CN114195681A - Preparation method of 1,2, 3-tri (cyanoethoxy) propane - Google Patents
Preparation method of 1,2, 3-tri (cyanoethoxy) propane Download PDFInfo
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- CN114195681A CN114195681A CN202010983170.1A CN202010983170A CN114195681A CN 114195681 A CN114195681 A CN 114195681A CN 202010983170 A CN202010983170 A CN 202010983170A CN 114195681 A CN114195681 A CN 114195681A
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- 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 discloses a preparation method of 1,2, 3-tri (cyanoethoxy) propane, which comprises the following steps: A1. stirring glycerin and a catalyst into a homogeneous phase, and adding a first part of acrylonitrile to form a two-phase system; A2. after the two-phase system reacts to form a homogeneous phase, adding a second part of acrylonitrile, and reacting to obtain a reactant; A3. the reactant is post-treated to obtain 1,2, 3-tri (cyanoethoxy) propane with the purity of more than 99.5 percent. The 1,2, 3-tri (cyanoethoxy) propane product prepared by the method has low content of alkene nitrile impurities and high product purity.
Description
Technical Field
The invention relates to synthesis of an electrolyte additive of a lithium ion battery, in particular to a preparation method of high-purity 1,2, 3-tri (cyanoethoxy) propane.
Background
Nitrile compounds are often used as additives in lithium ion battery electrolyte, and can effectively improve the high-temperature cycle and storage performance of the battery. But the use of nitrile additives also causes the problems of increased internal resistance of the cell and deterioration of normal temperature and low temperature cycle. 1,2, 3-tris (cyanoethoxy) propane is a nitrile compound and is also useful as an electrolyte additive.
At present, the preparation of 1,2, 3-tri (cyanoethoxy) propane mainly uses glycerol and acrylonitrile as raw materials and is obtained under the catalysis of alkali, and the reaction formula is as follows:
the reaction may be carried out in the presence of a solvent, such as:
patent EP2505622A discloses a process for the preparation of 1,2, 3-tris (cyanoethoxy) propane by reaction of glycerol (1eq) and acrylonitrile (7.5eq) in the presence of potassium hydroxide (0.6eq) in toluene solvent at room temperature. The reaction was separated by organic phase, dried and concentrated to give the product in 95% yield but unknown purity.
KR20150105790A discloses a process for the preparation of 1,2, 3-tris (cyanoethoxy) propane by reaction of glycerol (1eq) and acrylonitrile (16.5eq) in potassium hydroxide (0.8eq) in xylene solvent at room temperature. The product is obtained by washing, drying and vacuum desolventizing the reactant, the yield is 92 percent, and the purity is unknown.
Patent JP2013075837A discloses that glycerol (1eq) and acrylonitrile (3.6eq) are reacted in acetonitrile solvent at room temperature under the action of sodium tert-butoxide (0.001eq), and the reactants are desolventized to obtain 1,2, 3-tris (cyanoethoxy) propane, but the yield and purity are unknown.
The reaction can also be carried out in the absence of solvent, but the yield is slightly lower than in the case of the reaction with the participation of a solvent.
Such as: the article New Journal of Chemistry 2015,39(12),9155-9161 reports a process for preparing 1,2, 3-tris (cyanoethoxy) propane by reacting glycerol (1eq) and acrylonitrile (3.4eq) with sodium hydroxide (0.04eq) at room temperature. The product is obtained by purifying the reactant by column chromatography, the yield is 80 percent, and the GC purity is 99.9 percent. However, the method of column chromatography purification is expensive and is difficult to be industrially scaled up.
Patent JP2005263716A discloses a process for preparing 1,2, 3-tris (cyanoethoxy) propane by reacting glycerol (1eq) with acrylonitrile (3.1eq) at 60 ℃ under the action of sodium methoxide (0.04 eq). The process did not involve post-treatment of the reactants, the yield was 67%, and the purity was unknown.
Patent CN103562177A discloses a method for preparing 1,2, 3-tri (cyanoethoxy) propane by reacting glycerol (1eq) with acrylonitrile (3eq) at 40 ℃ under the action of potassium tert-butoxide (0.002 eq). The reactant in the method is dissolved by dichloromethane, and is concentrated and distilled under reduced pressure after being washed by water to obtain the 1,2, 3-tri (cyanoethoxy) propane, the yield is unknown, and the purity is 99 percent.
