Mechanistic Study on Effect of Electron Donors in Propylene Polymerization Using the Ziegler-Natta Catalyst

被引：28

作者：

Guo, Xing ^{[1
]}

Cui, Liang ^{[2
]}

Wang, Yisen ^{[2
]}

Yi, Jianjun ^{[2
]}

Sun, Jingwen ^{[1
]}

Liu, Zhen ^{[1
]}

Liu, Boping ^{[3
]}

机构：

[1] East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China

[2] Petrochina Petrochem Res Inst, Polyolefin Res Dept, Beijing 102206, Peoples R China

[3] South China Agr Univ, Coll Mat & Energy, Guangzhou 510642, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2021年 / 125卷 / 16期

基金：

中国国家自然科学基金;

关键词：

EXTERNAL DONORS; PROPENE POLYMERIZATION; MGCL2-SUPPORTED CATALYSTS; FUNDAMENTAL-ASPECTS; INTERNAL DONORS; ETHYL BENZOATE; ACTIVE-SITES; ALKOXYSILANE; STEREOSELECTIVITY; POLYPROPYLENE;

D O I：

10.1021/acs.jpcc.0c11273

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

TiCl4/MgCl2 catalysts are still the main industrial catalyst for isotactic polypropylene at present. However, the mechanism of isotactic polymerization of propylene has not been fully understood. DFT calculations revealed that the bare Ti active site was regioselective and nonstereoselective in the absence of an electron donor. The role of electron donor ethyl benzoate (EB), diethyl-2,3-diisobutylsuccinate (DiBS), cyclohexylmethyldimethoxysilane (CMDMS), and dicyclopentyldimethoxysilane (DCPDMS) on the active site was investigated. The presence of EB, DiBS, CMDMS, or DCPDMS around the Ti active site can promote the activity and retain the regioselectivity. It is worth noting that in the presence of EB and DCPDMS, the stereoselective behavior can be promoted with the advantage of 1 kcal/mol. The copresence of AlEt2Cl species and external donors can increase both the stereoselectivity and regioselectivity.

引用

页码：8533 / 8542

页数：10

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