Cobalt and nickel complexes （la-ld and 2a-2d, respectively） supported by 2-imidate-pyridine ligands were synthesized and used for 1,3-butadiene polymerization. The complexes were characterized by IR and element anal...Cobalt and nickel complexes （la-ld and 2a-2d, respectively） supported by 2-imidate-pyridine ligands were synthesized and used for 1,3-butadiene polymerization. The complexes were characterized by IR and element analysis, and complex la was further characterized by single-crystal X-ray diffraction. The solid state structure of complex la displayed a distorted tetrahedral geometry. Upon activation with ethylaluminum sesquichloride （EASC）, all the complexes showed high activities toward 1,3-butadiene polymerization. The cobalt complexes produced polymers with high cis-1,4 contents and high molecular weights, while the nickel complexes displayed low cis-l,4 selectivity and the resulting polymers had low molecular weights. The catalytic activities of the complexes highly depended on the ligand structure. With the increment of polymerization temperature, the cis-1,4 content and the molecular weight of the resulting polymer decreased.展开更多
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
Two novel Fe(Ⅱ) diimine complexes have been synthesized. In combination with MAO, they generate active catalytic systems that oligomerize ethylene with both high catalytic activity and high selectivity for a-olefins....Two novel Fe(Ⅱ) diimine complexes have been synthesized. In combination with MAO, they generate active catalytic systems that oligomerize ethylene with both high catalytic activity and high selectivity for a-olefins. The effects of substituents on the aryl ring, reaction temperatures and molar ratios of Al/Fe on catalytic activity and product distribution are studied.展开更多
The concentration of 39 trace elements in coal from the late Permian taken from the eastern Yunnan-western Guizhou region was determined using inductively coupled plasma mass spectrometry. It was found that the mean c...The concentration of 39 trace elements in coal from the late Permian taken from the eastern Yunnan-western Guizhou region was determined using inductively coupled plasma mass spectrometry. It was found that the mean content of Ti, V, Cr, Mo, Co, Ni, Y, and Zr is higher than the national average. The occurrence of Mn, Ni, and Co in the different coalfields is distinctly different. Most of the enriched transition metal elements exist mainly as inorganic minerals. In the Zhina coalfield, Co, Ni, and Nb are primarily associated with sulfur. Mn, Cs, and Mo are mostly sulfides. Almost all Co was organic and a significant part of the Ni is also organic in the Liupanshui coalfield. Cs, Co, and Ni are related to sulfur in the coal taken from eastern Yunnan. Carbonate is the main form of Mn in the coal from eastern Yunnan and the Liupanshui coalfield. Ti is the oxide in the coal samples where Ti is enriched. Zr is in the form of zircon in the samples where Zr is enriched. The situation for most of the transition metal elements is consistent with terrestrial genesis. Coal seams are universally influenced by the sea. The strongly seawater effected peat bog with a reductive and alkaline environment favors the relative enrichment of Mn. A reducing environment is conducive to transition metal element enrichment.展开更多
基金financially supported by the 973 Program(No.2015CB654700 or 2015654702)the National Natural Science Foundation of China(Nos.51473156 and 51203147)
文摘Cobalt and nickel complexes （la-ld and 2a-2d, respectively） supported by 2-imidate-pyridine ligands were synthesized and used for 1,3-butadiene polymerization. The complexes were characterized by IR and element analysis, and complex la was further characterized by single-crystal X-ray diffraction. The solid state structure of complex la displayed a distorted tetrahedral geometry. Upon activation with ethylaluminum sesquichloride （EASC）, all the complexes showed high activities toward 1,3-butadiene polymerization. The cobalt complexes produced polymers with high cis-1,4 contents and high molecular weights, while the nickel complexes displayed low cis-l,4 selectivity and the resulting polymers had low molecular weights. The catalytic activities of the complexes highly depended on the ligand structure. With the increment of polymerization temperature, the cis-1,4 content and the molecular weight of the resulting polymer decreased.
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.
基金This work was supported by the Special Funds for the Major State Basic Research Projects (Grant No. G1999064800)the National Natural Science Foundation of China (Grant No. 29734141) the State Key Laboratory of Engineering Plastics (Grant No. 0062).
文摘Two novel Fe(Ⅱ) diimine complexes have been synthesized. In combination with MAO, they generate active catalytic systems that oligomerize ethylene with both high catalytic activity and high selectivity for a-olefins. The effects of substituents on the aryl ring, reaction temperatures and molar ratios of Al/Fe on catalytic activity and product distribution are studied.
基金financially supported by the National Natural Science Foundation of China (No. 40730422)
文摘The concentration of 39 trace elements in coal from the late Permian taken from the eastern Yunnan-western Guizhou region was determined using inductively coupled plasma mass spectrometry. It was found that the mean content of Ti, V, Cr, Mo, Co, Ni, Y, and Zr is higher than the national average. The occurrence of Mn, Ni, and Co in the different coalfields is distinctly different. Most of the enriched transition metal elements exist mainly as inorganic minerals. In the Zhina coalfield, Co, Ni, and Nb are primarily associated with sulfur. Mn, Cs, and Mo are mostly sulfides. Almost all Co was organic and a significant part of the Ni is also organic in the Liupanshui coalfield. Cs, Co, and Ni are related to sulfur in the coal taken from eastern Yunnan. Carbonate is the main form of Mn in the coal from eastern Yunnan and the Liupanshui coalfield. Ti is the oxide in the coal samples where Ti is enriched. Zr is in the form of zircon in the samples where Zr is enriched. The situation for most of the transition metal elements is consistent with terrestrial genesis. Coal seams are universally influenced by the sea. The strongly seawater effected peat bog with a reductive and alkaline environment favors the relative enrichment of Mn. A reducing environment is conducive to transition metal element enrichment.