In the above-mentioned prior art, the method for obtaining the target product by desolventizing the reaction solution, except for the column chromatography post-treatment method unsuitable for industrial production, has been proved by a lot of experiments by the present inventors that the purity of the product is only about 90%. In contrast, in the method disclosed in CN103562177A, since the boiling point of the reaction solution is very high (>450 ℃), even if the boiling point of the reaction solution is higher than 200 ℃, alkene nitrile impurities are generated by decomposition during the distillation process, so that the purity of the actual product cannot reach the stated 99%.
The inventor of the invention discovers that the degrees of the normal temperature performance deterioration of the battery cell are inconsistent by adding 1,2, 3-tri (cyanoethoxy) propane with different purities into the electrolyte as an additive. Further studies have found that the presence of olefinic nitrile impurities in 1,2, 3-tris (cyanoethoxy) propane is critical in affecting performance. The concrete expression is as follows: the alkene nitrile compound contains double bonds in the structure, and electrons are easily obtained on the surface of an electrode to be reduced and decomposed. Tests show that the alkene nitrile compound has high film forming impedance, so that when the alkene nitrile impurity content in the electrolyte is high, the interface impedance of an electrode is increased, the internal resistance of the battery is increased, the cyclic attenuation is aggravated, and the normal-temperature performance and the low-temperature performance of the battery are worsened.
Therefore, it is necessary to prepare high-purity 1,2, 3-tris (cyanoethoxy) propane as an electrolyte additive so that the high-temperature performance of 1,2, 3-tris (cyanoethoxy) propane is efficiently utilized without deteriorating the normal-temperature performance and the low-temperature performance of the battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of 1,2, 3-tri (cyanoethoxy) propane, which has high product purity (low content of olefinic nitrile impurities), simple process and suitability for industrial production.
The purpose of the invention is realized by the following technical scheme:
a process for the preparation of 1,2, 3-tris (cyanoethoxy) propane, the process comprising:
A1. stirring glycerin and a catalyst into a homogeneous phase, and adding a first part of acrylonitrile to form a two-phase system;
A2. after the two-phase system reacts to form a homogeneous phase, adding a second part of acrylonitrile, and reacting to obtain a reactant;
A3. the reactant is subjected to post-treatment to obtain 1,2, 3-tri (cyanoethoxy) propane with the purity of more than 99.5%, and the structure of the 1,2, 3-tri (cyanoethoxy) propane is shown as the following formula (I):
the reaction formula of the invention is as follows:
the invention adopts a solvent-free reaction, so the catalyst is preferably a solid catalyst selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-pentoxide and potassium tert-pentoxide, and the molar amount of the catalyst is 0.001-0.1 eq of glycerol. More preferably, the catalyst is at least one selected from sodium hydroxide, potassium tert-butoxide and sodium tert-butoxide, and the molar amount of the catalyst is 0.002 to 0.04eq based on the glycerol.
Further, in the step A1, the glycerol and the catalyst are stirred under the heating condition to form a homogeneous phase, the heating temperature is 20-100 ℃, and the heating time is 1-6 hours. Preferably, the stirring and heating temperature is 40-80 ℃, and the heating time is 2-4 hours.
The reaction of glycerol and acrylonitrile is carried out in two stages, wherein the first stage of reaction is the reaction of a homogeneous mixture of the glycerol and a catalyst and a first part of acrylonitrile, the first stage of reaction is an exothermic reaction, and the reaction temperature is controlled to be 10-60 ℃; the first part of acrylonitrile can be added into the homogeneous mixture at one time or dripped into the homogeneous mixture as long as the reaction temperature is maintained between 10 and 60 ℃. Of course, for better control of the reaction temperature, the first portion of acrylonitrile is added dropwise in a molar amount of 0.5 to 2.0eq based on the amount of glycerol. The first stage of the reaction starts with the dropwise addition of a first portion of acrylonitrile until the reaction system is homogeneous.
After the first stage reaction becomes homogeneous phase from the two-phase system, adding a second part of acrylonitrile, and starting a second stage reaction. And (3) dropwise adding a second part of acrylonitrile (the sum of the molar amount of the second part of acrylonitrile and the molar amount of the first part of acrylonitrile is 3.0-4.0 eq of that of the glycerol), controlling the reaction temperature to be 0-50 ℃, and continuing to react for 2-10 hours after the dropwise adding is finished.
