郭康斌,钱超,陈新发,何潮洪

• 1:化学工程联合国家重点实验室(浙江大学)
• 2:浙江大学化学工程与生物工程学系
• 3:宁波永顺精细化工有限公司

摘要(Abstract)：

目前广泛使用的邻苯二甲酸酯类增塑剂有一定的毒性,并有可能诱发癌症。乙酰柠檬酸三丁酯有很好的安全性与出色的增塑性,被认为是邻苯二甲酸酯类增塑剂的合格替代品。以乙酸酐和自制的柠檬酸三丁酯为原料,以[NH(CH2)5CO]HSO4酸性离子液体为催化剂合成乙酰柠檬酸三丁酯,研究了原料摩尔配比、反应温度、反应时间和催化剂用量对乙酰柠檬酸三丁酯收率的影响。优化反应条件后,在乙酸酐用量较少的情况下,反应的收率可达到98.7%。此外,催化剂重复回收使用5次后,收率仍可达98.2%。表明该酸性离子液体在此反应中具有较高的催化活性和良好的重复使用性,是催化合成乙酰柠檬酸三丁酯的良好催化剂。

关键词(KeyWords)： 离子液体;催化;乙酰柠檬酸三丁酯(ATBC);增塑剂

Abstract:

Keywords:

基金项目(Foundation): 浙江省自然科学基金杰出青年团队项目(R4090358);; 浙江省重点科技创新团队(2009R50002)

作者(Author): 郭康斌,钱超,陈新发,何潮洪

参考文献(References)：

• [1]SHI Wan-cong(石万聪),SHENG Cheng-xiang(盛承祥).Plasticizer(增塑剂)[M].Beijing(北京):Chemical Industry Press(化学工业出版社),1989:249.
• [2]JIANG Ping-ping(蒋平平),CHONG Ming-ben(崇明本),ZHANG Dian-Peng(张典鹏),et al.The acceleration of research and application in China’s new environmental friendly citrate plasticizer(加快我国新型环境友好增塑剂柠檬酸酯研究与应用)[J].Plastic Additives(塑料助剂),2003,42(5):1-8.
• [3]Erceg M,KovaiT,KlariI.Thermal degradation of poly(3-hydroxybutyrate)plasticized with acetyl tributyl citrate[J].Polymer Degradation and Stability,2005,90(2):313-318.
• [4]XIE Wen-lei(谢文磊),FENG Guang-zhu(冯光炷).Study on the synthesis of tributyl acetyl citrate(乙酰柠檬酸三丁酯的合成研究)[J].Speciality Petrochemicals(精细石油化工),1998(4):7-9.
• [5]XIE Chun-he(谢春和),JIN Wei-guang(金伟光),ZHANG Jia-sen(张家森).Catalytic synthesis of acetyl tri-n-butyl citrate(乙酰柠檬酸三丁酯的催化合成)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2006,20(3):428-432.
• [6]CEN Lan(岑兰),SUN Ming-jian(孙鸣剑),WANG Xue-jing(王雪晶).Recent advance on application of non-toxic citrate esters plasticizer(环境友好无毒柠檬酸增塑剂的研究进展)[J].China Elastomerics(弹性体),2007,17(6):69-73.
• [7]Klaus B,Thomas K,Hans B.Method for producing esters of citric acids:Eu Pateut,1 231 203[P].2002-08-15.
• [8]Kolah A K,Asthana N S,Vu D T,et al.Reaction kinetics of the catalytic esterification of citric acid with ethanol[J].Industrial&Engineering Chemistry Research,2007,46(10):3180-3187.
• [9]JIANG Ping-ping(蒋平平),LI Liang-kuo(李良阔),LU Yun(卢云).A method suited industrialized production of acetyl citrate esters(一种适合工业化乙酰柠檬酸酯生产方法):CN,1 557 800A[P].2004-10-29.
• [10]GUO Hui(郭辉),WANG Jun-liang(王君良),LI Xia(李霞),et al.Oxa-Michael addition catalyzed by amide-based acidic ionic liquids(酰胺类酸性离子液体催化Oxa-Michael加成反应)[J].Chinese Journal of Catalysis(催化学报),2011,32(1):162-165.
• [11]Du Zheng-yin,Li Zuo-peng,Guo Shu,et al.Investigation of physicochemical properties of lactam-based bronsted acidic ionic liquids[J].J Phys Chem B,2005,109:19542-19546.
• [12]GUI J,LIU D,CHEN X,et al.Cyclotrimerization of an aliphatic aldehyde catalyzed by acidic ionic liquid[J].Reaction Kinetics Mechanisms and Catalysis Letters,2007,90(1):35-43.
• [13]QIAN De-sheng(钱德胜),CHENG Guang-bin(程广斌),LüChun-xu(吕春绪).Rare-earth metals catalyzed nitration of toluene in ionic liquid(稀土金属在离子液体中催化甲苯的硝化反应)[J].Chinese Journal of Appied Chemistry(应用化学),2009,26(7):757-761.
• [14]XIA Jun(夏军),SHI Gao-feng(史高峰),CHEN Xue-fu(陈学福).Study on synthesis of non-toxic acetyltributyl citrat(无毒增塑剂乙酰柠檬酸三丁酯的合成研究)[J].China Plastics Industry(塑料工业),2008,36(6):78-81.
• [15]LIU Ying(刘颖).Synthesis and application of TBC and ATBC(柠檬酸三丁酯及其乙酰化产物的合成与应用)[J].Rubber&Plastics Resources Utilization(橡塑资源利用),2007(4):3-7.
• [16]LüJin-kui(吕金魁).Synthesis of O-acetyl-tri-n-butyl citrate by polyvinyl pyridine as catalyst(聚乙烯吡啶催化合成乙酰柠檬酸酯)[J].Chemical Industry Times(化工时刊),2000(5):42-43.