双环戊二烯在水溶性铑膦络合催化体系中的氢甲酰化反应

研究了采用水溶性铑膦络合催化体系对双环戊二烯的氢甲酰化反应，考查了反应温度、相转移剂ＣＴＡＢ、铑催化剂浓度等对反应的影响。氢甲酰化反应的产物经ＧＣ／ＭＳ鉴定是不饱和的三环癸单醛     

三苯基膦功能化聚酰胺/铑催化烯烃氢甲酰化

以三(3-氨基苯基)膦与联苯-4,4′-二甲酸为原料合成了一种三苯基膦功能化的聚酰胺有机载体,并通过红外光谱、固体核磁对其结构进行表征。聚酰胺载体与Rh(acac)(CO)₂组成的多相催化体系可以有效地催化1-己烯的氢甲酰化反应。研究表明,该多相催化剂具有较好的化学稳定性和催化效果。在90℃下,甲苯溶剂中,催化剂在15 h内完全催化转化1-己烯生成庚醛和2-己烯,产物中醛的选择性为37.4%。通过离心的方法可以实现催化剂与产物的快速分离及多次利用。催化剂的循环使用研究表明,在使用5次后,对1-己烯的催化活性仍高达100%,醛的选择性在34.9%以上,产物醛的正异构比约为2.5。     

铑催化高碳烯烃氢甲酰化合成高碳醇进展

介绍了近年来铑／膦催化高碳烯烃氢甲酰化的研究和开发进展。特别是以ＴＰＰＯ／Ｒｈ为催化剂的Ｍｉｔｓｕｂｉｓｈｉ Ｋａｓｅｉ工艺和水／有机两相为主的各种两相催化技术。近年的进展表明,通过创新膦配体以及采用两相催化体系,有望使更有效,更经济的铑催化工艺在高碳烯烃氢甲酰化的应用中取得突破。     

水溶性过渡金属络合物催化两相氢甲酰化反应新进展

本文综述了水溶性膦配体的合成和水溶性过渡金属络合物催化剂在水／有机溶剂两相体系中催化氢甲酰化反应的近期进展。     

烯烃氢甲酰化反应的催化技术进展

综述了烯烃氢甲酰化反应工业化的不同催化体系,分析了各自的技术特点,阐述了其新进展情况,并对催化剂的今后发展进行了展望。     

均相铑膦催化体系下1-癸烯氢甲酰化反应研究

氢甲酰化反应是目前生产醛醇化合物最重要的反应之一,高碳烯烃氢甲酰化工艺改进是研究的难点和热点之一。探索了一种C10烯烃氢甲酰化反应的工艺,以三苯基膦（Ph₃P）和亚磷酸三（2-叔丁基-4-甲氧基苯基）酯（L_A）混合物为配体,与乙酰丙酮二羰基铑原位合成的催化体系催化1-癸烯氢甲酰化反应。系统考察了反应温度、反应压力、铑浓度、膦铑比、无机盐添加剂对反应的影响。结果表明,在n（Ph₃P）/n（L_A）=10、铑质量分数为280 mg/kg,1-癸烯用量（相对于甲苯）为0.3 g/mL,n（膦）/n（铑）=45、反应温度为90 ℃、反应压力为2.0 MPa、n（一氧化碳）/n（氢气）=1条件下反应4 h,1-癸烯转化率为98.1%、醛收率为93.2%、正异比为7.5。研究还发现,在减压蒸馏产物与催化剂分离时,加入无机盐添加剂能够提高催化剂的稳定性,减少铑损失。     

反应工程因素对十二碳烯氢甲酰化反应速率和正异比的影响

在研究烯烃氢甲酰化反应过程中 ,水溶性催化剂由于具有安全、易回收以及对环境友好等优点而受到广泛的关注[1] .水溶性铑膦络合物催化剂已成功用于丙烯氢甲酰化的工业生产 ,但 1-十二碳烯等长链烯烃的强烈憎水性使得氢甲酰化反应速率极低 .加入阳离子表面活性剂[2 ] ,在反应体系中形成胶束 ,可以提高 1-十二碳烯氢甲酰化反应速率 .水溶性铑膦络合物催化十二碳烯氢甲酰化反应是一个典型的气液液三相反应 ,影响宏观反应动力学和产物正异比的因素很多 .以前的实验已系统地研究了温度、压力、氢气与一氧化碳摩尔比、催化剂浓度、油水比、膦铑比…     

