【作者】 刘小华；

【导师】 胡家元；

【作者基本信息】 四川大学 ， 分析化学， 2003， 硕士

【摘要】 以水溶性有机金属配合物为催化剂的两相催化体系是“绿色化学”中发展迅速的前沿研究领域之一。1984年以水溶性铑-膦络合物为催化剂的水／有机两相催化新工艺----RCH／RP工艺，成功地应用于丙烯的氢甲酰化反应，为解决均相催化反应中催化剂与产物的分离问题开辟了新途径。丁烯为底物的氢甲酰化反应，生产成本低且有利于环境保护，因此引起国内外化学家的重视。本文在进行文献查阅的基础上，进行这方面的研究，主要工作包括以下三部分： 一、以水溶性铑-膦络合物RhCl（CO）（TPPTS）₂分别与配体TPPTS、BISBIS形成的复合体系为催化剂，研究不同条件对丁烯-1氢甲酰化反应的催化性能的影响。以BISBIS为配体，在较低的膦／铑比条件下，得到比TPPTS为配体更高的活性和对正构醛的选择性，130℃，2.0MPa条件下反应2小时成醛转化率达到73％，对正构醛的选择性高达98％。Rh-TPPTS催化体系，在膦／铑摩尔比为100，140℃，2.5MPa合成气压力下反应2小时，丁烯-1成醛转化率为70％左右，醛的正异比为7.3。 二、以水溶性络合物RhCl（CO）（TPPTS）₂为催化剂，TPPTS为配体，研究不同反应条件对混合丁烯（丁烯-1、顺，反-丁烯-2和丁烷混合物）氢甲酰化反应的影响。主要考察了温度、压力、膦铑比、表面活性剂等因素的变化对催化性能的影响。结果表明，CO分压增大，对丁烯-1双键异构有抑制作用，在100℃，2.0MPa（CO／H₂=1），TPPTS／Rh=25，[Rh]=1.024×10^-3mol／L的条件下，反应4h底物转化率接近35％，产物醛的正异比5.4。 三、对丁烯氢甲酰化反应产物戊醛（正戊醛和2-甲基-丁醛）进行催化加氢制备其重要衍生物戊醇。在较温和的反应条件下，以RuCl₃-TPPTS为催化剂前体的两相体系中，戊醛的转化率达95％以上，且反应中无缩聚副产物产生。更多还原

【Abstract】 Two-phase catalytic system with water-soluble organometallic complexes as catalysis is one of the frontier fields in the "Green Chemistry" that is progressing quickly recently. The most important industrial development in this area is the so called Ruchrchemie/Rhone-Poulenc process whose econmical advantages are based on simple principle of catalyst recycling and the low-cost catalyst/product separation and enviromental protenctiong. Nowdays, There is increasing interest in n-valeraldehyde achieved by the hydroformylation of the available feedstock base of "Raffinate-II ",which is a mixture of isomeric butenes (usually composed of 1- and 2-butenes,and a small amount of butane) .In this paper, the hydroformylation of butenes catalyzed by water-soluble rhodium complex and hydrogenation of its products-aldehyde were studied. The main works include:1.Butene-1 hydroformylation catalyzed by water-soluble rhodium complex RhCl(CO)(TPPTS)2, with the water-soluble phophine TPPTS or BISBIS as ligand, in the presence of cationic surfactant CTAB was studied. The effect of the reaction conditions, such as concentration of surfactant and rhodium complex, temperature, syngas pressure and the mole ratio of phosphine to rhodium on the activity and selectivity of hydroformylation was investigated. The comparison between phosphine ligand TPPTS and diphosphine ligand BISBIS indicated that Rh-BISBIS catalyst system shows higher activity and selectivity for forming normal aldehyde than the Rh-TPPTS system and Rh-TPPTS-CTAB system. The cationic surfactants could obviously accerate the reaction rate.In butene-1 hydroformylation under the optimum reaction conditions: 130 ℃,2.0MPa, [Rh]=1.0×10-3mol/L,[BISBIS]/[Rh]=5, TOF and selectivity for forming normal valeraldehyde were 1498 h-1 and 98%, respectively. In the other optimum system which were 140℃,2. 5MPa, [Rh]=l. 0×10-3 mol/L,[TPPTS]/[Rh]=100, the conversion of butene-1 reached to 70 % for two hours and the mole ratio of normal/iso aldehyde was 7.3.2. Based on the hydroformylation of butene-1, the hydroformylation of the mixture of isomeric butenes (1- and 2-butene,and butane) in biphasic catalytic system was studied in datail. The Rh/TPPTS catalysts is only applicable in water to the hydroformylation of terminal olefins. Butene-2 doesn’t react in the presence of butene-1. In this reaction, butene-1 is hydroformylated to n-valeraldehyde and 2-methyl butyraldehyde, and a part of butene-1 isomerized into butene-2 which decrease the formation of aldehyde. The results showed that higher CO partial pressure tend to suppress the isomerization of alpha olefin to internal olefine. Under the condition of 100℃, 2.0MPa, [Rh]=1.0×10-3mol/L,[TPPTS]/[Rh]=25, the conversion of the mixture of isomeric butenes and the selectivity for n-pentanal are 34.7% and 84.4%, respectively after four hours of reaction.3. Pentanal as the products of butene hydroformylation were hydrogenated in the RuCl3/TPPTS biphasic catalytic condition : [Ru]=6.0×10-3mol/L,[TPPTS]/[Ru] =3, 80℃,1.0MPa,the conversion of pentanals mixtures to pentanols was 95% and almost no by-products determined.更多还原