CN114621117A - Method for preparing ethylene glycol bis (propionitrile) ether crude product by anhydrous method - Google Patents
Method for preparing ethylene glycol bis (propionitrile) ether crude product by anhydrous method Download PDFInfo
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- CN114621117A CN114621117A CN202210528915.4A CN202210528915A CN114621117A CN 114621117 A CN114621117 A CN 114621117A CN 202210528915 A CN202210528915 A CN 202210528915A CN 114621117 A CN114621117 A CN 114621117A
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- ethylene glycol
- propionitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
The invention provides a method for preparing a crude product of ethylene glycol bis (propionitrile) ether by an anhydrous method, which relates to the technical field of chemical industry and comprises the following steps: s1, preparing materials: ethylene glycol and a catalyst are mixed according to the mass ratio of 100: (0.02-0.5) preparing, and uniformly stirring to form a mixed solution; the mass ratio of the total mass of the acrylonitrile to the mass of the ethylene glycol is (2.0-2.2): 1; s2, stage reaction: under the temperature condition of 20-80 ℃, adding acrylonitrile into the mixed liquid of S1 in stages, reacting for 3 hours to obtain a crude product, carrying out gas chromatography detection and calculating the yield; the whole preparation process of the invention has no water participation, and the problem that the water content of the ethylene glycol bis (propionitrile) ether exceeds the standard is effectively avoided; and the reaction is carried out by stages, so that the occurrence of side reaction is effectively avoided, and the reaction yield can reach 97.44%; meanwhile, the addition amount of the catalyst is small, and the difficulty in removing the catalyst is reduced.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method of a crude product of ethylene glycol bis (propionitrile) ether by an anhydrous method.
Background
Ethylene glycol bis (propionitrile) ether is a high-voltage lithium ion battery additive, can improve the high-temperature performance of a lithium ion battery, is widely used in lithium cobaltate batteries at present, and can be compounded with FEC to inhibit the high-temperature swelling of the batteries in the development of the lithium iron phosphate power battery. Ethylene glycol bis (propionitrile) ether as a lithium battery additive has high requirements on purity and water content, and most of products sold in the market at present have the purity of more than 99.5 percent and the water content of less than 100 ppm. Regarding the preparation method of ethylene glycol bis (propionitrile) ether, a plurality of patent documents have been reported at home and abroad, and ethylene glycol bis (propionitrile) ether crude products are prepared by respectively adopting different catalysts and reaction conditions, but most of the prior art is involved in the reaction of the preparation process with water, so that the problem of overproof water content in the later-stage products is caused; meanwhile, the catalyst in the prior art is used in a large amount, so that the difficulty in later-stage catalyst removal is increased; in addition, the prior art method can cause a large amount of acrylonitrile to generate self-polymerization reaction, increase side reactions and cause lower reaction yield.
Disclosure of Invention
Solves the technical problem
Aiming at the defects of the prior art, the invention provides a method for preparing a crude product of ethylene glycol bis (propionitrile) ether by an anhydrous method, and the method has no water participation in the whole process, so that the problem that the water content of the ethylene glycol bis (propionitrile) ether exceeds the standard is effectively avoided; the reaction is carried out by stages, so that the occurrence of side reaction is effectively avoided, and the reaction yield can reach more than 97 percent; the catalyst consumption is low, and the catalyst removal difficulty is reduced; high catalytic efficiency and short reaction time to about 3 hours.
Technical scheme
In order to achieve the above purpose, the invention is realized by the following scheme:
the preparation method of the crude product of the ethylene glycol bis (propionitrile) ether by the anhydrous method comprises the following steps:
s1, preparing materials: ethylene glycol and a catalyst are mixed according to the mass ratio of 100: (0.02-0.5) preparing, and uniformly stirring to form a mixed solution; the mass ratio of the total mass of the acrylonitrile to the mass of the ethylene glycol is (2.0-2.2): 1;
s2, stage reaction: and (3) adding acrylonitrile into the mixed solution S1 in stages at the temperature of 20-80 ℃, reacting for 3 hours to obtain a crude product, and performing gas chromatography detection and calculating the yield.
Preferably, the catalyst in S1 is formed by compounding sodium ethoxide, ethanolamine and ethylene glycol, wherein the mass content of sodium ethoxide is 20-50%, the mass content of ethanolamine is 10-40%, and the mass content of ethylene glycol is 30-70%.