一步法制备丙烯氢甲酰化制丁醛铑膦络合催化剂研究

采用一步法制备铑膦络合催化剂,考察了反应温度、反应时间、铑膦比、还原剂用量、氢源用量等因素对催化剂制备过程铑利用率的影响。在优化的工艺条件下,铑利用率达99%以上。在适宜的评价条件下,丙烯转化率为97.1%,丁醛选择性为98.1%,产物醛正异构比15∶1以上。     

混合C8烯烃氢甲酰化反应的实验研究

对几种铑膦络合物催化混合Ｃ８烯烃氢甲酰化反应作了实验研究了,结果表明,在一定反应条件下,「Ｒｈ（ＣＨ３ＣＯＯ）２」２,Ｒｈ（ＣＯ）ＰＰｈ３（ａｃａｃ）和Ｒｈ６（ＣＯ）１６均是有效的催化剂前体。配体。铑 的浓度及溶体对催化系性能影响的实验证明,外加ＯＰＰｈ３、选用适量Ｒｈ浓及加入二乙二醇二甲醚或四乙二醇二甲醚等溶剂对Ｃ８烯烃氢甲酰化反应生成Ｃ９醛是有利的。实验表明,对于「Ｒｈ（ＣＨ３ＣＯＯ２）２－Ｏ     

氢甲酰化反应失活铑催化剂的活化及回收研究进展

介绍了氢甲酰化反应中铑膦催化剂的两种失活机理-外部中毒和内部失活；详述了用氧化蒸馏、苯取、洗涤、沉淀和化学活化等方法活化部分失活催化剂，以及对全部失活催化剂进行回收利用的方法；还对这些方法的优缺点进行了比较。     

Rhodium catalyzed hydroformylation of 1-octene in microemulsion: comparison with various catalytic systems

In this work, we describe how addition of alkylpolyglycol ether type nonionic surfactant affects the hydroformylation of 1-octene in the presence of phosphine modified rhodium catalyst. Influence of different process parameters such as ligand excess and amount of surfactant on the reaction rate and selectivity were discussed. Direct comparison of microemulsion systems with classic processes was achieved by performing the reactions under comparable homogeneous and biphasic conditions. Thus, the experiments were carried out using catalysts such as unmodified rhodium carbonyl HRh(CO)₄ and HRh(CO)(PPh₃)₃ in homogeneous system, Rh–TPPTS complex in two-phase system and in association with co-solvent.     

混合C_8烯烃氢甲酰化反应的实验研究

对几种铑膦络合物催化混合 C8烯烃氢甲酰化反应作了实验研究 ,结果表明 ,在一定反应条件下 ,[Rh( CH3COO) 2 ]2 、Rh( CO) PPh3( acac)和 Rh6 ( CO) 16 均是有效的催化剂前体。配体、铑的浓度及溶剂对催化体系性能影响的实验证明 ,外加 OPPh3、选用适量 Rh浓度及加入二乙二醇二甲醚或四乙二醇二甲醚等溶剂对 C8烯烃氢甲酰化反应生成 C9醛是有利的。实验表明 ,对于 [Rh( CH3COO) 2 ]2 - OPPh3催化体系在 1 40℃及 1 0 .5MPa反应条件下 ,混合 C8烯烃氢甲酰化反应生成 C9醛的收率可达 90 %以上。     

Immobilization of rhodium catalysts in biphasic systems and in layered structures using phosphonated phosphines

Uncomplicated syntheses of phosphines substituted with phosphonic acid groups have been developed. The ligands were used to immobilize rhodium catalysts in aqueous biphasic systems and between the layers of zirconium phosphate hybrid materials. Effective immobilization, high activities (turnover frequencies higher than 600 h^-1) and selectivities were found in the hydroformylation of 1-octene to nonanal and 2-methyloctanal. This revised version was published online in June 2006 with corrections to the Cover Date.     

