CN-121990924-A - Preparation method of oxalic acid ligand binary quaternary ammonium salt

Abstract

The invention provides a preparation method of oxalic acid ligand binary quaternary ammonium salt, and relates to the technical field of organic synthesis. Mixing quaternary ammonium halide with sodium hydroxide solution, heating in a reaction kettle for reaction, cooling for phase separation to obtain trioctyl methyl ammonium hydroxide, mixing the obtained trioctyl methyl ammonium hydroxide with oxalic acid solution, heating again in the reaction kettle for reaction, cooling for phase separation to obtain a binary quaternary ammonium salt crude product, and washing and drying the obtained binary quaternary ammonium salt crude product to obtain the binary quaternary ammonium salt of oxalic acid ligand. The method has the advantages of simple operation, short reaction time, easy separation of products and high yield, and the obtained quaternary ammonium salt product can be used for green and environment-friendly extraction.

Inventors

• LIU ZISHUAI
• LI QIANWEN
• LUO HENG
• LIU WENBIN
• LV YANCHENG

Assignees

• 江西理工大学

Dates

Publication Date

20260508

Application Date

20251223

Claims (8)

1. 1. A method for preparing a binary quaternary ammonium salt of an oxalic acid ligand, the method comprising: S1, mixing quaternary ammonium halide with sodium hydroxide solution, heating in a reaction kettle for reaction, cooling, and separating phases to obtain trioctyl methyl ammonium hydroxide; s2, mixing the trioctyl methyl ammonium hydroxide obtained in the step S1 with oxalic acid solution, heating in a reaction kettle for reaction, cooling and then separating phases to obtain a binary quaternary ammonium salt crude product; And S3, washing and drying the binary quaternary ammonium salt crude product obtained in the step S2 to obtain the oxalic acid ligand binary quaternary ammonium salt.
2. 2. The method for preparing binary quaternary ammonium salt of oxalic acid ligand according to claim 1, wherein the quaternary ammonium salt of halide in S1 is one of trioctylmethyl ammonium chloride, trioctylmethyl ammonium iodide and trioctylmethyl ammonium bromide.
3. 3. The method for preparing the binary quaternary ammonium salt of oxalic acid ligand according to claim 1, wherein the molar ratio of the quaternary ammonium halide salt to the sodium hydroxide solution in the step S1 is 1:1-1:4.
4. 4. The method for preparing the binary quaternary ammonium salt of the oxalic acid ligand according to claim 1, wherein the heating temperature of the reaction kettle in the step S1 is 50-70 ℃ and the reaction time is 10-20 min.
5. 5. The method for preparing the binary quaternary ammonium salt of oxalic acid ligand according to claim 1, wherein the molar ratio of trioctyl methyl ammonium hydroxide to oxalic acid solution in S2 is 1:1-1:3.
6. 6. The method for preparing the binary quaternary ammonium salt of the oxalic acid ligand according to claim 1, wherein the heating temperature of the reaction kettle in the step S2 is 30-50 ℃ and the reaction time is 10-20 min.
7. 7. The method for preparing binary quaternary ammonium salt of oxalic acid ligand according to claim 1, wherein the crude product of binary quaternary ammonium salt in S3 is washed with deionized water for not less than 3 times.
8. 8. The method for preparing the binary quaternary ammonium salt of the oxalic acid ligand according to claim 1, wherein the binary quaternary ammonium salt crude product in the step S3 is washed and then dried in vacuum at 30-50 ℃ for at least 24 hours to obtain the binary quaternary ammonium salt of the oxalic acid ligand.

