MTO在离子液体中催化1-己烯环氧化研究

MTO在离子液体中催化1-己烯环氧化研究摘要铼是我国的特有资源之一，目前在国内关于铼作为催化剂的应用多为无机催化剂，但以铼的金属有机化合物作为催化剂使用却少见报道，有关铼的衍生物的研究工作也不多见，因此，开发新型高效的金属有机催化剂具有很大的理论及现实意义。甲基三氧化铼（CH3ReO3，简称MTO）是20世纪90年代涌现出来的一种高效的过渡金属有机催化剂，它具有许多优良的催化性能，多被用来完成烯烃的环氧化作用，大多都能获得很好的选择性和转化率。离子液体就是在室温(或稍高于室温)下呈液态的仅由离子所组成的液体。离子液体(ionicliquids),又称“室温熔融盐”(RoomtemperaturemoltenSalts),室温离子液体(Roomtemperatureionicliquids)，也称液态有机盐(liquidorganicsalt)等。本实验使用的离子液体为铼的离子液体（1-烷基-3-甲基咪唑-高铼酸盐）。实验以MTO为催化剂，UHP为氧化剂，以[C5mim][ReO4]离子液体作为溶剂对1-己烯进行催化环氧化，分别考察了氧化剂用量，催化剂用量、溶剂用量对1-己烯转化生成其环氧化物的影响，获得了实验组分最佳组分摩尔比为：底物：催化剂：氧化剂=50:1：125。因此，本实验使用直链烯烃做底物相对来说得到了较为理想的结果。同时实验对MTO在催化过程中的动力学过程进行了初步研究，并成功分离出MTO催化中间产物dpRe（MTO的双过氧化物，分子式：CH3ReO5）。关键词：离子液体；MTO；环氧化；UHP；1-己烯AbstractRheniumisourcountry'suniqueresourcesandiscurrentlyinthedomesticaboutoneoftheapplicationascatalystRheniumforinorganiccatalyst,butthemetalorganiccompoundswithRheniumbutareusedascatalysts,therelevantRheniumrarereportsderivativesisrare,sowork,exploitingnewefficientmetalorganiccatalysthasgreattheoreticalandrealisticsignificance.Methyl3oxidationRhenium(CH3ReO3,abbreviationMTO)isemergingin1990sanefficienttransitionmetalorganiccatalyst,ithasmanyfinecatalyticperformance,muchisusedtocompletetheroleofepoxyolefins,mostlycanobtainverygoodselectivityandconversionrate.Ionicliquidisinroomtemperature(orjustahigherthantemperature)consistingofonlybyionicliquid.Ionicliquids(RoomtemperaturemoltenSalt),alsocalledthemoltensalt(Roomtemperatureionicliquids),room-temperatureionicliquids(temperatureionicliquids),alsocalledliquidorganicsalt(liquidorganicsalt),etc.TheionicliquidsusedinthisexperimentisRheniumionicliquids(1-alky-3-methylperrhenateacidsalt).ExperimentstoMTOascatalyst,UHPastheoxidant,withC5mim][ReO4]ionicliquid,assolventto1-hexenecatalyticepoxidationoxidantamountused,theauthorexaminesthecatalyst,solventconsumption,on1-hexeneintotheepoxycureslimonenegeneratedtheinfluenceofcomponents,obtainedexperimentthanforbestcomponentsMooreofsubstrate:catalystoxidant=50:1:125.Therefore,thisexperimentusingolefindosubstrateunbranchedrelativelyidealresultobtained.MeanwhileexperimentincatalyticprocessofMTOkineticprocesswasstudied,andtheseparateMTOcatalyticmiddlesuccessdpRe(MTOproductofdoubleperoxide,molecularformula:CH3ReO5).Keywords：ionicliquid；MTO；epoxidation；UHP；1-hexene目录第一章序言..............................................................................................11.1MTO简介.....................................................................................................................11.2离子液体简介.............................................................................................................21.2.1离子液体的特点...............................................................................................................21.2.2离子液体的分类...............................................................................................................21.2.2离子液体的合成方法.......................................................................................................21.3MTO催化烯烃环氧化研究现状................................................................................31.4本课题研究目的与意义.............................................................................................31.5本实验设计方案优点及创新点.................................................................................7第二章实验部分......................................................................................82.1仪器与设备.................................................................................................................82.2药品与试剂.................................................................................................................92.3MTO的制备................................................................................................................92.3.1AgReO4的制备.................................................................................................................92.3.2MTO的制备......................................................................................................................92.4铼离子液体的合成...................................................................................................102.4.1溴盐的合成.....................................................................................................................102.4.2铼离子液体的合成1-烷基-3-甲基咪唑-高铼酸盐.........................................................X2.5MTO催化1-己烯环氧化正交试验..........................................................................102.6MTO催化机理研究..................................................................................................152.6.1MTO及其过氧化物最大吸收波长的确定.....................................................................162.6.2MTO氧化反应历程研究...............................................................................................XVI2.6.3dpRe的分离和催化烯烃环氧化反应历程的研究.........................................................17第三章结论与展望....................................................................................183.1结论................................................................................................