In this article, the effect of diethylaluminum chloride （DEAC） in propylene polymerization with MgC12-supported Ziegler-Natta catalyst was studied. Addition of DEAC in the catalyst system caused evident change in ca...In this article, the effect of diethylaluminum chloride （DEAC） in propylene polymerization with MgC12-supported Ziegler-Natta catalyst was studied. Addition of DEAC in the catalyst system caused evident change in catalytic activity and polymer chain structure. The activity decrease in raising DEAC/Ti molar ratio from 0 to 2 is a result of depressed production of isotactic polypropylene chains. The number of active centers in fractions of each polymer sample was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and fractionating the polymer into isotactic, medium- isotactic and atactic fractions. The number of active centers in isotactic fraction （[Ci＊]/[Ti]） was lowered by increasing DEAC/Ti molar ratio to 2, but further increasing the DEAC/Ti molar ratio to 20 caused marked increase of [Ci＊]/[Ti]. The number of active centers that produce atactic and medium-isotactic PP chains was less influenced by DEAC in the range of DEAC/Ti = 0-10, but increased when the DEAC/Ti molar ratio was further raised to 20. The propagation rate constant of Ci＊ （k^i） was evidently increased when DEAC/Ti molar ratio was raised from 0 to 5, but further increase in DEAC/Ti ratio caused gradual decrease in kpi. The complicated effect of DEAC on the polymerization kinetics, catalysis behaviors and polymer structure can be reasonably explained by adsorption of DEAC on the central metal of the active centers or on Mg atoms adjacent to the central metal展开更多
制备了N,N-二(2,6-二异丙基苯基)苊二亚胺氯化镍,与A lE t2C l组成催化体系,催化4-乙烯基吡啶(4-VP)的聚合。研究表明,该催化体系可以有效地催化4-乙烯基吡啶聚合,并具有较高的活性,聚合条件如单体浓度、铝镍摩尔比、聚合温度和聚合时...制备了N,N-二(2,6-二异丙基苯基)苊二亚胺氯化镍,与A lE t2C l组成催化体系,催化4-乙烯基吡啶(4-VP)的聚合。研究表明,该催化体系可以有效地催化4-乙烯基吡啶聚合,并具有较高的活性,聚合条件如单体浓度、铝镍摩尔比、聚合温度和聚合时间等对4-乙烯基吡啶的聚合反应活性有较大的影响。最佳反应条件是单体浓度为0.6 m o l/L、n(A l)/n(N i)为800、温度为30℃,这时催化活性达到47.2 kg P(4-VP)/m o l N i.h。展开更多
Diethylaluminum azide (DEAA) is an important compound in organoaluminum andes. But the synthesis and property of DEAA were reported a little. The DEAA is a liquid compound in literature that was synthesed by the react...Diethylaluminum azide (DEAA) is an important compound in organoaluminum andes. But the synthesis and property of DEAA were reported a little. The DEAA is a liquid compound in literature that was synthesed by the reaction of diethyl aluminum chloride (DEAC) and sodium azide. The solid product as a colorless crystal was first obtained by the reaction of DEAC and sodium azide in our work. The solid product was characterized as DEAA by IR spectrum and H NMR spectrum. The yield of crystal DEAA was increased as NaN3/DEAC (mol/mol) increased. When NaN3/DEAC = 1. 3 the yield of DEAA is increased from 74% in literature to 83%. The melting point of DEAA is 28 - 29℃ that was determined with two methods in the work. The DEAA containing trace DEAC (about 0. 2% of DEAC) is liquid which has been full proved by varied tests in this paper. The melting point of DEAA is - 130℃ in literature because the DEAA is not pure that may contain DEAC. The - 130℃ may be eutectic point of eutectic mixture forming of DEAA and DEAC. 27,Al NMR of DEAA is determined. At δ = 6. 4 there is a peak that 1/2 of the peak is 834Hz. The structure of crystal DEAA is inferred from 27Al NMR.展开更多
An α-4(20)-epoxy-5α-hydroxytaxinine B 1, when treated with diethylaluminum chloride, underwent reactions involving intramolecular substitution along with deacetylation or addition leading to new rings. Two novel 1-d...An α-4(20)-epoxy-5α-hydroxytaxinine B 1, when treated with diethylaluminum chloride, underwent reactions involving intramolecular substitution along with deacetylation or addition leading to new rings. Two novel 1-deoxy compounds 2 and 3 were isolated and fully characterized.展开更多