Preferably, the mass ratio of the ethylene glycol to the catalyst in the S1 is 100: (0.2-0.3), the total mass of the acrylonitrile is 2 times of that of the ethylene glycol.
Preferably, the temperature conditions in S2 are 30 ℃ to 70 ℃; the stage reaction in S2 is a reaction which is divided into different numbers of stages according to reaction time and temperature control conditions, wherein the distribution ratio of acrylonitrile in each stage is not fixed.
Preferably, the yield of S2 can reach 97.44%.
Advantageous effects
The method for preparing the crude product of the glycol bis (propionitrile) ether by the anhydrous method can provide an anhydrous, efficient and easy-to-purify glycol bis (propionitrile) ether preparation method which is suitable for industrialization, and the method has no water participation in the whole process, so that the problem that the water content of the glycol bis (propionitrile) ether exceeds the standard is effectively avoided; and the reaction is carried out by stages, so that the occurrence of side reaction is effectively avoided, and the reaction yield can reach 97.44%; meanwhile, the dosage of the catalyst is small, so that the difficulty in removing the catalyst is reduced; the catalyst has high efficiency, and the reaction time is shortened to about 3 hours.
Detailed Description
The following is a clear and complete description of the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of examples of the present invention, and not all implementation cases. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1:
105.65g of ethylene glycol, 90.90g of acrylonitrile # 1, 72.7g of acrylonitrile # 2 and 20.8g of acrylonitrile # 3 are weighed, and 0.35g of catalyst is taken, wherein the catalyst comprises the following components in percentage by mass: ethanolamine: the ethylene glycol is 5:1:4, the ethylene glycol and the catalyst are uniformly mixed in a 500ml flask at normal temperature, magnetic stirring is started, a dropping funnel is connected to the middle opening of the flask, a thermometer is arranged at one opening of the flask, the flask is fixed in a constant-temperature water bath kettle, 1# acrylonitrile is poured into the dropping funnel to perform first-stage reaction, the temperature is controlled to be 80 ℃, the time is 1 hour, and stirring is continued for 10 minutes until the dropping is finished; then pouring 2# acrylonitrile into the separating funnel, carrying out the second stage reaction, controlling the temperature at 50 ℃ for 1 hour, and continuing stirring for 20 minutes until the dripping is finished; and then pouring 3# acrylonitrile into the separating funnel, carrying out a third-stage reaction, controlling the temperature to be 30 ℃, continuing stirring for 30 minutes after finishing dripping, stopping the reaction, carrying out post-treatment, taking a crude product, and carrying out gas chromatography by using a gas chromatograph Agilent 8860 to detect that the purity is 94.63%, wherein the yield of the obtained target product is 96.41%.
Example 2:
weighing 201g of ethylene glycol, 270g of 1# acrylonitrile and 93.6g of 2# acrylonitrile, and taking 0.7g of catalyst, wherein the catalyst comprises the following components in percentage by mass: ethanolamine: the ethylene glycol is 2:3:5, the ethylene glycol and the catalyst are uniformly mixed in a 1000ml flask at normal temperature, magnetic stirring is started, a dropping funnel is connected to the middle opening of the flask, a thermometer is arranged at one opening of the flask, the flask is fixed in a constant-temperature water bath kettle, 1# acrylonitrile is poured into the dropping funnel to perform first-stage reaction, the temperature is controlled at 70 ℃ for 1 hour, and stirring is continued for 20 minutes until the dropping is finished; and then pouring 2# acrylonitrile into the separating funnel, carrying out a second-stage reaction, controlling the temperature at 30 ℃ for 1 hour until the dripping is finished, continuing stirring for 20 minutes after the dripping is finished, stopping the reaction, carrying out post-treatment, taking a crude product, and carrying out gas chromatography detection on the crude product by using a gas chromatograph Agilent 8860 to obtain the target product with the purity of 94.33% and the yield of 97.44%.
