带锚链固定的多相金属羰基络合物催化剂的制备及其性能研究
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摘要
本文首先在标准无水无氧操作系统内以三苯基膦与丙烯酸为原料合成了二苯基膦丙酸，并利用质谱、H-NMR及傅立叶变换红外光谱(FT-IR)对其结构进行了表征。在N-羟基琥珀酰亚胺和二环己基碳二亚胺存在下，其与胺丙基三乙氧基硅烷反应，使膦配体功能化，然后将[Rh(CO)_2Cl]_2与功能化的膦配体反应制得均相铑膦络合催化剂，最后与正硅酸乙酯一起通过溶胶-凝胶的方法制备带锚链固定的铑膦络合物催化剂。
通过实验考察了催化剂的制备过程中pH值、成胶温度、干燥温度、铑/膦比等对催化剂的催化活性的影响，找到了催化剂的最佳制备条件。并利用傅立叶变换红外光谱(FT-IR)、XPS、热重分析及N_2吸附对催化剂进行了表征，揭示了内部结构与催化活性的关系。
通过催化1-己烯的氢甲酰化反应考察了带锚链固定的铑膦络合物催化剂的催化性能。分别考察了反应温度、反应压力、反应时间、催化剂用量及反应溶剂对反应的影响。在最佳条件下进行反应，1-己烯的转化率为97.8％、生成醛的选择性99.9％、n/i比1.12。并对催化剂的可重复性进行考察，催化剂循环使用8次后仍具有较高的催化活性。通过ICP及XPS对催化剂的表征结果得知催化剂在使用过程中只是催化剂外表面铑原子的脱落造成少量的铑流失(占铑含量的12.68％)，部分解决了金属铑的流失问题，具有较好的可重复性。
此外，固相化铑膦络合物催化剂还用于其他烯烃的氢甲酰化反应，发现：
不同烯烃的氢甲酰化反应转化率：1-己烯＞1-辛烯＞1-十二烯＞苯乙烯
不同烯烃的氢甲酰化反应生成醛的正/异比：苯乙烯＞1-十二烯＞1-辛烯＞1-己烯
In the thesis, Ph2PCH2CH2COOH was prepared from Ph3P in the usual Schlenk technique and characterized by MS, H-NMR and FI-IR spectra first. Then let it react with H2NCH2CH2CH2Si(OEt)3 to give the ligand with function group -Si(OEt)3, which reacts with [Rh (CO)2Cl]2 to give the correspondent homogeneous catalyst. Finally, the anchored heterogenized complex catalyst was obtained from the copolymerization of the above ligand with TEOS by sol-gel method.
The factors affecting the properties of the catalysts in the preparation of the catalysts by the sol-gel method, which include pH, encapsulating temperature, drying temperature and Rh/P etc. were also investigated. The encapsulating conditions were optimized based on the results above. The catalyst was characterized by FI-IR spectra, XPS, TG-DTA and N2 absorption. The relationship between catalytic property and internal structure was revealed.
The catalytic property of the catalyst for hydroformylation of 1-hexene was studied. The effects on the catalytic activity and selectivity of reaction temperature, time, pressure, quantities of catalyst and the kinds of solvent were observed. It was found that the conversion of 1-hexene can go up to 97.8%, the selectivity of aldehyde can be 99.9% and the n/i is 1.12, when the reaction was run at the optimal reaction conditions. Furthermore, the catalyst can be run for 8 times without obvious loss of activity. From the result of ICP and XPS, we can know that the catalyst only 12.68% losing of Rh mainly coming from the outer surface of the matrix. Therefore the losing of Rh was resolved partly, and the catalyst has the better recyclable property.
Finally, the anchored heterogenized organometallic complex catalyst was applied to the hydroformylation of other olefins. It was found that conversion decreased as the order of 1-hexene >1-octylene > 1-dodecene > styrene. However the order of n/i of different olefms is styrene> 1-dodecene > 1-octylene > 1-hexene.
通过实验考察了催化剂的制备过程中pH值、成胶温度、干燥温度、铑/膦比等对催化剂的催化活性的影响，找到了催化剂的最佳制备条件。并利用傅立叶变换红外光谱(FT-IR)、XPS、热重分析及N_2吸附对催化剂进行了表征，揭示了内部结构与催化活性的关系。
通过催化1-己烯的氢甲酰化反应考察了带锚链固定的铑膦络合物催化剂的催化性能。分别考察了反应温度、反应压力、反应时间、催化剂用量及反应溶剂对反应的影响。在最佳条件下进行反应，1-己烯的转化率为97.8％、生成醛的选择性99.9％、n/i比1.12。并对催化剂的可重复性进行考察，催化剂循环使用8次后仍具有较高的催化活性。通过ICP及XPS对催化剂的表征结果得知催化剂在使用过程中只是催化剂外表面铑原子的脱落造成少量的铑流失(占铑含量的12.68％)，部分解决了金属铑的流失问题，具有较好的可重复性。
此外，固相化铑膦络合物催化剂还用于其他烯烃的氢甲酰化反应，发现：
不同烯烃的氢甲酰化反应转化率：1-己烯＞1-辛烯＞1-十二烯＞苯乙烯
不同烯烃的氢甲酰化反应生成醛的正/异比：苯乙烯＞1-十二烯＞1-辛烯＞1-己烯
In the thesis, Ph2PCH2CH2COOH was prepared from Ph3P in the usual Schlenk technique and characterized by MS, H-NMR and FI-IR spectra first. Then let it react with H2NCH2CH2CH2Si(OEt)3 to give the ligand with function group -Si(OEt)3, which reacts with [Rh (CO)2Cl]2 to give the correspondent homogeneous catalyst. Finally, the anchored heterogenized complex catalyst was obtained from the copolymerization of the above ligand with TEOS by sol-gel method.
The factors affecting the properties of the catalysts in the preparation of the catalysts by the sol-gel method, which include pH, encapsulating temperature, drying temperature and Rh/P etc. were also investigated. The encapsulating conditions were optimized based on the results above. The catalyst was characterized by FI-IR spectra, XPS, TG-DTA and N2 absorption. The relationship between catalytic property and internal structure was revealed.
The catalytic property of the catalyst for hydroformylation of 1-hexene was studied. The effects on the catalytic activity and selectivity of reaction temperature, time, pressure, quantities of catalyst and the kinds of solvent were observed. It was found that the conversion of 1-hexene can go up to 97.8%, the selectivity of aldehyde can be 99.9% and the n/i is 1.12, when the reaction was run at the optimal reaction conditions. Furthermore, the catalyst can be run for 8 times without obvious loss of activity. From the result of ICP and XPS, we can know that the catalyst only 12.68% losing of Rh mainly coming from the outer surface of the matrix. Therefore the losing of Rh was resolved partly, and the catalyst has the better recyclable property.
Finally, the anchored heterogenized organometallic complex catalyst was applied to the hydroformylation of other olefins. It was found that conversion decreased as the order of 1-hexene >1-octylene > 1-dodecene > styrene. However the order of n/i of different olefms is styrene> 1-dodecene > 1-octylene > 1-hexene.
引文
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