CAJ | 학술논문

利用环己亚胺与1,3-丙烷磺酸内酯生成的1-（3-磺丙基）环己亚胺盐,合成了2种新型Br nsted酸性离子液体1（-3-丙磺基）环己亚胺硫酸氢盐（[HMIPS]HSO4）和1-（3-丙磺基）环己亚胺对甲苯磺酸盐（[HMIPS]OTs）。采用1H NMR、FTIR、LC-ESI-MS及DSC-TG等方法对其进行了表征。结果表明,所合成的[HMIPS]HSO4和[HMIPS]OTs是一类新型的Br nsted酸性离子液体。该类型离子液体含有环己亚胺七元环,分解温度高于260℃,其水溶液的pH值与相同浓度的硫酸水溶液相近,具有较强的Br nsted酸性。考察了所合成的新型离子液体对柠檬酸和正丁醇酯化反应的催化性能,并与传统咪唑类离子液体进行了对比。结果显示,所合成的新型离子液体[HMIPS]HSO4具有良好的催化活性,在n（柠檬酸）∶n（正丁醇）∶n（[HMIPS]HSO4）=5∶1∶0.02、110～130℃和回流反应2 h的条件下,柠檬酸的转化率为98.3%,柠檬酸三丁酯的收率可达97.5%,[HMIPS]HSO4催化剂在重复使用10次后催化活性未见明显下降。
이용배기아알여1,3-병완광산내지생성적1-（3-광병기）배기아알염,합성료2충신형Br nsted산성리자액체1（-3-병광기）배기아알류산경염（[HMIPS]HSO4）화1-（3-병광기）배기아알대갑분광산염（[HMIPS]OTs）。채용1H NMR、FTIR、LC-ESI-MS급DSC-TG등방법대기진행료표정。결과표명,소합성적[HMIPS]HSO4화[HMIPS]OTs시일류신형적Br nsted산성리자액체。해류형리자액체함유배기아알칠원배,분해온도고우260℃,기수용액적pH치여상동농도적류산수용액상근,구유교강적Br nsted산성。고찰료소합성적신형리자액체대저몽산화정정순지화반응적최화성능,병여전통미서류리자액체진행료대비。결과현시,소합성적신형리자액체[HMIPS]HSO4구유량호적최화활성,재n（저몽산）∶n（정정순）∶n（[HMIPS]HSO4）=5∶1∶0.02、110～130℃화회류반응2 h적조건하,저몽산적전화솔위98.3%,저몽산삼정지적수솔가체97.5%,[HMIPS]HSO4최화제재중복사용10차후최화활성미견명현하강。
Two novel Br？nsted acidic ionic liquids,1-（3-sulfopropyl）hexamethyleneiminium hydrogen sulfate（HSO4）and 1-（3-sulfopropyl）hexamethyleneiminium tosilate（OTs）were prepared using hexamethyleneimine and 1,3-propane sultone,etc.They were characterized by 1H NMR,FT-IR,LC-ESI-MS and DSC-TG.The results proved that the ionic liquids synthesized contain a hexamethyleneimine with seven member ring and possess stronger Br？nsted acidity,decomposition temperayure are over 260 ℃ and the acidity of aqueous solution of HSO4 is similar to that of aqueous solution with the same concentration of sulfuric acid.Their catalytic activities for the esterification of citric acid with n-butanol were examined and compared with the imidazolium-based ionic liquids.The results showed that HSO4 exhibits excellent catalytic activity,the conversion of citric acid was 98.3% and the yield of tributyl citrate reached 97.5% under the conditions of n（citric acid）∶n（n-butyl alcohol）∶n（HSO4）=5∶1∶0.02,110—130 ℃ and reflux 2 h.Furthermore,The activity of HSO4 catalyst reused at least 10 times was not significantly decreased.