氧化还原法制备季铵盐离子液体
发布时间：2018-10-22 13:11
【摘要】：作为一种新型的“绿色溶剂”和催化剂,离子液体有望代替传统的有机溶剂和有机催化剂,实现绿色化学中绿色原料、绿色催化剂的需要。离子液体起了重要的作用,某种意义上说,离子液体是浓缩的绿色化学的符号。离子液体具有如下优异的物理化学性能:即使在真空下也难以察觉的蒸汽压;在较大的温度范围内仍呈现液态;电化学窗口宽;热稳定性高等。尽管近年来对于离子液体的应用方面的报道日益递增,但对于其制备及纯化却比较少。离子液体合成方法主要分为一步法和两步法。虽然一步法可以获得高纯度的离子液体,但是离子液体阴阳离子的种类会受到有限的烷基化试剂的限制,两步法还是离子液体的主要合成方法。但是传统两步法面临着诸多问题,例如收率低、合成时间长、反应温度高、杂质含量高。本文设计新型的合成方法—氧化还原法制备了一系列季铵盐离子液体,在含有目标阴离子的质子酸和1-己烯作为溴清除剂的情况下,使用双氧水与季铵溴盐反应合成离子液体,合成了一系列以四甲基铵,四乙基铵和四正丁基铵为阳离子与以5种酸根CH3SO3-、HSO4-、NO3-、CF3COO-和TsO-为阴离子的室温离子液体。合成的离子液体产品结构经过1H NMR和13C NMR表征确定为目标产品,用离子色谱和卡尔费休水份滴定仪分别测量了产品中的溴杂质和水分含量。结果表明,在室温条件下反应3~4h,离子液体收率高达98%,溴杂质含量和水分含量较低。该方法相比较于传统的方法,不仅可以制备高纯度和高收率的离子液体,而且简化实验条件,具有反应条件温和,反应时间短,产品收率和纯度高的优点。实验同时证明,含有双键官能团的离子液体和弱酸型离子液体不适合氧化还原法合成。
[Abstract]:As a new type of "green solvent" and catalyst, ionic liquids are expected to replace the traditional organic solvents and organic catalysts to meet the needs of green raw materials and catalysts in green chemistry. Ionic liquids play an important role. In a sense, ionic liquids are symbols of concentrated green chemistry. Ionic liquids have the following excellent physical and chemical properties: vapor pressure, which is difficult to detect even in vacuum; liquid state in large temperature range; wide electrochemical window; high thermal stability. Although the application of ionic liquids has been increasing in recent years, the preparation and purification of ionic liquids are relatively rare. The synthetic method of ionic liquid is mainly divided into one step method and two step method. Although high purity ionic liquids can be obtained by one step method, the species of anions and anions of ionic liquids will be limited by limited alkylation reagents, and the two-step method is still the main method for the synthesis of ionic liquids. However, the traditional two-step method is faced with many problems, such as low yield, long synthesis time, high reaction temperature and high impurity content. A series of quaternary ammonium salt ionic liquids were prepared by redox method. Ionic liquids were synthesized by the reaction of hydrogen peroxide with quaternary ammonium bromide with protonic acid and 1-hexene containing target anions as bromine scavengers. A series of room temperature ionic liquids with tetramethylammonium tetraethylammonium and tetra-Ding Ji ammonium as cations and CH3SO3-,HSO4-,NO3-,CF3COO- and TsO- as anions were synthesized. The synthesized ionic liquid product was characterized by 1H NMR and 13C NMR. The bromine impurity and water content in the product were measured by ion chromatography and Karl Fischer water titration apparatus. The results showed that the yield of ionic liquid was up to 98% at room temperature for 3 h, and the content of bromine impurity and water was lower. Compared with the traditional method, this method can not only prepare ionic liquids with high purity and high yield, but also simplify the experimental conditions. It has the advantages of mild reaction conditions, short reaction time, high yield and high purity. At the same time, it is proved that ionic liquids containing double bond functional groups and weak acid ionic liquids are not suitable for redox synthesis.
【学位授予单位】：沈阳化工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O645.1
本文编号：2287250
[Abstract]:As a new type of "green solvent" and catalyst, ionic liquids are expected to replace the traditional organic solvents and organic catalysts to meet the needs of green raw materials and catalysts in green chemistry. Ionic liquids play an important role. In a sense, ionic liquids are symbols of concentrated green chemistry. Ionic liquids have the following excellent physical and chemical properties: vapor pressure, which is difficult to detect even in vacuum; liquid state in large temperature range; wide electrochemical window; high thermal stability. Although the application of ionic liquids has been increasing in recent years, the preparation and purification of ionic liquids are relatively rare. The synthetic method of ionic liquid is mainly divided into one step method and two step method. Although high purity ionic liquids can be obtained by one step method, the species of anions and anions of ionic liquids will be limited by limited alkylation reagents, and the two-step method is still the main method for the synthesis of ionic liquids. However, the traditional two-step method is faced with many problems, such as low yield, long synthesis time, high reaction temperature and high impurity content. A series of quaternary ammonium salt ionic liquids were prepared by redox method. Ionic liquids were synthesized by the reaction of hydrogen peroxide with quaternary ammonium bromide with protonic acid and 1-hexene containing target anions as bromine scavengers. A series of room temperature ionic liquids with tetramethylammonium tetraethylammonium and tetra-Ding Ji ammonium as cations and CH3SO3-,HSO4-,NO3-,CF3COO- and TsO- as anions were synthesized. The synthesized ionic liquid product was characterized by 1H NMR and 13C NMR. The bromine impurity and water content in the product were measured by ion chromatography and Karl Fischer water titration apparatus. The results showed that the yield of ionic liquid was up to 98% at room temperature for 3 h, and the content of bromine impurity and water was lower. Compared with the traditional method, this method can not only prepare ionic liquids with high purity and high yield, but also simplify the experimental conditions. It has the advantages of mild reaction conditions, short reaction time, high yield and high purity. At the same time, it is proved that ionic liquids containing double bond functional groups and weak acid ionic liquids are not suitable for redox synthesis.
【学位授予单位】：沈阳化工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O645.1
【参考文献】
相关期刊论文 前1条
1 陈慧,戴立益,单永奎,何鸣元;新型离子液体体系催化苯与1-己烯的烷基化反应[J];应用化学;2003年09期
，本文编号：2287250
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