Example 3:
100.04g of ethylene glycol, 90.2g of acrylonitrile No. 1 and 86.2g of acrylonitrile No. 2 are weighed, and 0.42g of catalyst is taken, wherein the catalyst comprises the following components in percentage by mass: ethanolamine: the ethylene glycol is 3:4:3, the ethylene glycol and the catalyst are uniformly mixed in a 500ml flask at normal temperature, magnetic stirring is started, a dropping funnel is connected to the middle opening of the flask, a thermometer is arranged at one opening of the flask, the flask is fixed in a constant-temperature water bath kettle, 1# acrylonitrile is poured into the dropping funnel to perform first-stage reaction, the temperature is controlled at 60 ℃, the time is 1 hour, and stirring is continued for 20 minutes until the dropping is finished; and then pouring 2# acrylonitrile into the separating funnel, carrying out a second-stage reaction, controlling the temperature to be 25 ℃, keeping the reaction for 1 hour until the dripping is finished, continuing stirring for 20 minutes after the dripping is finished, stopping the reaction, carrying out post-treatment, taking a crude product, and carrying out gas chromatography detection on the crude product by using a gas chromatograph Agilent 8860 to obtain a target product with the purity of 94.53% and the yield of 97.10%.
Example 4:
weighing 200.2g of ethylene glycol, 235g of acrylonitrile No. 1, 95.6g of acrylonitrile No. 2 and 30g of acrylonitrile No. 3, and taking 0.74g of catalyst, wherein the catalyst comprises the following components in percentage by mass: ethanolamine: the ethylene glycol is 4:1:5, the ethylene glycol and the catalyst are uniformly mixed in a 1000ml flask at normal temperature, magnetic stirring is started, a dropping funnel is connected to the middle opening of the flask, a thermometer is arranged at one opening of the flask, the flask is fixed in a constant-temperature water bath kettle, 1# acrylonitrile is poured into the dropping funnel to perform first-stage reaction, the temperature is controlled to be 65 ℃, the time is 1.5 hours, and stirring is continued for 10 minutes until the dropping is finished; then 2# acrylonitrile is poured into the separating funnel to carry out the second stage reaction, the temperature is controlled to be 45 ℃, and the stirring is continued for 10 minutes until the dripping is finished; and then pouring 3# acrylonitrile into the separating funnel, carrying out a third-stage reaction, controlling the temperature at 20 ℃ for about 20 minutes, continuing stirring for 10 minutes after the dripping is finished, stopping the reaction, carrying out post-treatment, taking a crude product, and carrying out gas chromatography by using a gas chromatograph Agilent 8860 to detect that the purity is 95.94%, wherein the yield of the obtained target product is 97.42%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A method for preparing a crude product of ethylene glycol bis (propionitrile) ether by an anhydrous method is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing materials: ethylene glycol and a catalyst are mixed according to the mass ratio of 100: (0.02-0.5) preparing, and uniformly stirring to form a mixed solution; the mass ratio of the total mass of the acrylonitrile to the mass of the ethylene glycol is (2.0-2.2): 1, wherein the catalyst is formed by compounding sodium ethoxide, ethanolamine and ethylene glycol;
s2, stage reaction: and (3) adding acrylonitrile into the mixed solution S1 in stages at the temperature of 20-80 ℃, reacting for 3 hours to obtain a crude product, and performing gas chromatography detection and calculating the yield.
2. The method for preparing the crude ethylene glycol bis (propionitrile) ether product according to claim 1, wherein the method comprises the following steps: the mass content of the catalyst sodium ethoxide in the S1 is 20-50%, the mass content of the ethanolamine is 10-40%, and the mass content of the ethylene glycol is 30-70%.
3. The method for preparing the crude ethylene glycol bis (propionitrile) ether product according to claim 1, wherein the method comprises the following steps: the mass ratio of the ethylene glycol to the catalyst in the S1 is 100: (0.2-0.3), the total mass of the acrylonitrile is 2 times of that of the ethylene glycol.
4. The method for preparing the crude ethylene glycol bis (propionitrile) ether product according to claim 1, wherein the method comprises the following steps: the temperature conditions in S2 are 30 ℃ to 70 ℃.
5. The method for preparing the crude ethylene glycol bis (propionitrile) ether product according to claim 1, wherein the method comprises the following steps: the yield of S2 can reach 97.44%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012128462A1 (en) * | 2011-03-18 | 2012-09-27 | 주식회사 엘지화학 | Method for preparing a dinitrile compound |
| CN112898181A (en) * | 2019-11-18 | 2021-06-04 | 石家庄圣泰化工有限公司 | Preparation method of 1,2, 3-tri (2-cyanoxy) propane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012128462A1 (en) * | 2011-03-18 | 2012-09-27 | 주식회사 엘지화학 | Method for preparing a dinitrile compound |
| CN112898181A (en) * | 2019-11-18 | 2021-06-04 | 石家庄圣泰化工有限公司 | Preparation method of 1,2, 3-tri (2-cyanoxy) propane |
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Application publication date: 20220614 |