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1、物理化學(xué)學(xué)~(WuliHuaxueXuebao1FebruaryActa腳.一Chim.Sin.2015,31(2),337-343337[Article]doi:10.3866/PKU.WHXB201412101WWW.whxb.pku.edu.cn堿性離子液體催化合成三羥甲基丙烷龍金星’袁正求’馬浩舒日洋’李雪輝·(中國(guó)科學(xué)院廣州I能源研究所,中國(guó)科學(xué)院可再生能源重點(diǎn)實(shí)驗(yàn)室,廣J'l、l510640;華南理工大學(xué)化學(xué)與化工學(xué)院,廣州510640)摘要:以堿性離子液體為催化劑,構(gòu)建了一種新型、高效的合成三羥甲基丙烷(TMP)的方法.系統(tǒng)考察了催化劑類型、催
2、化劑用量、反應(yīng)溫度、反應(yīng)時(shí)間、甲醛與正丁醛用量比等因素對(duì)三羥甲基丙烷分離收率的影響.研究結(jié)果表明:堿性離子液體的催化性能與其堿強(qiáng)度息息相關(guān),堿性越強(qiáng)、催化活性越高.最優(yōu)條件下,經(jīng)離子液體【bmim]OH催化后,可得到84%的TMP分離收率。這一結(jié)果優(yōu)于傳統(tǒng)的有機(jī)無(wú)機(jī)堿催化體系且成功規(guī)避了傳統(tǒng)堿催化合成TMP過(guò)程中繁瑣的除鹽過(guò)程、降低了過(guò)程能耗.此外,離子液體催化劑和未反應(yīng)的丁醛均表現(xiàn)了良好的重復(fù)使用性能.關(guān)鍵詞:三羥甲基丙烷:離子液體:堿性強(qiáng)度:Cannizzaro縮合:重復(fù)使用性中圖分類號(hào):0643CatalyticSynthesisofTrimethyl
3、olpropaneinthePresenceofBasicIonicLiquidLONGJin—Xing’'’YUANZheng-Qiu’MAHaoSHURi—Yang’LIXue-Hui'’(KeyLaboratoryofRenewableEnergy,GuangzhouInstituteofEnergyConversion,ChineseAcademyofSciencesGuangzhou510640,R.China;SchoolofChem~tryandChemicalEngineering,SouthChinaUniversityofTechnolo
4、gy,Guangzhou510640,R.China)Abstract:Ionicliquid(1L)catalystattractsincreasingattentionduringlastfeWdecadesduetoitsexcellentadvantagesofbothhomogeneousandheter0qene0uscatalyst.Here,anovelandefficientstrategyfortheproductionoftrimethylolpropane(TMP)iSproposedwithbasicILcatalysts.Thec
5、atalyticactivitiesoftheILcatalystsarejnvestigated.Theeffectsofcatalystdosage,reactiontemperature,time,andthemolarratioofthereactantsarealsostudied.TheresultsshowthatthebasicityoftheILcatalysthasasignificantefectonthecatalyticactivity,wherestrongerbasicityindicateshighercatalyticact
6、ivity.TheIL1-buty1.3-methylimidazoliumhydroxyl(『bmim1OH)lSproventobethemosteficientcatalystwheremorethan84%isolatedyieldofTMPwasobtainedunderoptimizedconditions.Furthermore,boththelLcatalystandbutyraIdehVdeshowexcellentrecyclability.Moreover.thislLcatalyticsystemavoidstheinevitable
7、desalinationencounteredbycurrentprocessesutilizinginorganicalkalicatalysts.KeyWords:Trimethylolpropane;Ionicliquid;Basicstrength;CannizzarocondensationRecyclability1lntroductionmethylandneopentylfunctionalgroups,hasbeenregardedasanTrimethylolpropane(TMP).a(chǎn)polyolcontaining—hydroxy—i
8、mportantintermediateintheo