CN112939789B - Preparation method of methyl tributyl ammonium chloride - Google Patents
Preparation method of methyl tributyl ammonium chloride Download PDFInfo
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- CN112939789B CN112939789B CN202110144555.3A CN202110144555A CN112939789B CN 112939789 B CN112939789 B CN 112939789B CN 202110144555 A CN202110144555 A CN 202110144555A CN 112939789 B CN112939789 B CN 112939789B
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- ammonium chloride
- tributyl ammonium
- methyl tributyl
- dimethyl carbonate
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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Abstract
The invention relates to a preparation technology of methyl tributyl ammonium chloride. The preparation process comprises the steps of adding tributylamine hydrochloride, dimethyl carbonate and an acid catalyst into a reaction kettle, reacting at the temperature of 100-170 ℃ for 6-24 hours, cooling, crystallizing, filtering, and drying to obtain the high-purity methyl tributyl ammonium chloride. The method avoids using dangerous and high-toxicity raw materials such as methyl chloroformate and chloromethane, does not need repeated recrystallization and purification, and is a safe and environment-friendly preparation technology of the methyl tributyl ammonium chloride with high yield and low cost.
Description
Technical Field
The invention relates to a preparation method of a quaternary ammonium salt fine chemical, in particular to a preparation technology of methyl tributyl ammonium chloride.
Background
The ionic liquid is generally a liquid ionic compound at room temperature, has the characteristics of wide liquid range, excellent conductivity, wide electrochemical window, high thermodynamic stability, low vapor pressure, difficult volatilization, low toxicity and difficult combustion, can better dissolve most of biological macromolecules such as organic compounds, metal salts, cellulose and the like, and is called as a green solvent. The ionic liquid has designability, and the property and functionality of the ionic liquid can be adjusted by adjusting the structure and the type of anions and cations, so the ionic liquid is a soft functional material. Through development for many years, the ionic liquid is not only a green solvent or a catalyst, and has related researches in various subjects such as electrochemistry, material chemistry, organic chemistry, polymer chemistry, analytical chemistry, separation and purification technologies and the like, and the ionic liquid has good application prospects in the fields of clean energy, resource environment, biomedicine, aerospace and the like, and becomes an attractive frontier field.
An important class of ionic liquids is composed of quaternary ammonium cations matched with various anions, and different functionalities are endowed to the ionic liquids. Of which methyltributylammonium cation is a very common cationic constituent, with different anions such as OAc-，BF4 -,PF6 -,TFSI-Etc. may each constitute a different ionic liquid from it. Methyl tributyl ammonium chloride is a precursor for preparing such ionic liquids by anionThe corresponding ionic liquid can be conveniently prepared by the ion exchange reaction. Therefore, the preparation technology of methyl tributyl ammonium chloride with high purity and low cost becomes very important.
According to the existing method, the synthesis method of methyl tributyl ammonium chloride has three methods:
the first step is that tributylamine reacts with dimethyl carbonate and then is neutralized by hydrogen chloride. In the technical route, due to the chemical inertia of tributylamine, the tributylamine and dimethyl carbonate do not completely react, so that ammonium salt is generated with the rest tributylamine after the hydrogen chloride is neutralized, the product is impure, repeated recrystallization is needed, and the yield is low and the cost is high.
The second method is to react tributylamine with methyl chloroformate. Methyl chloroformate is decomposed at a certain temperature to generate methyl chloride to participate in the reaction, but the methyl chloroformate is highly toxic, inflammable, irritant and highly corrosive, belongs to dangerous chemicals, and is not a proper methylation raw material. The third method is the direct reaction of tributylamine with methyl chloride. This is currently the most common method and gives higher yields of product. But chloromethane is also a dangerous chemical, and is a gas, so that the storage, transportation and metering are inconvenient. And the chloromethane is easy to decompose at a certain temperature and in a solvent, so that the product contains a certain amount of tributylamine hydrochloride, which brings difficulty to subsequent treatment and can not obtain high-purity methyl tributyl ammonium chloride.
