Zhang, Liaoyun3; Li, Huayi2; Yu, Shu-Yuan1; Wang, Zhi-Xiang3
刊名JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
出版日期2013
卷号26期号:1页码:70-76
关键词Density Functional Theory Ethylene Polymerization Insertion Mechanism Octahedral Group 4 Polymerization Catalysts
ISSN号0894-3230
DOI10.1002/poc.3069
英文摘要Density functional theory (DFT) calculations at ?B97XD/SDD level have been conducted to study the differences between the insertions of ethylene into the non-metallocene octahedral group 4 catalysts and those into metallocene group 4 catalysts. The study shows that both can be described by the Cossess mechanim, but are different energetically. The latter have energy profiles involving stable p complexes between ethylene and catalysts prior to insertion and the insertion transition states (TSs) being lower than reactants, whereas the p complexes involved in the former are significantly less stable than their counterparts in the latter, and the insertion TSs are higher than or close to the reactants. The energy decomposition analyses on the activation energies indicate that the octahedral catalysts exert more significant steric effects than the metallocene catalysts, which are responsible for the differences. The cis arrangements of two chloride atoms in the precursors of metallocene catalysts were considered to be crucial for their catalytic activity, but the precursors of octahedral catalysts with either cis or trans arrangements of two chloride atoms exhibit activity. Nevertheless, the effective catalysts generated from octahedral precursors with cis chloride atoms have lower activation barriers than those from precursors with trans chloride atoms. Copyright (C) 2012 John Wiley & Sons, Ltd.
语种英语
WOS记录号WOS:000313614500013
出版者WILEY-BLACKWELL
源URL[http://ir.iccas.ac.cn/handle/121111/46373]  
专题中国科学院化学研究所
通讯作者Wang, Zhi-Xiang
作者单位1.Langfang Normal Coll, Dept Chem & Mat Sci, Langfang 065000, Peoples R China
2.Chinese Acad Sci, Joint Lab Polymer Sci & Mat, Key Lab Engn Plast, Inst Chem, Beijing 100190, Peoples R China
3.Univ Chinese Acad Sci, Coll Chem & Chem Engn, Beijing 100049, Peoples R China
推荐引用方式
GB/T 7714
Zhang, Cheng-Gen,Zhang, Liaoyun,Li, Huayi,et al. Differences between insertions of ethylene into metallocene and non-metallocene ethylene polymerization catalysts[J]. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY,2013,26(1):70-76.
APA Zhang, Cheng-Gen,Zhang, Liaoyun,Li, Huayi,Yu, Shu-Yuan,&Wang, Zhi-Xiang.(2013).Differences between insertions of ethylene into metallocene and non-metallocene ethylene polymerization catalysts.JOURNAL OF PHYSICAL ORGANIC CHEMISTRY,26(1),70-76.
MLA Zhang, Cheng-Gen,et al."Differences between insertions of ethylene into metallocene and non-metallocene ethylene polymerization catalysts".JOURNAL OF PHYSICAL ORGANIC CHEMISTRY 26.1(2013):70-76.

入库方式: OAI收割

来源:化学研究所

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