More preferably, the reaction temperature of the first stage is controlled to be 20-40 ℃, and the molar amount of the first part of acrylonitrile is 0.5-1.0 eq of that of glycerol; the second-stage reaction temperature is controlled to be 20-35 ℃, and the molar amount of the second part of acrylonitrile is 2.4-2.9 eq of that of the glycerol.
According to the above method for producing 1,2, 3-tris (cyanoethoxy) propane, the step a3 further comprises:
B1. adding an organic solvent into the reactant for dissolving, and washing with water to remove the catalyst in the reactant; drying and distilling the organic phase under reduced pressure to obtain a crude product;
B2. extracting the crude product by using a benzene solvent, and distilling the extract liquor under reduced pressure to obtain the 1,2, 3-tri (cyanoethoxy) propane.
Specifically, the B1 step may be: adding an organic solvent into the reactant for dissolving, washing for 2-3 times until the water phase is neutral, adding magnesium sulfate into the organic phase for drying, filtering, and concentrating the filtrate under reduced pressure to obtain an orange-red viscous liquid, namely a crude product of the 1,2, 3-tris (cyanoethoxy) propane.
Preferably, the organic solvent is at least one of diethyl ether, methyl tert-butyl ether, dichloromethane, dichloroethane, chloroform, n-hexane, n-heptane and ethyl acetate. More preferably, the organic solvent is at least one selected from dichloromethane, chloroform and ethyl acetate.
Preferably, the benzene-based solvent is at least one selected from the group consisting of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, chlorobenzene, and nitrobenzene. More preferably, the benzene-based solvent is at least one selected from benzene and toluene.
In order to improve the normal temperature performance and the low temperature performance of 1,2, 3-tris (cyanoethoxy) propane as an electrolyte additive, the product purity of 1,2, 3-tris (cyanoethoxy) propane needs to be further improved. The product purity of the 1,2, 3-tri (cyanoethoxy) propane is limited by the crude purity of the 1,2, 3-tri (cyanoethoxy) propane, and the crude purity of the 1,2, 3-tri (cyanoethoxy) propane prepared by the existing preparation process is lower, and the content of olefinic nitrile impurities is higher. The inventor of the invention has conducted extensive research and believes that the alkene nitrile impurities are caused by the incompatibility of glycerol and acrylonitrile, and are represented as follows: the glycerol and the acrylonitrile are not soluble, the direct reaction of the glycerol and the acrylonitrile is a two-phase reaction, the reaction is slow due to the fact that the contact area is small in the initial reaction stage, the contact area between the glycerol and the acrylonitrile is gradually increased along with stirring, the reaction is accelerated to cause heat release to be aggravated, the reaction is accelerated due to the rise of the temperature in the system, the macroscopic expression is that the temperature in the internal system is kept unchanged when the reaction is started for a long time, but the temperature rises by 20-30 ℃ suddenly in a short time, and then the temperature is gradually reduced. The system color changes from colorless to light yellow and then to brown yellow along with the temperature change, and the color change process is the process of polymerizing acrylonitrile into dimerization and trimer through heating, namely the process of generating acrylonitrile impurities which have great influence on the performance of the battery, so that the purity of a reaction crude product can only reach 90%.
Based on the above, the invention provides two-stage reaction of glycerol and acrylonitrile, which is different from the one-pot mixing reaction of glycerol and acrylonitrile in the prior art. According to the invention, the 3- (2, 3-dihydroxypropoxy) propionitrile intermediate is obtained by reacting glycerol with a small amount of acrylonitrile, the 3- (2, 3-dihydroxypropoxy) propionitrile intermediate has certain solubility with the glycerol and the acrylonitrile, so that the glycerol and the acrylonitrile which are originally immiscible form a homogeneous phase, and the subsequent second-stage reaction of adding a second part of acrylonitrile becomes a homogeneous reaction, so that the reaction is relatively stable, the phenomenon of greatly increasing the temperature can not occur, the byproducts of acrylonitrile polymerization are reduced, and the purity of the 1,2, 3-tri (cyanoethoxy) propane crude product reaches more than 95%.
Compared with the prior art, the invention has the beneficial effects that:
1. the reaction of the glycerol and the acrylonitrile is a two-stage reaction, and a 3- (2, 3-dihydroxypropoxy) propionitrile intermediate is formed by adding a first part of the acrylonitrile, so that the reaction becomes a homogeneous reaction, the content of olefinic nitrile impurities is greatly reduced, and the purity of a crude product is improved from 90% to 95%.
