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 |
| DOI | 10.1002/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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