新型负载水相催化剂(SAPC)的制备及其在丙烯氢甲酰化反应中的应用

Preparation and Application of a Novel Supported Aqueous-phase Catalysis (SAPC) in Propylene Hydroformylation Reaction

以新型水溶性二磺化 - 1-苯基二苯并膦 (简称 PDBPDS)为配体 ,制备了铑膦配合物 Rh(acac) (CO ) -(PDBPDS) 3.将其负载于高吸水性载体上 ,制得负载水相催化剂 ,并对催化剂的制备条件进行了优化 .以人造沸石为载体 ,在载水量 30 % ,[Rh]=2 .0× 10 - 5、 [P]/ [Rh]=40的条件下 ,筛选出丙烯氢甲酰化反应的最佳工艺条件 .在反应温度 10 0℃、压力 2 .0 MPa、搅拌速度为 5 0 0 r/ m in条件下 ,催化剂活性达 10 12 g丁醛 / (g Rh· h) ;正异比高达 43.5 ;在有机相中铑的浓度为 1.2× 10 - 9,解决了均相反应催化剂回收和循环使用的问题 .实验结果表明 ,新型配体二磺化 - 1-苯基二苯并膦是一性能较好的新配体 。

Using disodium\|1\|phenyl\|dibenzophosphole\|disulfonate (PDBPDS) as ligand, a high activity P\|Rh complex, Rh(acac)\-2(CO)\-2, was synthesized. Further, a novel supported aqueous\|phase catalyst was prepared by supporting a thin film of the solution of this water\|soluble organometallic complex on a high\|surface\|area hydrophilic permutite. When H\-2O content of SAPC is 30%, =2.0×10 -5 , /=40, the activity of the novel catalyst for propylene hydroformylation reaction under the optimium reaction conditions (temperatur 100 ℃, pressure 2.0 MPa, stirring speed 500 r/min), achieved 1 012 g aldehyde/\{(g Rh·h)\} and n/i =43.5. Rhodium in organic phase is only 1.2×10 -9 . The results show that the novel ligand( PDBPDS) and catalyst (SAPC) possess high activity and selectivity; and ability to reduce the loss of rhodium in organic phase.