锰卟啉仿生催化制备1,2-环氧丁烷  

Synthesis of butylene oxide catalyzed by Mn porphyrin

作　　者：张晶花 祁连山 田恒水[1] ZHANG Jing-hua;QI Lian-shan;TIAN Heng-shui(School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学化工学院

出　　处：《现代化工》2019年第12期105-110,共6页Modern Chemical Industry

摘　　要：制备了四苯基卟啉、四(4-甲基苯基)卟啉、四(4-甲氧基苯基)卟啉、四(4-氟苯基)卟啉、四(4-氯苯基)卟啉及其对应的锰卟啉,并对其结构进行了表征。以前述卟啉为催化剂,催化1-丁烯环氧化制备1,2-环氧丁烷。考察了催化剂种类、催化剂浓度、丁烯用量、共还原剂用量、溶剂用量、转速、反应时间、反应温度、反应压力对反应结果的影响。结果表明,以四(4-氟苯基)锰卟啉为催化剂,在催化剂浓度为8×10^-6mol/L、丁烯用量为1.9 L、丙烯醛用量为3 mL、溶剂用量为200 mL、转速为500 r/min、反应压力为1.6 MPa、反应温度为103℃、反应时间为60 min的条件下,1-丁烯转化率为96.39%,1,2-环氧丁烷收率为95.04%,选择性为98.61%。Tetraphenyl porphyrin,tetra(4-methylphenyl)porphyrin,tetra(4-methoxyphenyl)porphyrin,tetra(4-fluorophenyl)porphyrin,tetra(4-chlorophenyl)porphyrin and their corresponding Mn metalloporphyrin are synthesized and characterized.The catalytic oxidation of butylene to butylene oxide in molecular oxygen is catalyzed by the prepared Mn metalloporphyrins.The effects of the types of metalloporphyrin catalyst,the concentration of metalloporphyrin catalyst,the dosages of butylene,co-reduction agent and solvent,rotation rate,reaction time,reaction temperature and pressure on the reaction result are investigated.The optimum reaction conditions obtained are as follows:(p-F)TPPMnCl is used as catalyst with a concentration of 8×10^-6 mol·L^-1,the dosages of butylenes,acrolein and solvent are 1.9 L,3 mL and 200 mL respectively,rotation speed is 500 r·min-1,reaction lasts for 60 min,reaction temperature is set at 103℃,and reaction pressure is 1.6 MPa.The conversion rate of butylene reaches 96.39%,the yield of butylene oxide reaches 95.04%and the selectivity of butylene oxide reaches 98.61%under optimum reaction conditions.

关 键 词：金属卟啉 丁烯 环氧丁烷 仿生催化 环氧化 

分 类 号：TQ231[化学工程—有机化工]