The formations of defective MgC12 surfaces, and subsequent adsorption of Ti species and electron donor, as well as propylene polymerization over the Ziegler-Natta catalyst have been investigated using density function...The formations of defective MgC12 surfaces, and subsequent adsorption of Ti species and electron donor, as well as propylene polymerization over the Ziegler-Natta catalyst have been investigated using density functional theory （DFT） method. Twelve possible support models of regular and defective MgC12 （110） and （100） surfaces were built. The individual adsorptions of titanium chlorides as mononuclear or dinuclear, and ethyl benzoate （EB） as electron donor, on these models were evaluated. The analysis of energies presented the cases of EB adsorption were generally more stable than titanium chlorides on both surfaces. Thus, EB as internal electron donor mainly prevented TIC14 from coordinating on the MgC12 surfaces where mostly non-stereospecific active sites could be formed. Exceptionally, A5 the site model with terminal Cl-vacancy on the MgC12 support, presented stronger adsorption of TiCl4 than that of EB on （110） surface. Since the TIC14 and ethyl benzoate （EB） would compete to adsorb on the support surface, it seems reasonable to assume that TIC14 might predominately occupy this site, which can act as the most plausible active site for propylene polymerization. The first insertion of propylene monomer into the A5 active site model showed that it exhibited good regioselectivity but poor stereospecificity in the absence of electron donor.展开更多
基金supported by the Program of Introducing Talents of Discipline to Universities (B08021)Fundamental Research Funds for the Central Universities
文摘The formations of defective MgC12 surfaces, and subsequent adsorption of Ti species and electron donor, as well as propylene polymerization over the Ziegler-Natta catalyst have been investigated using density functional theory （DFT） method. Twelve possible support models of regular and defective MgC12 （110） and （100） surfaces were built. The individual adsorptions of titanium chlorides as mononuclear or dinuclear, and ethyl benzoate （EB） as electron donor, on these models were evaluated. The analysis of energies presented the cases of EB adsorption were generally more stable than titanium chlorides on both surfaces. Thus, EB as internal electron donor mainly prevented TIC14 from coordinating on the MgC12 surfaces where mostly non-stereospecific active sites could be formed. Exceptionally, A5 the site model with terminal Cl-vacancy on the MgC12 support, presented stronger adsorption of TiCl4 than that of EB on （110） surface. Since the TIC14 and ethyl benzoate （EB） would compete to adsorb on the support surface, it seems reasonable to assume that TIC14 might predominately occupy this site, which can act as the most plausible active site for propylene polymerization. The first insertion of propylene monomer into the A5 active site model showed that it exhibited good regioselectivity but poor stereospecificity in the absence of electron donor.
