Study On The Thermoregulated Phase-Separable Catalysis System And It's Applications In Hydroformylation Of Higher Olefins

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.