为了提出一种制备柠檬酸三丁酯的方法,提出了一种新型负载离子催化剂。采用键合法以N-甲基咪唑、三乙氧基氯硅烷及硫酸等为原料,堇青石、活性炭、蒙脱土及二氧化硅等为载体制备了MImHSO4/堇青石(MImHSO4/JQS)、MMImHSO4/活性炭(MMImHSO4/AC)、MImHSO4/蒙脱土(MImHSO4/MTT)和MImHSO4/二氧化硅(TMMImHSO4/SiO2)催化剂,并用于催化柠檬酸和正丁醇的反应中,结果表明:MImHSO4/JQS催化剂的催化性能最好。同时采用热重(TG)、低温氮气吸附(BET)、X射线衍射(XRD)及傅里叶红外光谱仪(FT-IR)等表征方法对合成的催化剂进行了表征。结果表明:离子液体被接枝到载体上。在酸醇摩尔比1∶3.5、反应温度145℃、反应时间9h、MImHSO4/JQS催化剂用量6%的反应条件下,柠檬酸的转化率达到91.1%。催化剂重复使用7次后,催化剂的活性基本保持不变,表明该功能化酸性离子液体是一种有潜力的新型酯化有机-无机杂化催化材料。
In order to present a green method to produce tributyl citrate(TBC),a series of novel supported ionic liquids (ILs) catalyst MImHSO4/JQS,MImHSO4/AC,MImHSO4/MTT and MImHSO4/SiO2 were synthesized by bonding method using N-methyl imidazole,triethoxylchlorosilane and sulfuric acid as materials.The catalysts were used to catalyze the esterification reaction of bitric acid and N-butyl alcohol.The results shown that MImHSO4/JQS had better esterification effection.The catalysts were characterized by thermogravimetric(TG),low temperature nitrogen adsorption method (BET),X-ray diffraction and fourier transform infrared(FT-IR).The results showed that the immobilized ILs were successfully grated onto the carriers.The results indicated that high conversion of 91.1% for the citric acid was achieved under the condition of n(citric acid)∶n(n-butyl alcohol)=1∶3.5,145℃,9h and the optimum catalyst dosage of 6%.The excellent activity and perfect reusability during seven-recycle test demonstrated that MImHSO4/JQS was potential organic-inorganic hybrid catalyst.
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