胆碱类低共熔溶剂组分间的氢键作用研究
发布时间：2018-09-09 11:10
【摘要】：传统的化学工业中大量挥发性有机溶剂的使用给环境造成了十分严重的污染,这就迫使人们寻找和开发绿色、无毒的溶剂来代替传统挥发性有机溶剂的使用。低共熔溶剂(DES)除了具有较低的熔点和蒸汽压、溶解能力强及导电性能优良等优点外,还具有无毒或低毒、价格低廉等优点,有望成为传统有机溶剂的优良替代品。正是这些优良的性质使其在化学化工方面展现出较好的应用前景。然而,在做这些应用过程中,对于DESs组分之间的相互作用研究较少,限制了人们对于其物理化学性质和微观结构的认识,进而阻碍了新的DESs的设计和开发。因此,研究DESs组分之间的相互作用具有重要的意义。基于此,本文作为国家自然科学基金项目(NO.21573060)的一部分,选取常见的氯化胆碱(ChCl)与不同的脂肪二醇、脂肪二羧酸和苯酚类化合物形成的DES为研究对象,采用多种方法研究了DES组分之间的氢键相互作用,主要研究内容如下:1.在293K下,利用FTIR、FIR、1H NMR、35Cl NMR和量子化学计算等方法研究了ChCl与脂肪二醇(1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、乙二醇、1,3-丙二醇、1,5-戊二醇、1,6-己二醇)之间的氢键相互作用。考查了醇分子中烷基链长度以及不同摩尔比对其与ChCl之间氢键相互作用的影响,讨论组分之间相互作用强度与其物理化学性质之间的关系。实验结果表明:脂肪二醇中的羟基氢原子与ChCl中的氯原子之间存在氢键作用,并且随着醇中两个羟基之间碳原子数的增多,醇与ChCl之间形成的氢键作用减弱,导致其表面张力增大,极性减小。随着混合物中ChCl含量的增加,醇对ChCl自身氢键的削弱能力降低,并且两种组分自身的氢键作用也会随着ChCl含量的增大而增强。2.在293K下,采用FTIR、FIR、1H NMR、35Cl NMR等方法来研究由草酸、丙二酸、丁二酸、戊二酸、己二酸与ChCl在一定比例条件下形成的DESs组分之间的氢键相互作用,分析了脂肪二酸分子中烷基链长度对其与ChCl之间氢键相互作用的影响。结果表明,ChCl中的氯原子与酸中羧基氢原子之间能够形成氢键作用,且该氢键比ChCl自身氢键作用强。随着脂肪二酸中两个羧基之间碳原子数的增多,酸与ChCl之间形成的氢键作用减弱,导致二者形成的DESs熔点值增大。3.在293K下,以苯酚、邻甲苯酚、间甲苯酚以及对甲苯酚与ChCl形成的DES为研究对象,采用FTIR、FIR、1H NMR和35Cl NMR等方法研究了二者之间的氢键相互作用,分析了苯酚类化合物中羟基与甲基的相对位置对其与ChCl之间氢键相互作用的影响。结果表明:四种苯酚类化合物与ChCl形成氢键的能力顺序为:苯酚对甲酚间甲酚邻甲酚。该顺序与四种苯酚类化合物的酸性强弱大小顺序相一致,也与形成DESs之后熔点的大小顺序相反。这说明DES组分之间的氢键相互作用愈强,能够更有效地破坏单组分自身分子间的氢键作用,进而造成DES的熔点愈低。苯酚类化合物/ChCl摩尔比为2/1时二者形成的DESs具有最低的熔点。
[Abstract]:The use of a large number of volatile organic solvents in the traditional chemical industry has caused serious environmental pollution, which forces people to find and develop green, non-toxic solvents to replace the use of traditional volatile organic solvents. In addition to these advantages, it has the advantages of non-toxicity, low toxicity and low price, and is expected to become an excellent substitute for traditional organic solvents. It is these excellent properties that make it show a good application prospect in chemical engineering. However, in the course of these applications, there is little research on the interaction between DESs components, which limits people's attention. Therefore, it is of great significance to study the interaction between DESs components. As part of the project of National Natural Science Foundation of China (NO. 21573060), this paper selects common choline chloride (ChCl) and different fatty glycols and lipids. The hydrogen bond interactions between the components of DES were studied by various methods. The main contents are as follows: 1. At 293 K, the interaction between ChCl and fatty diols (1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol) was studied by FTIR, FIR, 1H NMR, 35Cl NMR and quantum chemical calculation. Hydrogen bond interactions among butanediol, ethylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol were investigated. The effects of alkyl chain length and molar ratio on the hydrogen bond interaction between butanediol and ChCl were investigated. The relationship between the strength of the interaction and the physicochemical properties of fatty dimer was discussed. The hydrogen bond between hydroxyl hydrogen atoms in alcohols and chlorine atoms in CHCl decreases with the increase of the number of carbon atoms between two hydroxyl groups in alcohols, resulting in the increase of surface tension and the decrease of polarity. At 293 K, the hydrogen bond interaction between the DESs formed by oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and CHCl in a certain proportion was studied by FTIR, FIR, 1H NMR, 35Cl NMR and other methods. The results show that the hydrogen bond between chlorine atom in ChCl and carboxyl hydrogen atom in acid can be formed, and the hydrogen bond is stronger than that of ChCl itself. The melting point of DESs formed by phenol, o-cresol, m-cresol, p-cresol and CHCl was increased at 293K. The hydrogen bond interaction between them was studied by FTIR, FIR, 1H NMR and 35Cl NMR. The relative positions of hydroxyl and methyl groups in phenols and the relationship between them and CHCl were analyzed. The results show that the order of the hydrogen bonding ability of the four phenolic compounds to CHCl is phenol-p-cresol-o-cresol. The order is consistent with the order of the acidity of the four phenolic compounds and the order of the melting point after the formation of DES. The stronger the interaction is, the more effective it is to destroy the hydrogen bonds between the molecules of the single component, thus resulting in the lower melting point of DES. The lowest melting point is found when the molar ratio of phenolic compounds to ChCl is 2/1.