Aqueous Biphasic Hydroformylation of Higher Olefins Catalyzed by Rhodium Complexes with Amphiphilic Ligands of Sulfonated Triphenylphosphine Analog

The catalytic performances of rhodium complexes with three new amphiphilic phosphine ligands, bis-(3-sodium sulfonatophenyl)-(4-tert-butylphenyl)-phosphine (3), phenyl-(3-sodium sulfonatophenyl)-(4-tert-butyl-phenyl)-phosphine (4) and bis-(4-tert-butylphenyl)-(3-sodium sulfonatophenyl) phosphine (5), in hydroformylation of 1-hexene, 1-octene and 1-dodecene have been studied. The steric attributes of free ligands are investigated by Tolman's cone angle method through geometric optimizations. The results reveal that the new phosphines are surface-active as the typical surfactants and the corresponding rhodium complexes show significant enhancements in the reaction rate and higher selectivities toward the normal aldehydes in comparison with those obtained by triphenylphosphine trisulfonate (TPPTS)- and triphenylphosphine disulfonate (TPPDS) rhodium complexes under identical conditions.     

Hydroformylation with rhodium phosphine-modified catalyst in a microemulsion: comparison of organic and aqueous systems for styrene, cyclohexene and 1,4-diacetoxy-2-butene

Use of microemulsion as a reaction media in the hydroformylation of different alkenes, namely styrene, cyclohexene and 1,2-diacetoxy-2-butene have been studied using alkylpolygylcol ether-type nonionic surfactant in the presence of phosphine-modified rhodium catalyst. The combination of the experiments under comparable homogeneous and biphasic conditions were performed in order to make direct comparison of microemulsion with classical systems. Thus, the experiments were also carried out using catalysts such as unmodified rhodium carbonyl H Rh(CO)₄ and H Rh(CO)(PPh₃)₃ in homogeneous system, Rh–TPPTS complex in two-phase system and in association with co-solvent.     

Thermoregulated Phase-Separable Phosphine Rhodium Complex Catalyst for Hydroformylation of Cyclohexene

Based on the critical solution temperature of nonionic tensioactive phosphine ligand, a novel process termed as thermoregulated phase-separable catalysis has been applied for the first time in the hydroformylation of cyclohexene. The catalyst is formed in situ from P[p-C₆H₄O(CH₂CH₂O)_nH]₃ (PETPP) and RhCl₃·3H₂O. Under the conditions of T=130 °C, P=5.0 Mpa, the conversion of cyclohexene and yield of aldehyde are 98.4%. The catalyst was reused four times and no loss in activity has been observed.     

铑络合物催化1,3—丁二烯与苯酚调聚合反应的研究

报道了铑事物催化１，３－丁二烯酚的调聚合反应。结果表明，催化剂活怀差异与铑原子上除三苯基之外的其它配体有关。Ｒｈ（ＰＰｈ３）３Ｐｈ是最好的催化剂，能使苯酚转化率达６６．５％，８－苯氧基－１，６－辛二烯的选择性达８９．４０％，研究了反应条件对调聚合瓜的和最适宜的温度 １２０℃，反应时间是２４ｈ。     

Gas phase hydroformylation of ethylene using organometalic Rh-complexes as heterogeneous catalysts

The heterogeneously catalysed gas phase hydroformylation of ethylene to propionaldehyde was studied over solid RhCl(PPh₃)₃ and RhCl(CO)(PPh₃)₂. At 3 bar and 185 °C, an active phase formed from RhCl(PPh₃)₃ which was different from RhCl(CO)(PPh₃)₂ under the reaction conditions studied. The selectivity of RhCl(PPh₃)₃ to propanal was much better than that of supported Rh-metal. Thus, solid metal-complexes operated in gas phase reactions clearly hold promise as a new class of heterogeneous catalysts.