Description

Preparation method of oxalic acid ligand binary quaternary ammonium salt Technical Field The invention relates to the technical field of organic synthesis, in particular to a preparation method of binary quaternary ammonium salt of oxalic acid ligand. Background Quaternary ammonium salts are a class of cationic surfactants and are also commonly used extractants in hydrometallurgy. The quaternary ammonium salt comprises a halogenating agent ammonium salt compound and an acid radical quaternary ammonium salt compound, and the quaternary ammonium salt compound plays a main role in various fields of daily chemical industry, textile, mining, asphalt, construction, plastic processing, petroleum exploitation, petrochemical industry and the like. The common quaternary ammonium salt is mainly trioctyl methyl ammonium chloride, and the extraction mechanisms of trioctyl methyl ammonium nitrate and trioctyl methyl ammonium bromide are all anion exchange mechanisms. The quaternary ammonium salts which are synthesized at present and used for extraction belong to quaternary ammonium salts of inorganic ligands, and when the quaternary ammonium salts are used as an extractant, a large amount of extraction waste liquid which contains Cl -、NO3-, br - and the like and is difficult to treat is generated, so that the wastewater treatment cost is high and the environment is polluted. The method for synthesizing quaternary ammonium salt from carbonic diester and ammonium salt under the action of catalyst is disclosed in ZL 200510061094.4. The method uses ammonium salt to replace amine or amide as an initial reactant, uses carbonic acid diester to replace halohydrocarbon or sulfate as a quaternizing reagent, has obvious advantages compared with the traditional process, on one hand, anions of a target product can be selected manually, if the anions are to be synthesized into quaternary ammonium salt of fluorine, sulfate radical, acetate radical, oxalate radical, nitrate radical or phosphate radical, the one-step reaction is also needed, an ion exchange process is not needed, on the other hand, the phosphoric acid diester is nontoxic, exists in the form of alcohol and carbon dioxide after the reaction, and is easy to separate from the product. However, according to the patent application, the preparation method must be realized under the action of a proper catalyst, wherein the ionic liquid 1-methyl-3-ethylimidazole and the product belong to quaternary ammonium salt, separation is a problem, the catalyst and the product have anion exchange reaction, and anions in the catalyst can be doped into the product, so that the product is impure. ZL 200910131461.1 is prepared by reacting trioctyl ammonium and methyl chloride in the presence of a catalyst to directly generate trioctyl methyl ammonium chloride, wherein the reaction temperature is 75-95 ℃, the reaction pressure is less than 0.2MPa, the reaction time is 10-15 h, and the temperature is kept for 2-3 h at 84-95 ℃ after the reaction is finished. The process synthesizes trioctyl methyl ammonium chloride at high temperature and high pressure, and has high purity, high equipment requirement, long reaction time and high production cost. When trioctylmethyl ammonium chloride is used for extraction, chloride ions in the extractant can enter raffinate according to an anion exchange mechanism, so that a large amount of chlorine-containing wastewater which is difficult to treat is generated, and the environment is polluted. In summary, the existing process for synthesizing the quaternary ammonium salt is complex and has the problems of long reaction time, difficult product separation, low yield, and the like, which are usually carried out under the conditions of high temperature and high pressure. Therefore, a preparation method of quaternary ammonium salt which is easy to operate is needed. Disclosure of Invention In order to solve the technical problems in the prior art, the embodiment of the invention provides a preparation method of oxalic acid ligand binary quaternary ammonium salt. The technical scheme is as follows: a method for preparing a binary quaternary ammonium salt of an oxalic acid ligand, the method comprising: S1, mixing quaternary ammonium halide with sodium hydroxide solution, heating in a reaction kettle for reaction, cooling, and separating phases to obtain trioctyl methyl ammonium hydroxide; s2, mixing the trioctyl methyl ammonium hydroxide obtained in the step S1 with oxalic acid solution, heating in a reaction kettle for reaction, cooling and then separating phases to obtain a binary quaternary ammonium salt crude product; And S3, washing and drying the binary quaternary ammonium salt crude product obtained in the step S2 to obtain the oxalic acid ligand binary quaternary ammonium salt. The quaternary ammonium halide in the S1 is one of trioctylmethyl ammonium chloride, trioctylmethyl ammonium iodide and trioctylmethyl ammonium bromide. And the molar ratio of the quater