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3
本文编号：2232205
[Abstract]:The use of a large number of volatile organic solvents in the traditional chemical industry has caused serious environmental pollution, which forces people to find and develop green, non-toxic solvents to replace the use of traditional volatile organic solvents. In addition to these advantages, it has the advantages of non-toxicity, low toxicity and low price, and is expected to become an excellent substitute for traditional organic solvents. It is these excellent properties that make it show a good application prospect in chemical engineering. However, in the course of these applications, there is little research on the interaction between DESs components, which limits people's attention. Therefore, it is of great significance to study the interaction between DESs components. As part of the project of National Natural Science Foundation of China (NO. 21573060), this paper selects common choline chloride (ChCl) and different fatty glycols and lipids. The hydrogen bond interactions between the components of DES were studied by various methods. The main contents are as follows: 1. At 293 K, the interaction between ChCl and fatty diols (1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol) was studied by FTIR, FIR, 1H NMR, 35Cl NMR and quantum chemical calculation. Hydrogen bond interactions among butanediol, ethylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol were investigated. The effects of alkyl chain length and molar ratio on the hydrogen bond interaction between butanediol and ChCl were investigated. The relationship between the strength of the interaction and the physicochemical properties of fatty dimer was discussed. The hydrogen bond between hydroxyl hydrogen atoms in alcohols and chlorine atoms in CHCl decreases with the increase of the number of carbon atoms between two hydroxyl groups in alcohols, resulting in the increase of surface tension and the decrease of polarity. At 293 K, the hydrogen bond interaction between the DESs formed by oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and CHCl in a certain proportion was studied by FTIR, FIR, 1H NMR, 35Cl NMR and other methods. The results show that the hydrogen bond between chlorine atom in ChCl and carboxyl hydrogen atom in acid can be formed, and the hydrogen bond is stronger than that of ChCl itself. The melting point of DESs formed by phenol, o-cresol, m-cresol, p-cresol and CHCl was increased at 293K. The hydrogen bond interaction between them was studied by FTIR, FIR, 1H NMR and 35Cl NMR. The relative positions of hydroxyl and methyl groups in phenols and the relationship between them and CHCl were analyzed. The results show that the order of the hydrogen bonding ability of the four phenolic compounds to CHCl is phenol-p-cresol-o-cresol. The order is consistent with the order of the acidity of the four phenolic compounds and the order of the melting point after the formation of DES. The stronger the interaction is, the more effective it is to destroy the hydrogen bonds between the molecules of the single component, thus resulting in the lower melting point of DES. The lowest melting point is found when the molar ratio of phenolic compounds to ChCl is 2/1.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3
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