A new carbon bridged cyclopentadienyl chromium complex of the type [（C5H4）C（CH3）2 CH2（C5H4N）]CrCl2 was prepared by treatment of CrCl3·（THF）3 in THF solution with the lithium salt of ligand containing cycl...A new carbon bridged cyclopentadienyl chromium complex of the type [（C5H4）C（CH3）2 CH2（C5H4N）]CrCl2 was prepared by treatment of CrCl3·（THF）3 in THF solution with the lithium salt of ligand containing cyclopentadienyl and pyridyl groups. The chromium complex was characterized by 1H NMR and elemental analysis（EA）, and the crystal structure was determined by X-ray diffraction analysis. Activated by Al（i-Bu）3, the chromium complex displayed a very high activity for methyl methacrylate（MMA） polymerization. After 24 hours,more than 95.5% MMA was converted to polymethyl methacrylate（PMMA） with a viscosity average molecular weight（Wη） of 416000 g·mol-1 at 60 ℃ for MMA/ Al（i-Bu）3 /chromium catalyst molar ratio of up to 2000：20：1. Effects of temperature, molar ratios of MMA/catalyst and catalyst/cocatalyst on the polymerization have been studied. The high conversion of MMA and high molecular weight of PMMA with narrow molecular weight distribution is caused by the unique stable active site formed by the new chromium complex and aluminum cocatalyst.展开更多
Tri(4-methoxy-1-benzyloxyl)(pentamethylcyclopentadienyl)titanium(Cp*Ti(OBzOCH3)3) in conjunction with modified methylalumoxane(mMAO) was an efficient catalyst for the living polymerization of butene-1. The steric and ...Tri(4-methoxy-1-benzyloxyl)(pentamethylcyclopentadienyl)titanium(Cp*Ti(OBzOCH3)3) in conjunction with modified methylalumoxane(mMAO) was an efficient catalyst for the living polymerization of butene-1. The steric and highly electron-releasing nature of the catalyst was probably responsible for the resulting polymers with high molecular weight and narrow molecular weight distribution(Mw/Mn=1.25 to 1.36). The effects of polymerization conditions on the catalytic activity, molecular weight and stereo-regularity of the products were investigated in detail. Especially, the content of TMA in MAO used in polymerization of butene-1 had a profound influence on polymer microstructure. The structural properties of the polybutene-1 product were characterized by 13 C NMR, GPC, DSC and WAXD. The results indicated that the polybutene-1 was isotacticity-rich(at 0 ℃, [mmmm] reached up to 60.3%) and the relative content of methylene pentad sequences [mmmm] of the polymer increased with a decreasing temperature.展开更多
基金Funded by the National Natural Science Foundation of China(No.51204125)the Natural Science Foundation of Hubei Province(Nos.2014CFB812 and 2014CFB810)the Open Fund Project Funded by the Key Laboratory of Coal Conversion and New Carbon Materials of Hubei Province in China(No.WKDM201302)
文摘A new carbon bridged cyclopentadienyl chromium complex of the type [（C5H4）C（CH3）2 CH2（C5H4N）]CrCl2 was prepared by treatment of CrCl3·（THF）3 in THF solution with the lithium salt of ligand containing cyclopentadienyl and pyridyl groups. The chromium complex was characterized by 1H NMR and elemental analysis（EA）, and the crystal structure was determined by X-ray diffraction analysis. Activated by Al（i-Bu）3, the chromium complex displayed a very high activity for methyl methacrylate（MMA） polymerization. After 24 hours,more than 95.5% MMA was converted to polymethyl methacrylate（PMMA） with a viscosity average molecular weight（Wη） of 416000 g·mol-1 at 60 ℃ for MMA/ Al（i-Bu）3 /chromium catalyst molar ratio of up to 2000：20：1. Effects of temperature, molar ratios of MMA/catalyst and catalyst/cocatalyst on the polymerization have been studied. The high conversion of MMA and high molecular weight of PMMA with narrow molecular weight distribution is caused by the unique stable active site formed by the new chromium complex and aluminum cocatalyst.
基金the National Natural Science Foundation of China (No. 21174011)the Natural Science Foundation of Beijing, China (No. 2102036)
文摘Tri(4-methoxy-1-benzyloxyl)(pentamethylcyclopentadienyl)titanium(Cp*Ti(OBzOCH3)3) in conjunction with modified methylalumoxane(mMAO) was an efficient catalyst for the living polymerization of butene-1. The steric and highly electron-releasing nature of the catalyst was probably responsible for the resulting polymers with high molecular weight and narrow molecular weight distribution(Mw/Mn=1.25 to 1.36). The effects of polymerization conditions on the catalytic activity, molecular weight and stereo-regularity of the products were investigated in detail. Especially, the content of TMA in MAO used in polymerization of butene-1 had a profound influence on polymer microstructure. The structural properties of the polybutene-1 product were characterized by 13 C NMR, GPC, DSC and WAXD. The results indicated that the polybutene-1 was isotacticity-rich(at 0 ℃, [mmmm] reached up to 60.3%) and the relative content of methylene pentad sequences [mmmm] of the polymer increased with a decreasing temperature.
