三苯基膦功能化聚酰胺/铑催化烯烃氢甲酰化

Hydroformylation of Olefins Catalyzed by Triphenylphosphine Functionalized Polyamide/Rhodium Catalyst

以三(3-氨基苯基)膦与联苯-4,4′-二甲酸为原料合成了一种三苯基膦功能化的聚酰胺有机载体,并通过红外光谱、固体核磁对其结构进行表征。聚酰胺载体与Rh(acac)(CO)_(2)组成的多相催化体系可以有效地催化1-己烯的氢甲酰化反应。研究表明,该多相催化剂具有较好的化学稳定性和催化效果。在90℃下,甲苯溶剂中,催化剂在15 h内完全催化转化1-己烯生成庚醛和2-己烯,产物中醛的选择性为37.4%。通过离心的方法可以实现催化剂与产物的快速分离及多次利用。催化剂的循环使用研究表明,在使用5次后,对1-己烯的催化活性仍高达100%,醛的选择性在34.9%以上,产物醛的正异构比约为2.5。

A triphenylphosphine functionalized porous organic polyamide was synthesized using tri(3-aminophenyl)phosphine and biphenyl-4,4′-dicarboxylic acid as starting materials.The structure of the isolated polyamide was identified by Fourier transform infrared spectroscopy and solid-state nuclear magnetic resonance.A heterogeneous catalyst was prepared by combination of the porous polyamide and Rh(acac)(CO)_(2)for catalytic hydroformylation of 1-hexene.It was shown that the heterogeneous catalyst displayed good chemical stability and catalytic performance.The conversion of 1-hexene to heptal and 2-hexene was 100%at 90℃for 15 h with toluene as the reaction solvent,and the selectivity of aldehyde products was 37.4%.Furthermore,the heterogeneous catalyst can be rapidly separated from the reaction mixtures by centrifugation and recycled for multiple uses.The heterogeneous catalyst showed excellent catalytic activity after 5 runs.The conversion of 1-hexene was still as high as 100%,with the selectivity for aldehyde products higher than 34.9%.Meanwhile,the ratio of the linear aldehyde to the branched product was approximately 2.5.