有机羧酸络合萃取及其QSAR研究

【作者】 徐明礼；

【导师】 彭盘英；

【作者基本信息】 南京师范大学 ， 应用化学， 2007， 硕士

【摘要】 有机羧酸是重要的化工原料和中间体，络合萃取是分离提纯有机羧酸稀溶液的重要方法，其平衡常数是络合萃取的重要热力学性质。本文应用原子类型电拓扑指数（ETSI）为描述子对有机物分子结构进行有效表征。以文献记载658种有机物及其在水中的溶解度性质为研究对象，对其进行结构-性质关联，以多元线性回归法（MLR）建立数学模型。结果表明，ETSI描述子能够完全分辨所研究的化合物；所建模型以14个描述子为自变量，模型估计相关系数γ和LOO交互检验相关系数q分别为0.9074、0.9019。以三辛胺（TOA）为萃取剂，以氯仿、正辛醇、甲苯、二甲苯为稀释剂对羟基乙酸进行萃取；以正辛醇为稀释剂对甲酸、乙酸、丙酸、丁酸、乳酸、丙烯酸、丙二酸、丁二酸、苹果酸、酒石酸、马来酸、水杨酸和间硝基苯甲酸等羧酸进行萃取。讨论了影响萃取的各种因素。在所假设的萃取机理基础上对萃取过程建立数学模型，通过该模型对实验数据进行线性和非线性回归，得出络合萃取平衡常数K₁₁、K₁₂。结果表明，假设的萃取机理与实验数据符合情况良好，所建模型能够较好预测萃取情况。同时，本文对有机羧酸络合萃取平衡常数与其分子结构的关系（QSAR）进行研究，以多元线性回归法（MLR）对其建立模型，以6种ETSI描述子为自变量，模型估计相关系数，和LOO交互检验系数q分别达到0.9987、0.9721。结果表明，该模型具有良好的估计和预测性能。更多还原

【Abstract】 Carboxylic acids are important chemical industrial material and intermediate product. Reactive extraction, the equilibrium constant of which, is important thermodynamic property, is a kind of important separation method to thin solution of carboxylic acids.In the present paper, the structure of studied compounds molecule were described by Electrotopological State Indices for atom type（ETSI）. The structure and solubility of 658 organic compounds cited from literatures were related and their models were established by Multiple Linear Regress（MLR）. The results showed that ETSI descriptors were sufficient for differentiating the structure of 658 studied compounds; the model based on MLR had 14 ETSI descriptors as its independent variables, and its modeling estimate relative coefficient（r） and Leave-One- Out cross validation relative coefficient（q） were 0.9074 and 0.9019. Estimating accuracy was satisfying.Glycolic acid was extracted with tri-octylamine（TOA） as extraction reagent and chloroform, n-octanol, toluene, xylene as diluent. Formic, acetic, propyl, butyl, lactic, crylic, malonic, succinic, malic, tartaric, maleic, salicylic and p-nitryl benzyl acid were extracted with n-octanol as diluent. Factors affecting the extraction resut had been discussed. Models based on supposed reaction mechanism were built; reactive extraction equilibrium constant K₁₁, K₁₂ were got by linear or non-linear regression of experiment data. The results showed that supposed reaction mechanism fit experiment data well and the model was also able to predict experiment data well.Meanwhile, the quantitative relationship between carboxylic acids reaction extraction equilibrium constant and their structures（QSAR） was studied. The model built by MLR had 6 ETSI descriptor as its independent variables, and its modeling estimate relative coefficient（r） and Leave-One- Out cross validation relative coefficient（q） were 0.9987,0.9721.更多还原