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
制备了一种含有胺基官能团的α-二亚胺镍配合物,并将该配合物负载在AlEt_3改性的SiO_2-MgCl_2复合载体上制备负载催化剂,不用昂贵的MAO(甲基铝氧烷)而用AlEt_2Cl作助催化剂,研究了其对乙烯的聚合性能。并采用高温^(13)CNMR、高温GPC、...制备了一种含有胺基官能团的α-二亚胺镍配合物,并将该配合物负载在AlEt_3改性的SiO_2-MgCl_2复合载体上制备负载催化剂,不用昂贵的MAO(甲基铝氧烷)而用AlEt_2Cl作助催化剂,研究了其对乙烯的聚合性能。并采用高温^(13)CNMR、高温GPC、差示扫描量热法(DSC)等对得到的聚合物进行了研究。结果发现,该催化剂具有很高的催化活性(1.89×10~6g of PE/mol of Ni h),得到的聚乙烯产品含有各种短支链(甲基、乙基、丙基、丁基)和长支链,分子量在2.15×10~5～9.27×10~5之间,分子量分布为3.12～4.23。展开更多
Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS a...Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.展开更多
In situ FT-IR of SiO2-supported (pph3)Hpt(μ-pph2)(μ-CO)Mo(co)4heterobinuclear hydrido carbonyl catalyst in the CO hydrogenation condition has been investigated.
The SiO2-Supported (PPh3)2HPt(μ-CO) (μ-PPh2)M(CO) 4 (M-Cr.Mo, W) complel catalysts catalyzing CO2 hydrogenation are reported.The catalysts exhibited high catalytic activity and selectivity toward oxygenates
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.
文摘制备了一种含有胺基官能团的α-二亚胺镍配合物,并将该配合物负载在AlEt_3改性的SiO_2-MgCl_2复合载体上制备负载催化剂,不用昂贵的MAO(甲基铝氧烷)而用AlEt_2Cl作助催化剂,研究了其对乙烯的聚合性能。并采用高温^(13)CNMR、高温GPC、差示扫描量热法(DSC)等对得到的聚合物进行了研究。结果发现,该催化剂具有很高的催化活性(1.89×10~6g of PE/mol of Ni h),得到的聚乙烯产品含有各种短支链(甲基、乙基、丙基、丁基)和长支链,分子量在2.15×10~5～9.27×10~5之间,分子量分布为3.12～4.23。
基金The Executive Programme for Cooperation between Italy and India (Prot.No.MAE01054762017)。
文摘Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.
文摘In situ FT-IR of SiO2-supported (pph3)Hpt(μ-pph2)(μ-CO)Mo(co)4heterobinuclear hydrido carbonyl catalyst in the CO hydrogenation condition has been investigated.
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.
