温控相分离催化及其在高碳烯烃氢甲酰化反应中的应用
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摘要
本论文通过测定非离子表面活性膦配体在非极性非质子溶液中溶解规律，发现P[p-C_6H_4O(CH_2CH_2O)_nH]_3(PETPP,N=3n)在甲苯、苯中有临界溶解温度(CST)特性，为设计具有温控相分离功能的催化体系奠定了基础，这种具有“一相反应，两相分离”新型液／液两相催化体系—温控相分离催化，将为解决均相贵金属催化剂的分离回收提供一条新的途径。
作者重点考察了以PETPP／Rh络合物为催化剂的温控相分离高碳烯烃氢甲酰化反应及其分离、循环使用效果。实验结果表明，温控相分离催化体系可很好地催化C_(6-14)直链高碳烯烃氢甲酰化反应。以甲苯为溶剂，在最佳反应条件下：130℃，6.0MPa(CO／H_2=1／1)，P／Rh=10，S／Rh=1000，反应4h，1-癸烯的转化率和醛收率分别达到98.7％和96.0％。作者发现使用窄分子量分布的PETPP和甲苯／正庚烷混合溶剂可使铑流失较纯甲苯溶剂降低50％以上；PETPP／Rh络合物循环使用十次，催化剂活性基本保持不变，催化剂总流失量(质量百分比)为3.44％。这表明温控相分离催化体系兼具了均相催化和多相催化的优点。同时，温控相分离催化体系对支链内烯烃氢甲酰化反应也有很好的催化活性，在最佳反应条件下，三聚丙烯转化率和醛收率分别达到83.6％和81.1％。
作者还研究了温控相分离催化的苯乙烯氢化反应，扩大了温控相分离催化体系的应用范围。
In this paper, the solubility of nonionic tensioactive phosphine ligand P[p-C6H4O(CH2CH20)nH]3 (PETPP, n=6-12, N=3n)in different nonpolar and aprotic solvent was investigated. It was found that PETPP (N=18-36) possess distinct critical solution temperature (CST) in toluene and benzene. A novel concept (Thermoregulated Phase-Separable Catalysis, TPSC) based on CST of PETPP for separating catalyst from the reaction mixture is proposed.
The catalytic properties and recycling efficiency of PETPP/Rh complex on the hydroformylation of higher olefins were throughout investigated. The experiment results indicated that the hydroformylation of C6-14 straight chain higher olefins could well conduct under TPSC system. Under the optimum condition, 130 C, 6.0 MPa (CO/H2=1/1), P/Rh = 10, S/Rh =1000, the conversion and yield for aldehyde of 1-decene reached 98.7% and 96.0%, respectively. When narrow molecular distribution of PETPP and mixed solvent used, the loss of rhodium could decrease by 50% percent compared with normal PETPP and toluene. After 10 times recycling of the catalyst, the total loss of rhodium was 3.44% mass percent, and the conversion of 1-decene was still more than 94.9%. It indicated that TPSC system was characterized by homogeneous catalysis coupled with two-phase separation. Meanwhile, the PETPP/Rh complex was very effective on the hydroformylation of tripropene. Under appropriate conditions, the conversion and yield for aldehyde of tripropene was 83.6% and 81.1%, respectively.
Ru3(CO)12/ PETTP complex was introduced as TPSC catalyst for hydrogenation of styrene which expanded the application range of TPSC system.
作者重点考察了以PETPP／Rh络合物为催化剂的温控相分离高碳烯烃氢甲酰化反应及其分离、循环使用效果。实验结果表明，温控相分离催化体系可很好地催化C_(6-14)直链高碳烯烃氢甲酰化反应。以甲苯为溶剂，在最佳反应条件下：130℃，6.0MPa(CO／H_2=1／1)，P／Rh=10，S／Rh=1000，反应4h，1-癸烯的转化率和醛收率分别达到98.7％和96.0％。作者发现使用窄分子量分布的PETPP和甲苯／正庚烷混合溶剂可使铑流失较纯甲苯溶剂降低50％以上；PETPP／Rh络合物循环使用十次，催化剂活性基本保持不变，催化剂总流失量(质量百分比)为3.44％。这表明温控相分离催化体系兼具了均相催化和多相催化的优点。同时，温控相分离催化体系对支链内烯烃氢甲酰化反应也有很好的催化活性，在最佳反应条件下，三聚丙烯转化率和醛收率分别达到83.6％和81.1％。
作者还研究了温控相分离催化的苯乙烯氢化反应，扩大了温控相分离催化体系的应用范围。
In this paper, the solubility of nonionic tensioactive phosphine ligand P[p-C6H4O(CH2CH20)nH]3 (PETPP, n=6-12, N=3n)in different nonpolar and aprotic solvent was investigated. It was found that PETPP (N=18-36) possess distinct critical solution temperature (CST) in toluene and benzene. A novel concept (Thermoregulated Phase-Separable Catalysis, TPSC) based on CST of PETPP for separating catalyst from the reaction mixture is proposed.
The catalytic properties and recycling efficiency of PETPP/Rh complex on the hydroformylation of higher olefins were throughout investigated. The experiment results indicated that the hydroformylation of C6-14 straight chain higher olefins could well conduct under TPSC system. Under the optimum condition, 130 C, 6.0 MPa (CO/H2=1/1), P/Rh = 10, S/Rh =1000, the conversion and yield for aldehyde of 1-decene reached 98.7% and 96.0%, respectively. When narrow molecular distribution of PETPP and mixed solvent used, the loss of rhodium could decrease by 50% percent compared with normal PETPP and toluene. After 10 times recycling of the catalyst, the total loss of rhodium was 3.44% mass percent, and the conversion of 1-decene was still more than 94.9%. It indicated that TPSC system was characterized by homogeneous catalysis coupled with two-phase separation. Meanwhile, the PETPP/Rh complex was very effective on the hydroformylation of tripropene. Under appropriate conditions, the conversion and yield for aldehyde of tripropene was 83.6% and 81.1%, respectively.
Ru3(CO)12/ PETTP complex was introduced as TPSC catalyst for hydrogenation of styrene which expanded the application range of TPSC system.
引文
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2 Kuntz K E, Homogeneous catalysis in water, Chemtech, 1987, 17:570-575
3 Kalck P, Dessoudeix M, Inter-facial catalysis using various water-compatible ligands in supramolecular systems, Coordination Chem. Reviews, 1999, 190-192:1185-1198
4 吴己丑，袁刚，周启召，用水溶性铑膦络合催化剂制备高碳醛，石油化工，1991，20(2)，79-85．
5 Lekhal A, Chaudhari R V, Wilhelm A M, Delmas H, Mass transfer effect on hydro -formylation catalyzed by a water soluble complex Catal. Today, 1999, 48: 265.
6 Monteil F, Queau R, Kalck P H, Behaviour of watersoluble dinuclear rhodium complexes in the hydroformylation of 1-octene, J. Organomet. Chem., 1994, 480:177-184
7 Chen H, Li Y Z, Chen J R, Cheng P M, He Y, Li X J, Micellar effect in high olefin hydroformylation catalyzed bywater-soluble rhodium complex, J. Mol. Catal. A: Chem.,1999, 149: 1-6,
8 陈华，黎耀忠，程溥明，扬清，李贤均，水溶性铑-膦配合物催化1-十二碳烯常压氢甲酰化反应研究，分子催化，1994，8(5)：347-352．
9 陈华，刘海超，黎耀忠，程溥明，李贤均，水溶性铑-膦配合物催化高碳烯烃氢甲酰化反应研究-反应条件的影响，分子催化，1995，9(2)：145-151．
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