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Experimental and Computational Approaches on the Isospecific Role of Monoester‐Type Internal Electron Donor for TiCl 4 /MgCl 2 Ziegler‐Natta Catalysts
Author(s) -
Liu Boping,
Cheng Ruihua,
Liu Zhen,
Qiu Pengyuan,
Zhang Shiliang,
Taniike Toshiaki,
Terano Minoru,
Tashino Kunihiko,
Fujita Takashi
Publication year - 2008
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.200751429
Subject(s) - catalysis , natta , polymerization , chemistry , density functional theory , ziegler–natta catalyst , crystallography , dipole , computational chemistry , polymer chemistry , organic chemistry , polymer
In this work, a combination of experimental and computational approaches on the isospecific role of monoester‐type internal electron donors (ED) such as phenylpropionate (PhP), ethylheptanoate (EH), methylbenzoate (MB), ethylbenzoate (EB) for TiCl 4 /ED/MgCl 2 Ziegler‐Natta catalysts had been performed. The propylene polymerization results revealed that the isospecificity of catalysts increases in the following order: PhP < EH < MB < EB. The subsequent molecular modeling on the electronic properties of the donors and two kinds of cluster model catalysts: TiCl 4 /ED/MgCl 2 and TiCl 4 /ED/(MgCl 2 ) 4 based on density functional theory (DFT) method was carried out. Two kinds of ED coordination on MgCl 2 clusters through either O or O within the monoester‐type ED had been disclosed. A perfect correlation between the dipole moment of ED, the coordination bond length of O … Mg, the competitive coordination from O with Mg ion and the isospecificity of the catalysts had been established.