Chinese patent 200510061094.4 discloses that dimethyl carbonate and ammonium salt are used as raw materials to synthesize quaternary ammonium salts of different anions under the action of ionic liquid [ Emim ] Br catalyst. The catalyst and the product have similar properties and are difficult to separate.
Chinese patent 200710008626.7 makes an important improvement on the method of Chinese patent 200510061094.4, and dimethyl carbonate and ammonium salt are used as raw materials to directly synthesize quaternary ammonium salts of different anions in the absence of a catalyst, but the reaction cannot be completely completed, and the product purity cannot meet the requirement.
In view of the above-mentioned method for preparing methyl tributyl ammonium chloride, the problems that exist include: (1) dangerous and high-toxicity raw materials such as methyl chloroformate and methyl chloride need to be used, so that the risk is brought to the production process; (2) a small amount of free amine salt is often generated in the reaction process and included in the product, so that the product purity is not high, the product needs to be purified through recrystallization operation, the operation is complicated, and the yield is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a safe, environment-friendly, high-yield and high-purity preparation method of methyl tributyl ammonium chloride.
In order to achieve the purpose, the invention adopts the following technical scheme:
under the action of catalytic amount of acid, tributylamine hydrochloride can react with dimethyl carbonate completely to obtain almost quantitatively methyl tributyl ammonium chloride, and the residual amount of tributylamine hydrochloride is very small, so that high-purity methyl tributyl ammonium chloride product can be obtained without recrystallization and refining.
To achieve the above object, the technical idea of the present invention is as follows: tributylamine hydrochloride and dimethyl carbonate are used as raw materials, and methylation reaction is carried out in the presence of catalytic amount of acid, wherein the dimethyl carbonate is used as a solvent and a reactant.
The technical scheme of the invention comprises the following steps: adding tributylamine hydrochloride, dimethyl carbonate and an acid catalyst in a certain proportion into a pressure kettle, stirring and heating to a certain temperature, reacting for a certain time at a constant temperature, cooling and crystallizing, washing with a small amount of dimethyl carbonate, and performing suction filtration and drying to obtain a methyl tributyl ammonium chloride product.
The tributylamine hydrochloride used as the raw material can be purchased from commercial sources or prepared by self. If self-made, the method comprises the following steps: under the cooling condition, tributylamine and hydrochloric acid water solution with equal molar ratio are neutralized to neutral pH, and the water is evaporated under reduced pressure and then dried.
Preferably, the acid catalyst of the present invention includes commonly used inorganic acids and organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, alcoholic hydrogen chloride solution, and the like. Hydrochloric acid and alcoholic hydrogen chloride solutions are preferred.
Preferably, the reaction solvent in the invention is dimethyl carbonate or a mixture of dimethyl carbonate and a C1-C6 alcohol solvent, and preferably dimethyl carbonate.
Preferably, the molar ratio of tributylamine hydrochloride to dimethyl carbonate is 1: (2.0-5.0), preferably 1: 3.0.
Preferably, the molar ratio of tributylamine hydrochloride to acid catalyst in the invention is 1: (0.005-0.10), preferably 1: 0.01.
Preferably, the reaction temperature is 100-170 ℃, and preferably 120-130 ℃.
Preferably, the reaction time is 6-24 hours, and preferably 12-18 hours.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the method avoids using dangerous and high-toxicity raw materials such as methyl chloroformate and chloromethane, uses nontoxic and environment-friendly dimethyl carbonate as a raw material for methylation reaction, and is beneficial to industrial production.
The methyl tributyl ammonium chloride product prepared by the method has high purity, wherein the content of free amine salt impurities is extremely low, so that the high-purity methyl tributyl ammonium chloride can be prepared, and the purity is generally more than 99%.
The invention does not need recrystallization operation for purification, simplifies the preparation procedure, improves the yield and reduces the manufacturing cost.
Detailed Description
The invention is further described below by means of specific embodiments.
