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161.
Tadatomi Nishikubo Atsushi Kameyama Jun Yamashita Masao Tomoi Wakichi Fukuda 《Journal of polymer science. Part A, Polymer chemistry》1993,31(4):939-947
The addition reaction of oxiranes ( 26a—e ) with carbon dioxide (CO2) was performed using insoluble polystyrene beads containing pendant quaternary ammonium or phosphonium salts as catalysts under atmospheric pressure. The reaction of 26a—e with CO2 proceeded smoothly catalyzed by 1–2 mol % of the polymer-supported quaternary onium salts to give the corresponding cyclic carbonates ( 27a—e ) in high yields at 80–90°C. In this reaction system, the catalytic activity of the polymer-supported quaternary onium salts was strongly affected by the following factors: degree of ring substitution (DRS) of the onium salt residues to the polymer, degree of crosslinking (DC) of the polystyrene beads, chain length of the alkylene spacer between the polymer back-bone and the onium salt, hydrophobicity of the alkyl group on the onium salts, and kind of onium salts. That is, the polymer-supported quaternary phosphonium salts with low DRS and DC and with long alkylene spacer chain were found to have higher catalytic activity than low molecualr weight quaternary onium salts. The above polymer-supported catalysts can easily be separated at the end of a reaction by filtration and can be reused for at least seven runs. It was also found that the rate of reaction was proportional to the products of catalyst concentration and oxirane concentration. © 1993 John Wiley & Sons, Inc. 相似文献
162.
Radoslav D. Mii Radmila P. Marinkovi-Neduin Zoltán Schay István Nagy Jelena S. Kiurski Ern E. Kiss 《Reaction Kinetics and Catalysis Letters》2007,91(1):85-92
Investigations of a commercial NiMo/Al2O3 hydrodesulfurization (HDS) catalyst are directed towards optimization of the activation procedure of HDS catalyst concerning
active phase formation and thermal stability. Structural and textural data obtained with XRD, IR-FTIR, XPS and LTNA reveal
that the optimal temperature for the formation of active species on the catalyst surface and an appropriate pore structure
is 300°C. 相似文献
163.
在固定床反应器上,评价了不同温度下钙钛矿型复合氧化物SrTiO3和CaTiO3的组成变化对甲烷氧化偶联反应的影响.同时,利用XPS和CO2-TPD对催化剂的结构及其氧物种的反应特性进行了表征.结果表明:SrTiO3和少量Ca掺杂的CaxSrl-xTiO3有利于在较低温度(923K)下催化反应的活性和选择性,而CaTiO3体系则在高温(1073K)下表现出较好的活性和选择性.钙钛矿型复合氧化物SrTiO3和CaTiO3组成变化对不同温度下反应活性的影响与CO2-TPD的脱附谱图有很好的平行关系. 相似文献
164.
甲烷在SrO-La2O3/CaO催化剂上的氧化偶联Ⅱ.反应动力学的研究 总被引:1,自引:0,他引:1
在20%La2O3/CaO(LC)催化剂中添加SrO(添加SrO的LC以SLC表示)明显地提高了反应活性和C2选择性。反应动力学研究表明,LC和SLC催化剂在甲烷氧化偶联反应中,在表观活化能和表观反应级数上存在很大的差异。LC催化剂在CH4转化以及C2和COx形成过程中,表观活化能大于SLC催化剂,而SLC催化剂的指前因子小于LC体系,两者存在着补偿形象。SLC催化剂的反应速率常数比kc2/kCH 相似文献
165.
Highly enantioselective 1,4-addition of alkenylzirconocene chlorides to α,β-enones was found to be catalyzed by a chiral rhodium complex generated from [Rh(cod)(MeCN)2]BF4 and (S)-BINAP. The reaction can be applied to either cyclic or acyclic enones and the optical yield was up to 99% ee. The reaction mechanism would involve the transmetalation between the alkenylzirconocene chloride and the rhodium complex to give the alkenylrhodium species as a key intermediate. 相似文献
166.
A nickel catalyst was nodeled with ligand L^2,[NH=CH-CH=CH-0]^-,which should have potential use as a syndiotactic plyolefin catalyst,and the reaction mechanism was studied by theoretical calculations using the density functinal method at the B3LYP/LANL2MB level.The mechanism involves the formation of the intermediate [NiL^2Me]^ ,in which the metal occupies a T-shaped geometry.This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L^2.The results show that both structures can lead to the desired product via similar reaction paths,A and B.Thus,the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-0 or trans to the Ni-N bond in the catalyst.The polymerization process thus favors the catalysis of syndiotactic polyolefins.The syndiotactic synthesis effects could also be enhanced by varations in the ligand substituents.From energy considerations,we can conclude that it is more favorable for the methyl ttrans-O position to form a complex than to occupy the trans-N position.From bond length considerations,it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position. 相似文献
167.
168.
169.
以有机高价碘杂环化合物1,2为底物,在Pd(PPh3)2Cl2-CuCl催化剂存在下与末端炔烃进行交叉偶联反应,实验发现该反应为--化学选择性反应,控制反应体系的物料比、温度及反应时间可以分别得到单偶联或双偶联产物,从而证实了有机高价碘杂环化合物的碘盐在进行交叉偶联反应时的反应活性比sp2的碘化物高. 相似文献
170.
考察了茂环上不同取代基及钛上阴离子配体对茂基钛配合物/正丁基锂催化体系加氢活性和稳定性的影响。在充分发挥该体系催化活性的条件下,由配合物Cp2TiCl2、Cp2TiF2和Cp2Ti[OC6H3(CH3-2)Cl-4]2组成的催化体系对辛烯-1加氢的最高活性(或初活性)达到46 ̄58s^-1。 相似文献