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

作　　者：张志超[1] 李璐 韩双[1] ZHANG Zhi-chao;LI Lu;HAN Shuang(School of Science,Shenyang University of Chemical Technology,Shenyang 110142,China)

机构地区：[1]沈阳化工大学理学院,辽宁沈阳110142

出　　处：《化学试剂》2023年第10期70-76,共7页Chemical Reagents

基　　金：中国科学院长春应用化学研究所电分析化学国家重点实验室开放课题基金项目(SKLEAC202204);辽宁省自然科学基金项目(2022-MS-293)。

摘　　要：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.

关 键 词：多相催化 膦-铑催化剂 聚合物载体 氢甲酰化反应 1-己烯 

分 类 号：O62[理学—有机化学]