2. On the basis of obtaining a crude product with higher purity, the invention obtains a1, 2, 3-tri (cyanoethoxy) propane product with the alkene nitrile impurity content of less than or equal to 100ppm and the purity of more than or equal to 99.5 percent by a benzene solvent extraction mode, and the product is applied to the electrolyte of a lithium ion battery, so that the deterioration of the nitrile additive on the high-temperature performance and the low-temperature performance of the battery is greatly reduced on the basis of improving the high-temperature performance of the battery.
3. The preparation process combining the two-stage reaction and the benzene solvent extraction is suitable for industrial production, and improves the product yield and the product purity compared with the existing solvent-free reaction.
4. The organic solvent and the benzene solvent can be recycled after distillation, thereby reducing the production cost and the environmental pollution.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
46g (0.5mol) of glycerol and 0.5g (0.0125mol) of sodium hydroxide were added to a 500mL three-necked flask at room temperature, and the mixture was heated to 60 ℃ and stirred for 2 hours to completely dissolve the glycerol and the sodium hydroxide. Cooling to 20-25 ℃, dropwise adding 26.5g (0.5mol) of acrylonitrile into the system, after the dropwise adding is finished, enabling the two phases of the reaction system to be immiscible, and stirring for 2 hours until the reaction system is homogeneous (the temperature is raised by about 10 ℃); slowly adding the residual 63.6g (1.2mol) of acrylonitrile (controlling the internal temperature not to exceed 30 ℃) dropwise, finishing dropping for about 2 hours, and continuing the reaction for 5 hours after finishing dropping. After the reaction is finished, 300mL of dichloromethane is added into the system for dissolving, 200mL of distilled water is washed for 3 times until the water phase is neutral, magnesium sulfate is added for drying, the filtrate is decompressed and concentrated to be dried to obtain 122g of yellow viscous liquid, and the purity of a GC crude product is 95.2%.
The viscous liquid was further extracted with 500mL of toluene 2 times, the remaining red residue was discarded, the toluene phases were combined and concentrated under reduced pressure to remove toluene and obtain 108g of 1,2, 3-tris (cyanoethoxy) propane product. The product yield is 86%, the GC product purity is 99.6%, and the acrylonitrile impurities are not detected by GC-MS (gas chromatography-mass spectrometry) (< 0.01%).
Example 2
46g (0.5mol) of glycerol and 0.5g (0.0125mol) of sodium hydroxide were added to a 500mL three-necked flask at room temperature, and the mixture was heated to 60 ℃ and stirred for 2 hours to completely dissolve the glycerol and the sodium hydroxide. Cooling to 20-25 ℃, dropwise adding 19.88g (0.375mol) of acrylonitrile into the system, after the dropwise adding is finished, enabling the two phases of the reaction system to be immiscible, and stirring for 3 hours until the reaction system is homogeneous (the temperature is raised by 5-10 ℃); slowly adding the residual 70.22g (1.325mol) of acrylonitrile (controlling the internal temperature not to exceed 30 ℃) dropwise, finishing dropping for about 2 hours, and continuing the reaction for 5 hours after finishing dropping. After the reaction is finished, 300mL of dichloromethane is added into the system for dissolving, 200mL of distilled water is washed for 3 times until the water phase is neutral, magnesium sulfate is added for drying, the filtrate is decompressed and concentrated to be dry after being filtered, and light yellow viscous liquid 124g is obtained, and the purity of a GC crude product is 95.7%.
The viscous liquid was further extracted with 500mL of toluene 2 times, and the remaining yellow residue was discarded, and the toluene phases were combined and concentrated under reduced pressure to remove toluene and obtain 110g of 1,2, 3-tris (cyanoethoxy) propane product. The product yield was 88%, the GC product purity was 99.7%, and the acrylonitrile type impurities were not detected by GC-MS (< 0.01%).
Example 3
46g (0.5mol) of glycerol and 0.5g (0.0125mol) of sodium hydroxide were added to a 500mL three-necked flask at room temperature, and the mixture was heated to 60 ℃ and stirred for 2 hours to completely dissolve the glycerol and the sodium hydroxide. Cooling to 20-25 ℃, dropwise adding 13.25g (0.25mol) of acrylonitrile into the system, after the dropwise adding is finished, enabling the two phases of the reaction system to be immiscible, and stirring for 4 hours until the reaction system is homogeneous (no obvious temperature rise phenomenon is observed); the remaining 76.85g (1.45mol) of acrylonitrile was slowly added dropwise (the internal temperature was controlled not to exceed 30 ℃) and the reaction was continued for 5 hours after the completion of the addition of the dropwise addition. After the reaction is finished, 300mL of dichloromethane is added into the system for dissolving, 200mL of distilled water is washed for 3 times until the water phase is neutral, magnesium sulfate is added for drying, the filtrate is decompressed and concentrated to be dry after being filtered, yellow viscous liquid 115g is obtained, and the purity of a GC crude product is 95.4%.
