A facile and user friendly technique to immobilize the late-transition metal complexes on spherical MgCl2/SiO2/THF support has been developed. The spherical MgCl2/SiO2/THF-supported late-transition metal catalysts 2,6...A facile and user friendly technique to immobilize the late-transition metal complexes on spherical MgCl2/SiO2/THF support has been developed. The spherical MgCl2/SiO2/THF-supported late-transition metal catalysts 2,6-bis-[1-(2,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride(SC-A) and 1,4-bis(2,6-dimethylphenyl)- acenaphthene diimine nickel(II) dibromide(SC-B) for ethylene polymerization has been prepared by spray-drying technique using tetrahydrofuran suspension containing MgCl2, SiO2 and late-transition metal complexes. The catalysts were characterized by BET, XRD, SEM and the polymers were analyzed using GPC, DSC and 13C-NMR. The test results show that spray-drying is a very effective method for immobilizing late-transition metal catalysts for ethylene polymerization. Among six kinds of cocatalysts for olefin polymerization, TMA and TEA were confirmed to be more effective than other compounds for the ethylene polymerization system using the catalyst SC-A. For the case of the catalyst SC-B, DEAC showed the best performance as cocatalysts in ethylene polymerization. The replication of the catalyst morphology was found in the resultant polyethylene.展开更多
A diphenoxybis(β diketonato)titanium complex, (dbm) 2Ti(OPh) 2, was synthesized and the corresponding MgCl 2\|supported catalyst was prepared by impregnation method. The polymerization activity was drastically improv...A diphenoxybis(β diketonato)titanium complex, (dbm) 2Ti(OPh) 2, was synthesized and the corresponding MgCl 2\|supported catalyst was prepared by impregnation method. The polymerization activity was drastically improved by using MgCl 2\|supported (dbm) 2Ti(OPh) 2 activated by aluminoxane (MAO) for ethylene polymerization (1.5×10 5 g/molTi with the heterogeneous catalyst and 1.3×10\+3 g/molTi with the homogeneous one). When the molar ratio of Al to Ti increased from 50 to 1000, the crystallinity and molecular weight of polyethylene were decreased rapidly. Also, the molecular weight of polyethylene was decreased from 5.1×10 5 to 2.8×10\+5 by increasing the molar content of titanium of the supported catalyst from 0.5×10 -5 to 3.42 ×10 -5 . After 60 min of the reaction, the molecular weight was at 5.0×10 5 or so. It is revealed that the MgCl 2\|supported β diketonato titanium complex is influenced by the polymerization conditions markedly.展开更多
基金supported by the National Natural Science Foundation of China (Grant No.U1162114)the Science Foundation of Tianjin University of Science & Technology (20090420)
文摘A facile and user friendly technique to immobilize the late-transition metal complexes on spherical MgCl2/SiO2/THF support has been developed. The spherical MgCl2/SiO2/THF-supported late-transition metal catalysts 2,6-bis-[1-(2,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride(SC-A) and 1,4-bis(2,6-dimethylphenyl)- acenaphthene diimine nickel(II) dibromide(SC-B) for ethylene polymerization has been prepared by spray-drying technique using tetrahydrofuran suspension containing MgCl2, SiO2 and late-transition metal complexes. The catalysts were characterized by BET, XRD, SEM and the polymers were analyzed using GPC, DSC and 13C-NMR. The test results show that spray-drying is a very effective method for immobilizing late-transition metal catalysts for ethylene polymerization. Among six kinds of cocatalysts for olefin polymerization, TMA and TEA were confirmed to be more effective than other compounds for the ethylene polymerization system using the catalyst SC-A. For the case of the catalyst SC-B, DEAC showed the best performance as cocatalysts in ethylene polymerization. The replication of the catalyst morphology was found in the resultant polyethylene.
文摘A diphenoxybis(β diketonato)titanium complex, (dbm) 2Ti(OPh) 2, was synthesized and the corresponding MgCl 2\|supported catalyst was prepared by impregnation method. The polymerization activity was drastically improved by using MgCl 2\|supported (dbm) 2Ti(OPh) 2 activated by aluminoxane (MAO) for ethylene polymerization (1.5×10 5 g/molTi with the heterogeneous catalyst and 1.3×10\+3 g/molTi with the homogeneous one). When the molar ratio of Al to Ti increased from 50 to 1000, the crystallinity and molecular weight of polyethylene were decreased rapidly. Also, the molecular weight of polyethylene was decreased from 5.1×10 5 to 2.8×10\+5 by increasing the molar content of titanium of the supported catalyst from 0.5×10 -5 to 3.42 ×10 -5 . After 60 min of the reaction, the molecular weight was at 5.0×10 5 or so. It is revealed that the MgCl 2\|supported β diketonato titanium complex is influenced by the polymerization conditions markedly.
