Coadsorption Model for First-Principle Description of Roles of Donors in Heterogeneous Ziegler-Natta Propylene Polymerization

• Taniike, Toshiaki

• Terano, Minoru

Abstract

Systematic periodic density functional calculations were conducted to clarify the mechanism for donors to exert steric and electronics influences on propylene polymerization using heterogeneous Ziegler–Natta catalysts. It was concluded that TiCl_4 preferentially adsorbs as mononuclear species on the MgCl_2 (1 1 0) surface, and the coadsorption of donors with it is energetically viable. The coadsorption of donors on the (1 1 0) surface reinforces the electron density of the Ti mononuclear species, and sterically transfers the underlying C_2 symmetry to convert the originally aspecific mononuclear species into isospecific one. The nearest coadsorption of ethylbenzoate (EB) not only sterically induces the isospecificity of the Ti mononuclear species but also electrostatically improves the regiospecificity in propylene insertion. In addition, EB prevents sterically-demanding chain transfer to propylene, increasing the molecular weight of the produced polypropylene. Thus theoretically derived “coadsorption model” is highly consistent with a variety of experimentally known facts and believed to be useful for the ab initio prediction of new donor structures.

identifier:https://dspace.jaist.ac.jp/dspace/handle/10119/11452

Journal

• Journal of Catalysis

  Journal of Catalysis 293 39-50, 2012-07-04

  Elsevier

Keywords

• Ziegler–Natta propylene polymerization
• Density functional theory
• Donor
• Mechanism
• Coadsorption
• Active site

Details

• CRID: 1050845762468527104
• NII Article ID: 120005316221
• ISSN: 00219517
• Web Site: http://hdl.handle.net/10119/11452
• Text Lang: en
• Article Type: journal article
• Data Source:
  • IRDB
  • CiNii Articles
  • KAKEN