【作者】 张圆圆； 刘哲琳； 吴克； 王斌； 徐玲； 刘宗瑞； 段莉梅；

【Author】 Zhang Yuan-Yuan;Liu Zhe-lin;Wu Ke;Wang Bin;X u Ling;Liu Zong-Rui;Duan Li-mei;College of Chemistry and Chemical Engineering,Inner Mongolia University for the Nationalities;School of Chemistry & Environment Engineering,Changchun University of Science and Technology;

【机构】 内蒙古民族大学化学化工学院； 长春理工大学化学与环境工程学院；

【摘要】 柠檬酸三丁酯（TBC）是一种具有可降解且增塑效果优良的增塑剂,被广泛应用于医疗用具、食品包装等高分子材料领域的一类绿色环保添加剂。本文通过离子交换法合成了一系列Keggin型杂多酸H_nXW₁₂O₄₀(X=P⁵⁺、Si⁴⁺、B³⁺;n=3、4、5),并利用XRD、FTIR对其结构进行表征。以Keggin型杂多酸为固体酸催化剂、柠檬酸三丁酯的合成为研究对象,对3种含不同中心杂原子、氢离子数目的 Keggin型杂多酸H_nXW₁₂O₄₀(X=P⁵⁺、Si⁴⁺、B³⁺; n=3、4、5)催化合成柠檬酸三丁酯的活性进行比较,三种多酸催化剂催化合成柠檬酸三丁酯的活性顺序为:H₄SiW₁₂O₄₀>H₃PW₁₂O₄₀>H₅BW₁₂O₄₀,其中硅钨酸催化合成柠檬酸三丁酯的酯化率可达到98.79。通过考察催化剂用量、醇酸摩尔比、反应温度、反应时间对柠檬酸三丁酯的酯化率的影响,获得了催化合成柠檬酸三丁酯的最佳实验条件:催化剂用量0.3g、酸醇摩尔比1:4、反应温度130℃、反应时间4h。该催化工艺条件稳定、后处理方便、环境污染小,为TBC的绿色合成提供了一类有应用前景的催化剂.更多还原

【Abstract】 Tri-butyl citrate（TBC） is a kind of plasticizer with good degradation and good plasticizing effect and is widely used as a kind of green environmental additive in the fields of medical appliances, food packaging and other polymer materials. In this article, a series of Keggin-type heteropoly acids HnXW₁₂O₄₀(X = P⁵⁺, Si⁴⁺, B³⁺; n = 3, 4, 5) were synthesized by ion exchange method. The structures were characterized by XRD and FTIR spectrum. The Keggin-type heteropoly acids were used as the solid acid catalysts and the synthesis of tributyl citrate was studied. The catalytic activity of three kinds of Keggin-type heteropoly acids HnXW₁₂O₄₀(X = P⁵⁺, Si⁴⁺, B³⁺; n = 3, 4, 5) with different central heteroatoms and external hydrogen ions in the synthesis of tributyl citrate was compared. The catalytic activity of the three Keggin-type heteropoly acids catalysts for the synthesis of tri-butyl citrate was in the order: H₄SiW₁₂O₄₀ > H₃PW₁₂O₄₀ > H₅BW₁₂O₄₀. And the esterification rate of tri-butyl citrate catalyzed by H₄SiW₁₂O₄₀ can reach 98.79. The effects of catalyst dosage, acid-alcohol molar ratio, reaction time and reaction temperature on the catalytic synthesis of tributyl citrate esterification rate were investigated, the optimum experimental conditions for the catalytic synthesis of three butyl citrate were obtained: the amount of catalyst was 0.3 g, the molar ratio of acid alcohol was 1:4, the reaction temperature was 130, and the reaction time was 4 h. The catalytic process conditions are stable, post-processing is convenient and environmental pollution is small. It provides a kind of application for the green synthesis of TBC.更多还原