The viscous liquid was further extracted with 500mL of toluene 2 times, the remaining red residue was discarded, the toluene phases were combined and concentrated under reduced pressure to remove toluene and obtain 101g of 1,2, 3-tris (cyanoethoxy) propane product. The product yield is 80%, the GC product purity is 99.6%, and the acrylonitrile impurities are not detected by GC-MS (gas chromatography-mass spectrometry) (< 0.01%).
Example 4
A500 mL three-necked flask was charged with 46g (0.5mol) of glycerin and 0.14g (0.00125mol) of potassium tert-butoxide at room temperature, and heated to 60 ℃ to be stirred for 2 hours to be completely dissolved. Cooling to 40-45 ℃, dropwise adding 26.5g (0.5mol) of acrylonitrile into the system, after the dropwise adding is finished, enabling the two phases of the reaction system to be immiscible, and stirring for 2 hours until the reaction system is homogeneous; slowly adding the residual 63.6g (1.2mol) of acrylonitrile (controlling the internal temperature to be 40-50 ℃) dropwise, finishing dropping for about 2 hours, and continuing the reaction for 5 hours after finishing dropping. After the reaction is finished, 300mL of dichloromethane is added into the system for dissolving, 200mL of distilled water is washed for 3 times until the water phase is neutral, magnesium sulfate is added for drying, the filtrate is decompressed and concentrated to be dried to obtain 120g of yellow viscous liquid, and the purity of GC crude product is 95.1%.
The viscous liquid was further extracted with 500mL of toluene 2 times, and the remaining yellow residue was discarded, and the toluene phases were combined and concentrated under reduced pressure to remove toluene and obtain 106g of 1,2, 3-tris (cyanoethoxy) propane product. The product yield is 84%, the GC product purity is 99.5%, and the acrylonitrile impurities are not detected by GC-MS (gas chromatography-mass spectrometry) (< 0.01%).
Example 5
46g (0.5mol) of glycerol and 0.7g (0.0125mol) of potassium hydroxide were added to a 500mL three-necked flask at room temperature, and the mixture was heated to 60 ℃ and stirred for 2 hours to completely dissolve the glycerol and the potassium hydroxide. Cooling to 20-25 ℃, dropwise adding 26.5g (0.5mol) of acrylonitrile into the system, after the dropwise adding is finished, enabling the two phases of the reaction system to be immiscible, and stirring for 2 hours until the reaction system is homogeneous; slowly adding the residual 63.6g (1.2mol) of acrylonitrile (controlling the internal temperature not to exceed 30 ℃) dropwise, finishing dropping for about 2 hours, and continuing the reaction for 5 hours after finishing dropping. After the reaction is finished, 300mL of dichloromethane is added into the system for dissolving, 200mL of distilled water is washed for 3 times until the water phase is neutral, magnesium sulfate is added for drying, the filtrate is decompressed and concentrated to be dry after being filtered, yellow viscous liquid 116g is obtained, and the purity of a GC crude product is 95.0%.
The viscous liquid was further extracted with 500mL of toluene 2 times, and the remaining red residue was discarded, and the toluene phases were combined and concentrated under reduced pressure to remove toluene, whereby 102g of 1,2, 3-tris (cyanoethoxy) propane was obtained. The product yield is 81%, the GC product purity is 99.5%, and the acrylonitrile impurities are not detected by GC-MS (gas chromatography-mass spectrometry) (< 0.01%).
Comparative example 1
46g (0.5mol) of glycerol and 0.5g (0.0125mol) of sodium hydroxide were added to a 500mL three-necked flask at room temperature, and the mixture was heated to 60 ℃ and stirred for 2 hours to completely dissolve the glycerol and the sodium hydroxide. Cooling to 20-25 ℃, slowly dripping 90.1g (1.7mol) of acrylonitrile into the system, after dripping, ensuring that the two phases of the reaction system are immiscible, stirring for 2 hours, suddenly raising the internal temperature to 55 ℃, slowly cooling to room temperature, ensuring that the reaction system becomes homogeneous and yellow, and continuously reacting for 5 hours. After the reaction is finished, 300mL of dichloromethane is added into the system for dissolving, 200mL of distilled water is washed for 3 times until the water phase is neutral, magnesium sulfate is added for drying, the filtrate is decompressed and concentrated to be dry after being filtered, and orange-red viscous liquid 132g is obtained, and the purity of GC crude product is 90.3%.