Thermal stabilities of diethylaluminum azide were studied by means of theoretical analysis and expriments.The results have shown that diethylaluminum and azid be heated to vigorous refluxing under vacuum(400 Pa) at te...Thermal stabilities of diethylaluminum azide were studied by means of theoretical analysis and expriments.The results have shown that diethylaluminum and azid be heated to vigorous refluxing under vacuum(400 Pa) at temperature as high as 420℃ without incident of explosion and decomposes smoothly during 460 ～580℃ to form nanometric particles of aluminum nitride in the aerosol synthesis reactor. A new way of preparing nanometric parties of aluminum nitrideis found.展开更多
基金supported by the National Natural Science Foundation of China (No. 21074108)the Major State Basic Research Programs (No. 2011CB606001)
文摘In this article, the effect of diethylaluminum chloride （DEAC） in propylene polymerization with MgC12-supported Ziegler-Natta catalyst was studied. Addition of DEAC in the catalyst system caused evident change in catalytic activity and polymer chain structure. The activity decrease in raising DEAC/Ti molar ratio from 0 to 2 is a result of depressed production of isotactic polypropylene chains. The number of active centers in fractions of each polymer sample was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and fractionating the polymer into isotactic, medium- isotactic and atactic fractions. The number of active centers in isotactic fraction （[Ci＊]/[Ti]） was lowered by increasing DEAC/Ti molar ratio to 2, but further increasing the DEAC/Ti molar ratio to 20 caused marked increase of [Ci＊]/[Ti]. The number of active centers that produce atactic and medium-isotactic PP chains was less influenced by DEAC in the range of DEAC/Ti = 0-10, but increased when the DEAC/Ti molar ratio was further raised to 20. The propagation rate constant of Ci＊ （k^i） was evidently increased when DEAC/Ti molar ratio was raised from 0 to 5, but further increase in DEAC/Ti ratio caused gradual decrease in kpi. The complicated effect of DEAC on the polymerization kinetics, catalysis behaviors and polymer structure can be reasonably explained by adsorption of DEAC on the central metal of the active centers or on Mg atoms adjacent to the central metal
文摘制备了N,N-二(2,6-二异丙基苯基)苊二亚胺氯化镍,与A lE t2C l组成催化体系,催化4-乙烯基吡啶(4-VP)的聚合。研究表明,该催化体系可以有效地催化4-乙烯基吡啶聚合,并具有较高的活性,聚合条件如单体浓度、铝镍摩尔比、聚合温度和聚合时间等对4-乙烯基吡啶的聚合反应活性有较大的影响。最佳反应条件是单体浓度为0.6 m o l/L、n(A l)/n(N i)为800、温度为30℃,这时催化活性达到47.2 kg P(4-VP)/m o l N i.h。
文摘Diethylaluminum azide (DEAA) is an important compound in organoaluminum andes. But the synthesis and property of DEAA were reported a little. The DEAA is a liquid compound in literature that was synthesed by the reaction of diethyl aluminum chloride (DEAC) and sodium azide. The solid product as a colorless crystal was first obtained by the reaction of DEAC and sodium azide in our work. The solid product was characterized as DEAA by IR spectrum and H NMR spectrum. The yield of crystal DEAA was increased as NaN3/DEAC (mol/mol) increased. When NaN3/DEAC = 1. 3 the yield of DEAA is increased from 74% in literature to 83%. The melting point of DEAA is 28 - 29℃ that was determined with two methods in the work. The DEAA containing trace DEAC (about 0. 2% of DEAC) is liquid which has been full proved by varied tests in this paper. The melting point of DEAA is - 130℃ in literature because the DEAA is not pure that may contain DEAC. The - 130℃ may be eutectic point of eutectic mixture forming of DEAA and DEAC. 27,Al NMR of DEAA is determined. At δ = 6. 4 there is a peak that 1/2 of the peak is 834Hz. The structure of crystal DEAA is inferred from 27Al NMR.
基金Giant-in-Aid for scientific reserch from the Ministry of Education, Science and Culture of JapanJSPS fellowship to DL Q. Che
文摘An α-4(20)-epoxy-5α-hydroxytaxinine B 1, when treated with diethylaluminum chloride, underwent reactions involving intramolecular substitution along with deacetylation or addition leading to new rings. Two novel 1-deoxy compounds 2 and 3 were isolated and fully characterized.
文摘Thermal stabilities of diethylaluminum azide were studied by means of theoretical analysis and expriments.The results have shown that diethylaluminum and azid be heated to vigorous refluxing under vacuum(400 Pa) at temperature as high as 420℃ without incident of explosion and decomposes smoothly during 460 ～580℃ to form nanometric particles of aluminum nitride in the aerosol synthesis reactor. A new way of preparing nanometric parties of aluminum nitrideis found.
