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SIMULATION MODELING ON THE COORDINATION MECHANISM OF ETHYLENE MONOMER ON VARIOUS PREREDUCED Cr(Ⅱ)Ox/SiO2 PHILLIPS POLYETHYLENE MODEL CATALYSTS
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作者 刘柏平 《Chinese Journal of Polymer Science》 SCIE CAS CSCD 2008年第5期579-587,共9页
As one of the most important catalysts in polyethylene industry,Phillips catalyst(CrO_x/SiO_2)was quite unique for its activation by ethylene monomer without using any activator like alkyl-aluminium or MAO.In this wor... As one of the most important catalysts in polyethylene industry,Phillips catalyst(CrO_x/SiO_2)was quite unique for its activation by ethylene monomer without using any activator like alkyl-aluminium or MAO.In this work,the density functional theory(DFT)calculation combined with paired interacting orbitals(PIO)method was applied for the theoretical studies on coordination reaction mechanism between ethylene monomer and two model catalysts namely Cr(Ⅱ)(OH)_2(M1) and silsesquioxane-supported Cr(Ⅱ)(M2)as surfac... 展开更多
关键词 phillips catalyst(CrO_x/SiO_2) POLYETHYLENE Model catalysts Density functional theory(DFT) Paired interacting orbitals(PIO).
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Study of the coordinative nature of alkylaluminum modified Phillips CrO_x/SiO_2 catalyst by multinuclear solid-state NMR
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作者 Zhang Qin-Hui Yan Fang +1 位作者 Xia Wei Liu Chenguang 《Petroleum Science》 SCIE CAS CSCD 2013年第4期577-583,共7页
Solid-state nuclear magnetic resonance spectroscopy was used to investigate the coordinative states of surface Al species on various alkylaluminum-modified Phillips CrOx/SiO2 catalysts.The alkylaluminum-modified Phill... Solid-state nuclear magnetic resonance spectroscopy was used to investigate the coordinative states of surface Al species on various alkylaluminum-modified Phillips CrOx/SiO2 catalysts.The alkylaluminum-modified Phillips CrOx/SiO2 catalysts were examined via ethylene homopolymerization.1H and 27Al magic angle spinning(MAS) nuclear magnetic resonance(NMR) spectra clearly demonstrated that the existing states of surface Al species in alkylaluminum-modified catalysts strongly depended on the type of alkylaluminum cocatalyst,concentration of alkylaluminum and the calcination temperature.1H MAS NMR spectra of alkylaluminum-modified Phillips CrOx/SiO2 catalysts,calcined at two different temperatures,exhibited similar trends in peak shift.1H spectra showed that with an increase of Al/Cr ratio and calcination temperature,the main peak shifted to high field,indicating that the dominant surface proton species changed from hydroxyl to ethoxyl and ethyl groups.27Al MAS NMR spectra showed the presence of three different coordination states(6-,5-,and 4-coordinated Al species) in the alkylaluminummodified Phillips catalysts.In comparison of different alkylaluminum cocatalysts,it was found that the reactivity of alkylaluminum modified Phillips catalyst decreased in the order of TEA〉DEAH〉DEAE.The amount of 4-coordinated Al species of Phillips catalysts modified by TEA,DEAE and DEAH also decreased in the order of TEA〉DEAH〉DEAE,indicating that the presence of 4-coordinated Al species is related to the polymerization activity. 展开更多
关键词 phillips catalyst ALKYLALUMINUM ethylene polymerization solid-state NMR
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