摘要
为实现1-丁烯高效、绿色环氧化制备1,2-环氧丁烷(BO),结合仿生催化氧气活化的反应思路,以1-丁烯为原料、邻苯二甲酰亚胺(PI)为催化剂、空气为氧化剂,经催化环氧化反应制备了BO。通过单因素实验,考察了递氢体类型和用量、1-丁烯用量、PI用量、溶剂种类、空气压力、反应时间、反应温度对1-丁烯转化率和BO选择性的影响。对优化后反应体系的底物普适性进行了分析,并通过自由基检测和识别实验,探究了反应机理。结果表明,在1-丁烯8 mmol、递氢体正丁醛8 mmol、溶剂乙腈20 mL、催化剂PI 5 mg、氧化剂空气压力1.6 MPa、反应温度75℃、反应时间3.0 h的最优条件下,1-丁烯转化率可达到50.0%,BO选择性达到96.0%。PI/正丁醛环氧化体系对正构烯烃、线型内烯烃、卤代烯烃等多种类型烯烃具有较好的普适性。在PI催化作用下,递氢体正丁醛脱氢原位产生高活性酰基自由基,其与空气中的O_(2)结合形成高活性的过氧自由基物种,过氧自由基辅助过氧酸是促进烯烃环氧化的途径。
In order to achieve highly efficient and green epoxidation of 1-butene to 1,2-butane epoxide(BO),and based on inspiration from biomimetic catalytic oxidation,BO was synthesized via catalytic epoxidation with 1-butene as raw material,phthalimide(PI)as catalyst,and air as oxidant.The effects of hydrogen transmitter type and amount,1-butene amount,PI amount,solvent type,air pressure,reaction time,and reaction temperature on 1-butene conversion and BO selectivity were analyzed by single factor experiments.The substrate universality of the optimized reaction system was evaluated,while the reaction mechanism was further explored through free radical detection and recognition experiments.The results showed that the conversion rate of 1-butene could reach 50.0% and the selectivity of BO could reach 96.0% under the optimal conditions of 1-butene 8 mmol,hydrogen transfer n-butanal 8 mmol,solvent acetonitrile 20 mL,catalyst PI 5 mg,oxidizer air pressure 1.6 MPa,reaction temperature 75℃ and reaction time 3.0 h.Meanwhile,PI/n-butanal epoxidation system exhibited good universality to many types of alkenes,such as normal alkenes,linear internal alkenes,halogenated alkenes.Under the catalysis of PI,the dehydrogenation of n-butanal generated highly active acyl free radicals in-situ,which combined with oxygen molecules in the air to form highly active peroxide radical species,and the peroxide free radical assisted peroxide acid was the way to promote olefin epoxidation.
作者
刘金成
李琛
高萌
熊超
赵光辉
纪红兵
LIU Jincheng;LI Chen;GAO Meng;XIONG Chao;ZHAO Guanghui;JI Hongbing(Daqing Petrochemical Research Center,PetroChina Petrochemical Research Institute,Daqing 163714,Heilongjiang,China;State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology,Institute of Green Petroleum Processing and Light Hydrocarbon Conversion,College of Chemical Engineering,Zhejiang University of Technology,Hangzhou 310014,Zhejiang,China;School of Chemistry,Sun Yat-sen University,Guangzhou 510275,Guangdong,China)
出处
《精细化工》
北大核心
2025年第11期2543-2552,共10页
Fine Chemicals
基金
国家重点研发计划纳米技术专项(2020YFA0210900)
国家自然科学基金项目(21938001,21961160741,42177029)。
关键词
仿生催化
空气氧化
轻质烯烃
环氧化
氧化机理
精细化工中间体
biomimetic catalysis
air oxidation
light olefins
epoxidation
oxidation mechanism
fine chemical intermediates