The viscous liquid was further extracted with 500mL of toluene 3 times, the remaining red residue was discarded, the toluene phases were combined and concentrated under reduced pressure to remove toluene and obtain 107g of 1,2, 3-tris (cyanoethoxy) propane product. The product yield is 85 percent, the GC product purity is 97.9 percent, and the alkene nitrile impurities are 1.3 percent.
Comparative example 2
This comparative example was conducted in the same manner as in example 1 to obtain a crude product.
And (3) carrying out reduced pressure distillation on the crude product, wherein the oil pump pressure is 40Pa, and the product distillation temperature is 225-228 ℃, so as to obtain 98g of 1,2, 3-tris (cyanoethoxy) propane product. The product yield is 78 percent, the GC product purity is 98.2 percent, and the alkene nitrile impurities are 1.1 percent.
Claims (10)
1. A preparation method of 1,2, 3-tri (cyanoethoxy) propane is characterized by comprising the following steps: the preparation method comprises the following steps:
A1. stirring glycerin and a catalyst into a homogeneous phase, and adding a first part of acrylonitrile to form a two-phase system;
A2. after the two-phase system reacts to form a homogeneous phase, adding a second part of acrylonitrile, and reacting to obtain a reactant;
A3. the reactant is post-treated to obtain 1,2, 3-tri (cyanoethoxy) propane with the purity of more than 99.5 percent.
2. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 1, characterized in that: the catalyst is a solid catalyst and is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-pentoxide and potassium tert-pentoxide.
3. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 1, characterized in that: the reaction temperature in the step A1 is 10-60 ℃, and the reaction temperature in the step A2 is 0-50 ℃.
4. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 3, characterized in that: the reaction temperature of the step A1 is 20-40 ℃, and the reaction temperature of the step A2 is 20-35 ℃.
5. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 3 or 4, characterized in that: in the step A1, the molar amount of the first part of acrylonitrile is 0.5-2.0 eq of that of glycerol, and the molar amount of the catalyst is 0.001-0.1 eq of that of the glycerol; the sum of the molar amount of the second part of acrylonitrile and the molar amount of the first part of acrylonitrile in the step A2 is 3.0-4.0 eq of that of glycerol.
6. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 5, characterized in that: and in the step A2, adding a second part of acrylonitrile in a dropwise adding mode, and continuing to react for 2-10 hours after the dropwise adding is finished.
7. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 1, characterized in that: the glycerol and the catalyst are stirred into a homogeneous phase under the heating condition, the heating temperature is 20-100 ℃, and the heating time is 1-6 hours.
8. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 1, characterized in that: the step A3 further comprises:
B1. adding an organic solvent into the reactant for dissolving, and washing with water to remove the catalyst in the reactant; drying and distilling the organic phase under reduced pressure to obtain a crude product;
B2. extracting the crude product by using a benzene solvent, and distilling the extract liquor under reduced pressure to obtain the 1,2, 3-tri (cyanoethoxy) propane.
9. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 8, characterized in that: the organic solvent is at least one of diethyl ether, methyl tert-butyl ether, dichloromethane, dichloroethane, chloroform, n-hexane, n-heptane and ethyl acetate.
10. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 8, characterized in that: the benzene solvent is at least one selected from benzene, toluene, ethylbenzene, xylene, trimethylbenzene, chlorobenzene and nitrobenzene.
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| CN116606219A (en) * | 2023-06-06 | 2023-08-18 | 山东永浩新材料科技有限公司 | Production method and system of 1,2, 3-tri (cyanoethoxy) propane |
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| RATUSKY, J. ET AL.: "Preparation and use of β-cyanoethylated polyhydric alcohols in gas chromatography", COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, vol. 29, no. 12, pages 3066 - 3088 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116606219A (en) * | 2023-06-06 | 2023-08-18 | 山东永浩新材料科技有限公司 | Production method and system of 1,2, 3-tri (cyanoethoxy) propane |
| CN116606219B (en) * | 2023-06-06 | 2024-02-23 | 山东永浩新材料科技有限公司 | Production method and system of 1,2, 3-tri (cyanoethoxy) propane |
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