Example 1: 111g tributylamine hydrochloride, 130ml dimethyl carbonate and 0.6ml 30% hydrochloric acid solution are weighed and added into a 500ml pressure kettle in sequence, the pressure kettle is sealed, and the temperature is raised to 120 ℃ under stirring for constant temperature reaction for 15 hours. Naturally cooling to room temperature, leaching the precipitated crystals, washing with 50ml of dimethyl carbonate, and drying in vacuum to obtain 109.9g of methyl tributyl ammonium chloride with the yield of 93.2%. The quantitative analysis of the content of methyl tributyl ammonium chloride is 99.3 percent, the content of free tributyl amine hydrochloride is 0.2 percent, and the water content is 0.5 percent.
Example 2: 111g tributylamine hydrochloride, 130ml dimethyl carbonate and 0.3ml 30% hydrochloric acid solution are weighed and added into a 500ml pressure kettle in sequence, the pressure kettle is sealed, and the temperature is raised to 120 ℃ under stirring for constant temperature reaction for 15 hours. Naturally cooling to room temperature, leaching the precipitated crystals, washing with 50ml of dimethyl carbonate, and drying in vacuum to obtain 105.6g of methyl tributyl ammonium chloride with the yield of 89.5%. The quantitative analysis of the content of methyl tributyl ammonium chloride is 99.1 percent, the content of free tributyl amine hydrochloride is 0.4 percent, and the water content is 0.5 percent.
Example 3: 111g tributylamine hydrochloride, 130ml dimethyl carbonate and 2ml 1.25M hydrogen chloride methanol solution are weighed and added into a 500ml pressure kettle in sequence, sealed and stirred, and the temperature is raised to 120 ℃ for constant temperature reaction for 15 hours. Naturally cooling to room temperature, filtering the precipitated crystals by suction, washing with 50ml of dimethyl carbonate, and drying in vacuum to obtain 114.0g of methyl tributyl ammonium chloride with the yield of 96.6%. The quantitative analysis of the content of methyl tributyl ammonium chloride is 99.4 percent, the content of free tributyl amine hydrochloride is 0.2 percent, and the water content is 0.4 percent.
Example 4: 111g tributylamine hydrochloride, 130ml dimethyl carbonate and 4ml 1.25M hydrogen chloride methanol solution are weighed and added into a 500ml pressure kettle in sequence, the pressure kettle is sealed, and the temperature is raised to 120 ℃ under stirring for constant temperature reaction for 15 hours. Naturally cooling to room temperature, leaching the precipitated crystals, washing with 50ml of dimethyl carbonate, and drying in vacuum to obtain 115.7g of methyl tributyl ammonium chloride with the yield of 98.1%. The quantitative analysis of the content of methyl tributyl ammonium chloride is 99.6 percent, the content of free tributyl amine hydrochloride is 0.1 percent, and the water content is 0.3 percent.
Example 5: 111g tributylamine hydrochloride, 130ml dimethyl carbonate and 0.2ml 98% concentrated sulfuric acid are weighed and added into a 500ml pressure kettle in sequence, the pressure kettle is sealed, and the temperature is raised to 120 ℃ under stirring for constant temperature reaction for 15 hours. Naturally cooling to room temperature, filtering the precipitated crystals by suction, washing with 50ml of dimethyl carbonate, and drying in vacuum to obtain 106.8g of methyl tributyl ammonium chloride with the yield of 90.5%. The quantitative analysis of the content of methyl tributyl ammonium chloride is 99.1 percent, the content of free tributyl amine hydrochloride is 0.5 percent, and the water content is 0.4 percent.
Example 6: 111g tributylamine hydrochloride, 200ml dimethyl carbonate and 0.6ml 30% hydrochloric acid solution are weighed and added into a 500ml pressure kettle in sequence, sealed, stirred and heated to 120 ℃ for constant temperature reaction for 15 hours. Naturally cooling to room temperature, leaching the precipitated crystals, washing with 50ml of dimethyl carbonate, and drying in vacuum to obtain 109.5g of methyl tributyl ammonium chloride with the yield of 92.8%. The quantitative analysis of the content of methyl tributyl ammonium chloride is 99.5 percent, the content of free tributyl amine hydrochloride is 0.1 percent, and the water content is 0.4 percent.
