新型离子液体型固体酸的合成及其在酯化反应中的应用  

Synthesis of Novel Ionic Liquid-Based Solid Acids and Their Catalytic Performances in Esterifications

作　　者：李工[1] 徐小军[1] 徐恒[1] 吴非克[1] 佟惠娟[1] 

机构地区：[1]常州大学石油化工学院,江苏常州213164

出　　处：《石油化工》2012年第6期641-646,共6页Petrochemical Technology

基　　金：江苏省自然科学基金项目(BK2007043)

摘　　要：利用环己亚胺、1,3-丙烷磺酸内酯和Keggin型杂多酸合成了两种新型离子液体型固体酸1-(3-磺丙基)环己亚胺十二磷钨酸盐([HMIPS]3PW12O40)和1-(3-磺丙基)环己亚胺十二磷钼酸盐([HMIPS]3PMo12O40),采用1H NMR,31P NMR,FTIR,TG等方法对反应中间体和产物进行了表征。表征结果显示,所合成的[HMIPS]3PW12O40和[HMIPS]3PMo12O40是含Br?nsted酸的离子液体型固体酸,在室温下均为固体,能溶于水,其熔点分别为175.4℃和182.3℃。在酯化反应中,[HMIPS]3PW12O40和[HMIPS]3PMo12O40是一类反应控制自分离催化剂。以[HMIPS]3PW12O40为催化剂,在n(乙酸):n(环己醇)=5:1、反应温度90℃和反应时间2.0 h的条件下,环己醇的转化率和乙酸环己酯的选择性分别为96.31%和99.26%;在n(柠檬酸):n(正丁醇)=1:5、反应温度120℃和反应时间3.0 h的条件下,柠檬酸的转化率和柠檬酸三丁酯的选择性分别为97.89%和98.49%。Two novel ionic liquid-based solid acids, 1-（3-sulfopyl） hexamethyleneiminium phosphotungstic acid（ I HMIPS 13PW12040） and 1-（3-sulfopyl） hexamethyleneiminium phosphomolybdic acid（EHMIPS 3PMot204o）, were synthesized from hexamethyleneimine, 1, 3-propane sultone and Keggin heteropoly acids. The novel ionic liquid-based solid acids and the intermediate 1-（3- sulfopropyl） hexamethyleneiminium（HMIPS） were characterized by means of H NMR, 31p NMR, FTIR and TG. The results showed that IHMIPSI 3PW12040 and IHMIPSJ 3PMo12040 were ionic liquid-based solid acids with Br6nsted acidity, their melting points were 175.4℃ and 182.3℃ respectively, and they could dissolve in water and were solid at room temperature. [ HMIPS 13PW2040 and [HMIPS ] 3PMo12040 were reaction-controlled self-separated catalysts in esterification. Some esterification reactions on [HMIPS ] 3PW12040 catalyst were studied. The conversion of cyclohexanol and the selectivity to cyclohexyl acetate could reach 96.31% and 99.26% respectively under the appropriate reaction conditions of n（acetic acid） ： n（cyclohexanol） 5 ： 1, reaction temperature 90 ℃ and reaction time 2.0 h. The conversion of citric acid and the selectivity to tributyl citrate could reach 97.89% and 98.49% respectively under the condition of n（citric acid） ： n（n-butanol） 1 ： 5, reaction temperature 120 ℃ and reaction time 3.0 h.

关 键 词：离子液体型固体酸催化剂 环己亚胺 KEGGIN型杂多酸 酯化 乙酸环己酯 柠檬酸三丁酯 

分 类 号：TQ032.4[化学工程]