甲基磺酸镧催化合成柠檬酸三(2-乙基己基)酯的研究2008102315517281.docVIP

甲基磺酸镧催化合成柠檬酸三(2-乙基己基)酯的研究 杜晓晗，陆豪杰 （健雄职业技术学院 化工系，江苏 太仓 215411三(2-乙基己基)酯中图分类号：文献标识码：AStudy On Catalytic Synthesis of Tri(2-ethylhexyl) Citrate with Lanthanum Methanesulfonate DU Xiao-han, LU Hao-jie (Chemical Engineering Department, Chien-Shiung Institute of Technology, Taicang 215411, China) Abstract：Lanthanum Methanesulfonate was synthesized and then characterized by thermogravimetry and infrared. The result of TGA indicated that four crystal-water are presented in the formula. The content of lanthanum oxide determined by TGA is in good agreement with theoretical calculated value. It was used as the catalyst in the esterification of citric acid with 2-ethylhexanol. The effects of reaction temperature, amount of catalyst and alcohol ∕ acid molar ratio have been investigated. The products were analyzed by means of FT-IR. The yield can be over 97.5% under the optimum conditions that molar ratio of 2-ethylhexanol to citric acid, 3.60:1; amount of catalyst, 0.25 % (molar percentage of citric acid) and reaction temperature, 120～130 ℃, reaction pressure: vacuum. The catalyst can be reused by simple phase-separation after reaction. It is used repeatedly for 5 times without obvious loss of activity and with the yield still over 90.0%. Key words: lanthanum methanesulfonate; tri(2-ethylhexyl) citrate; esterification; catalytic synthesis 作者简介：杜晓晗（1976—），男，江苏睢宁人，健雄职业技术学院化学工程系教师，助理工程师，硕士，主要从事有机及精细有机合成方面的教学与科研工作。 PVC塑料助剂的主增塑剂邻苯二甲酸酯类在过去几十年得到广泛应用[1]，近年来研究发现，这类增塑剂用于食品包装材料、玩具等可诱发致癌，特别是对婴儿和儿童的生长发育影响更大[2-3]。柠檬酸酯系列增塑剂具有无毒、生物降解性好、挥发性小、抗细菌，增塑效率高等优点，被FDA认为是最安全的增塑剂之一[4]，已被FDA批准为无毒增塑剂。这类增塑剂中，目前研究较多的是柠檬酸三丁酯。而柠檬酸三(2-乙基己基)酯则研究较少。 柠檬酸三(2-乙基己基)酯由柠檬酸和2-乙基己醇在催化剂作用下酯化而成。目前报道的催化剂有浓硫酸和稀土[5-6]。但硫酸是一种强质子酸，副反应较多，产品的色泽深，成品的收率低，腐蚀设备；反应后还需中和水洗等操作，废水量较大。Lewis酸催化剂因活性高、选择性好、反应条件温和而受到人们重视，但普通Lewis 酸易与水反应而失活[7]，近年来研究发现，稀土三氟甲基磺酸盐Sc (Of)3，Yb (OTf)3等[7-9]在有水存在的有机反应中很稳定，HfCl4和HfCl4 (THF)2对酯化反应有很高的催化活性，而且选择性高[10]，但这些催化剂价格昂贵，制备困难。受此启发，笔者参照文献[7]合成甲基磺酸镧，这是一种耐水性非常好的Lewis酸。该催化剂具有催化活性高、可重复使用对环境友好等优点，是一种绿色酯化催化剂。关于该催化剂在合