Comparative example 1: 111g tributylamine hydrochloride and 130ml dimethyl carbonate are weighed and added into a 500ml pressure kettle in sequence, sealed and stirred, and the temperature is raised to 120 ℃ for constant temperature reaction for 15 hours. Naturally cooling to room temperature, leaching the precipitated crystals, washing with 50ml of dimethyl carbonate, and drying in vacuum to obtain 109.9g of methyl tributyl ammonium chloride with the yield of 88.6%. The content of methyl tributyl ammonium chloride is analyzed quantitatively, wherein the content of methyl tributyl ammonium chloride is 98.3%, the content of free tributyl amine hydrochloride is 1.2%, and the content of water is 0.5%. The above description is only for the purpose of further illustrating the present invention and should not be construed as limiting the scope of the present invention, and any modifications, variations and adaptations made to the above embodiments based on the technical essence of the present invention are within the technical scope of the present invention.
Claims (7)
1. The preparation method of methyl tributyl ammonium chloride is characterized by comprising the following steps:
adding tributylamine hydrochloride, dimethyl carbonate and an acid catalyst in a certain proportion into a pressure kettle, stirring and heating to a certain temperature, reacting for a certain time at a constant temperature, cooling and crystallizing, washing a small amount of dimethyl carbonate, and performing suction filtration and drying to obtain a high-purity methyl tributyl ammonium chloride product;
the acid catalyst is hydrochloric acid and hydrogen chloride alcohol solution.
2. The method for preparing methyl tributyl ammonium chloride according to claim 1, wherein the method comprises the following steps: the reaction solvent is dimethyl carbonate or a mixture of dimethyl carbonate and C1-C6 alcohol solvents.
3. The method for preparing methyl tributyl ammonium chloride according to claim 1, wherein: after the reaction is finished, the methyl tributyl ammonium chloride product with the purity of more than 99 percent can be obtained without recrystallization.
4. The method for preparing methyl tributyl ammonium chloride according to claim 1, wherein the method comprises the following steps: the molar ratio of tributylamine hydrochloride to dimethyl carbonate is 1: (2.0-5.0).
5. The method for preparing methyl tributyl ammonium chloride according to claim 1, wherein: the molar ratio of the tributylamine hydrochloride to the acid catalyst is 1: (0.005-0.10).
6. The method for preparing methyl tributyl ammonium chloride according to claim 1, wherein the method comprises the following steps: the reaction temperature is 100-170 ℃.
7. The method for preparing methyl tributyl ammonium chloride according to claim 1, wherein the method comprises the following steps: the reaction time is 6-24 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
| CN101245019A (en) * | 2007-02-14 | 2008-08-20 | 邱建兴 | Novel technique for synthesizing quaternary ammonium salt |
| CN101624347A (en) * | 2008-07-07 | 2010-01-13 | 翟和生 | Novel method for synthesizing quaternary ammonium salts |
| CN103351301A (en) * | 2013-07-01 | 2013-10-16 | 安徽奔马先端科技有限公司 | Synthetic method for high-purity quaternary ammonium salt |
| CN104163763A (en) * | 2014-07-14 | 2014-11-26 | 安徽奔马先端科技有限公司 | New synthesis method of high purity quaternary ammonium salt |
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- 2021-02-02 CN CN202110144555.3A patent/CN112939789B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
| CN101245019A (en) * | 2007-02-14 | 2008-08-20 | 邱建兴 | Novel technique for synthesizing quaternary ammonium salt |
| CN101624347A (en) * | 2008-07-07 | 2010-01-13 | 翟和生 | Novel method for synthesizing quaternary ammonium salts |
| CN103351301A (en) * | 2013-07-01 | 2013-10-16 | 安徽奔马先端科技有限公司 | Synthetic method for high-purity quaternary ammonium salt |
| CN104163763A (en) * | 2014-07-14 | 2014-11-26 | 安徽奔马先端科技有限公司 | New synthesis method of high purity quaternary ammonium salt |
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