双亚磷酸酯和双膦混合配体在丁烯氢甲酰化反应中的应用研究

Study on Hydroformylation of Butene with Diphosphite and Diphosphine Mixed-Ligands Modified Catalysts

考察了双亚磷酸酯配体Bisphosphite 1、Bisphosphite 2及双膦配体DPPE、DPPP、DPPB、BISBI在丁烯氢甲酰化反应中的反应活性和选择性,并对双亚磷酸酯配体和双膦配体进行混合,应用到丁烯氢甲酰化反应当中,对混合配体进行筛选发现Bisphosphite 1与DPPB混合配体的反应效果最佳,明显提高了1-丁烯氢甲酰化产物醛的正异构比,并通过31P NMR等方法推测了混合配体与铑配位的关键配合物中间体.通过正交实验优选了铑催化剂浓度、Bisphosphite 1浓度与DPPB浓度,其优化的催化剂配方对1-丁烯氢甲酰化的正异构比达到76.3,平均TOF 1821 h-1.

The reaction activity and selectivity for hydroformylation of butene was investigated by using the diphosphite ligand such as bisphosphite 1、bisphosphite 2 and diphosphine ligands such as DPPE、DPPP、DPPB、BISBI.In addition,diphosphite and diphosphine ligands were mixed and the n-aldehyde / iso-aldehyde ration was improved by bisphosphite 1 and DPPB mixed ligands modified rhodium catalyzed hydroformylation of 1-butene. The mixed ligands coordinate with rhodium to form proposed key complex by31 P NMR method. The optimum catalyst composition such as rhodium concentration,bisphosphite 1 concentration and DPPB concentration was screened by using the orthogonal lexperimental design. The n-aldehyde / iso-aldehyde ration for 1-butene hydroformylation was increased to 76. 3 and the average TOF was 1 821 h- 1in the optimum catalyst composition.