Page 154 - 《精细化工》2023年第12期

第 40 卷第 12 期 精 细 化 工 Vol.40, No.12
2 023 年 12 月 FINE CHEMICALS Dec. 2023

催化与分离提纯技术
氨基甲酸酯型有机催化剂的制备及应用

杨建国，李金柱，徐 琰，翟留宾，张洪波

（安徽工业大学 化学与化工学院，安徽 马鞍山 243032）

摘要：碳酸乙烯酯（EC）和四乙烯五胺（TEPA）通过加成反应制备了用于酯交换合成碳酸甲乙酯（EMC）的
氨基甲酸酯型有机催化剂（TEPA-EC）。采用 FTIR、NMR 对其结构进行了表征，分析了其催化机理，考察了合
成和使用条件对催化效率的影响，对 TEPA-EC 的稳定性和耐水性进行了测试。结果表明，TEPA-EC 中的叔胺
基甲酸羟乙酯基团通过协同氢键催化酯交换反应；EC 与 TEPA 按物质的量比 5∶1 在 140 ℃反应 2 h 制得的
TEPA-EC 具有较高的催化活性。对于 n(DMC)∶n(EtOH)=2∶1 在 78 ℃反应 7 h 的酯交换反应，当 EtOH 4.60 g、
TEPA-EC 用量为 1%时（以原料总质量计，下同），EtOH 的转化率为 59.50%、EMC 的选择性为 83.77%，催化
效率与工业化应用的乙醇钠相当；用量 3%的 TEPA-EC 在 8 次重复使用和 14 次带水循环使用过程中，EtOH 的
转化率、EMC 的选择性分别在 62.35%、86.03%和 57.33%、87.91%左右，优于乙醇钠的稳定性和耐水性。
关键词：碳酸甲乙酯；四乙烯五胺；合成；氨基甲酸酯；有机催化剂；氢键；酯交换
中图分类号：TQ225.52；TQ426 文献标识码：A 文章编号：1003-5214 (2023) 12-2696-09

Preparation and application of carbamate organocatalyst

YANG Jianguo, LI Jinzhu, XU Yan, ZHAI Liubin, ZHANG Hongbo
（School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243032, Anhui, China）

Abstract: A carbamate organocatalyst (TEPA-EC) for the synthesis of methyl ethyl carbonate (EMC) was
synthesized from addition reaction of tetraethylenepentamine (TEPA) and ethylene carbonate (EC), then
characterized by FTIR and NMR, and further analyzed for its catalytic mechanism. The influence of
synthesis and application conditions on the catalytic activity and transesterification efficiency of TEPA-EC
were investigated, followed by assessment on its stability and water resistance. The results showed that the
hydroxyethyl tert-aminoformate group in TEPA-EC could facilitate the transesterification between
dimethyl carbonate (DMC) and ethyl alcohol (EtOH) via synergistic hydrogen bonds. The TEPA-EC with
high catalytic activity could be obtained under reaction conditions of n(EC)∶n(TEPA)=5∶1, temperature
140 ℃ and reaction time 2 h. The conversion of EtOH and selectivity of EMC reached 59.50% and
83.77%, respectively, when DMC reacted with EtOH (4.60 g) by a molar ratio of 2∶1 at 78 ℃ for 7 h
with 1% (based on the total mass of raw materials, the same below) TEPA-EC. The TEPA-EC displayed
comparable catalytic efficiency to that of sodium ethoxide used in industrial application. When 3%
TEPA-EC was recycled 8 times alone and 14 times with water, the conversion of EtOH and the selectivity
of EMC fluctuated around 62.35%, 86.03% and 57.33%, 87.91%, respectively, demonstrating much better
stability and water resistance than sodium ethoxide.
Key words: methyl ethyl carbonate; tetraethylenepentamine; synthesis; carbamate; organocatalysts;
hydrogen bonds; transesterification

碳酸甲乙酯（EMC）在有机合成、锂电池和环 气法、酯交换法和氧化羰基化法等 [1-3] 。其中，利用
保型溶剂等领域具有重要的应用，其合成方法有光 碳酸二甲酯（DMC）与乙醇（EtOH）酯交换合成

收稿日期：2023-03-22; 定用日期：2023-05-12; DOI: 10.13550/j.jxhg.20230223
作者简介：杨建国（1973—），男，副教授，E-mail：jgyang@ahut.edu.cn。