Preparation method of 1, 2, 3, 4, 5-cyanoethoxy pentane
Through a simplified process route, pentaol and acrylonitrile catalyzed by inorganic base, controlling temperature and pressure, the high-purity 1,2,3,4,5-cyanoethoxypentane was successfully prepared, and lithium was solved The safety and non-combustibility of ion battery electrolytes have achieved efficient and economical production results.
Patent Information
- Application Number
- CN202311051256.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-08-21
- Publication Date
- 2025-02-21
AI Technical Summary
The prior art is difficult to effectively improve the safety and non-combustibility of lithium-ion battery electrolytes, especially in the additives of electrolytes.
A preparation method of 1,2,3,4,5-cyanoethoxypentane, which includes mixing pentahydric alcohol and acrylonitrile, using an inorganic alkali aqueous solution as a catalyst, controlling the temperature and pressure, and adding dropwise Reaction with concentration, and finally, high-purity product is obtained by crystallization and recrystallization.
It has achieved simplification of the process route, gentle and controllable reaction conditions, high purity and high yield of the product, meet the purity requirements of lithium-ion battery electrolyte additives, and reduces production costs.
Smart Images
Figure CN119490434A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a method in the technical field of compound synthesis, and in particular to a method for preparing 1,2,3,4,5-cyanoethoxypentane. Background Art
[0002] As an important component of lithium-ion batteries, the electrolyte system is also developing continuously. In the electrolyte system, whether it is the research of electrolyte lithium salts, or the research of new organic solvents or electrolyte additives, it has been ongoing. Since additives can have a great impact on battery performance, they have received widespread attention.
[0003] It is recorded in the literature that carbonate containing cyano structure can improve the non-flammability of electrolyte and enhance the safety of electrolyte. To this end, the present invention aims to provide a method for preparing 1,2,3,4,5-cyanoethoxypentane. Summary of the invention
[0004] The purpose of the present invention is to provide a method for preparing 1,2,3,4,5-cyanoethoxypentane. The method has a simple process route, mild and controllable conditions, and the prepared product has high purity and good yield.
[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present invention is: a method for preparing 1,2,3,4,5-cyanoethoxypentane, comprising the following steps: 1. After mixing and stirring the pentavalent alcohol and acrylonitrile, the temperature is controlled at 30-50°C, and the catalyst is an inorganic alkali aqueous solution, which is added dropwise at a dropping speed of 0.025g / min-0.15 g / min to ensure that the acrylonitrile reaction is complete. The purpose of slow dripping is to prevent acrylonitrile from self-polymerizing; 2. The reaction solution is heated and concentrated to a temperature of 100°C and a pressure of 1mmHg without obvious low boiling point. The concentrated reaction solution is added to alcohol and stirred for crystallization. The obtained solid is washed with deionized water for recrystallization, purified, and dried to obtain the product. The structural formula of the product 1,2,3,4,5-cyanoethoxypentane is as follows:
[0006] Furthermore, in the aforementioned method for preparing 1,2,3,4,5-cyanoethoxypentane, the pentavalent alcohol is selected from one of adonitol, xylitol and arabitol.
[0007] Furthermore, in the aforementioned method for preparing 1,2,3,4,5-cyanoethoxypentane, the molar ratio of acrylonitrile to pentahydric alcohol is 6 to 10:1.
[0008] Furthermore, in the aforementioned method for preparing 1,2,3,4,5-cyanoethoxypentane, the inorganic alkali aqueous solution is one selected from a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a lithium hydroxide aqueous solution, a tetramethylammonium hydroxide (TMAH) aqueous solution, and a calcium hydroxide aqueous solution; and the ratio of the molar amount of the alkali to the molar amount of the pentahydric alcohol is 0.1 to 0.2.
[0009] Furthermore, in the aforementioned method for preparing 1,2,3,4,5-cyanoethoxypentane, the mass fraction of the inorganic base aqueous solution is 1 to 5%.
[0010] Furthermore, in the aforementioned method for preparing 1,2,3,4,5-cyanoethoxypentane, the alcohol used for crystallization after concentration is selected from one of methanol, ethanol, propanol and butanol, and the amount used is 20 to 30 times the mass of the pentavalent alcohol.
[0011] Furthermore, in the aforementioned method for preparing 1,2,3,4,5-cyanoethoxypentane, a mixed solvent is used for recrystallization, the mixed solvent is a mixed solution of ethyl acetate and n-hexane, the mixing ratio is 1:0.5-1, and the amount used is 1-2 times the mass of the crystal. The mixed solvent can greatly improve the crystallization effect.
[0012] Furthermore, in the aforementioned method for preparing 1,2,3,4,5-cyanoethoxypentane, the solid obtained by adding alcohol and stirring and crystallizing is washed three times with deionized water.
[0013] Furthermore, in the aforementioned method for preparing 1,2,3,4,5-cyanoethoxypentane, the mixed solvent is recrystallized twice.
[0014] Furthermore, the aforementioned method for preparing 1,2,3,4,5-cyanoethoxypentane is characterized in that after purification, it is dried at 40° C. and 1 mmHg.
[0015] The advantages of the present invention are: 1. The process route is simple, the reaction conditions are mild and controllable, the steps are few, the post-treatment is convenient, and the purification is easy. 2. The solvents used can be recycled and reused, which effectively reduces the production cost, and the product purity is high, which can reach more than 99%, meeting the purity requirements of the additives of lithium ion battery electrolyte. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 It is the NMR carbon spectrum of the product obtained in Example 1.
[0017] Figure 2 It is the H NMR spectrum of the product obtained in Example 1. Implementation
[0018] The preparation method of 1,2,3,4,5-cyanoethoxypentane is described in detail below through specific examples.
[0019] Example 1: After mixing and stirring 152g of xylitol and 318g of acrylonitrile, the temperature was controlled at 30-35°C, and 160g of a 5% sodium hydroxide aqueous solution was added dropwise at a dropping speed of 0.04g / min. Prolonging the dropping time can effectively prevent acrylonitrile from self-polymerizing. After the reaction is completed, the reaction solution is concentrated to 100°C (1mmHg) without obvious low boiling. The concentrated reaction solution is added to 3040g of methanol and stirred for crystallization. The obtained solid is washed three times with an equal mass of deionized water to obtain 401g of crude product, which is then recrystallized twice with 802g of ethyl acetate-n-hexane (mass ratio of 1:1). After purification, it is dried at 40°C (1mmHg) to finally obtain 257g of finished product with a purity of 99.4% and a yield of 62%. See the NMR carbon spectrum of the product. Figure 1 , the product's H NMR spectrum can be found at Figure 2 .
[0020] Example 2: After 152g of Adonitol and 371g of acrylonitrile were mixed and stirred, the temperature was controlled at 35-40°C, and 182g of a 5% TMAH aqueous solution was added dropwise at a rate of 0.05g / min. After the reaction was completed, the reaction solution was concentrated to 100°C (1mmHg) without obvious low boiling. The concentrated reaction solution was added to 4560g of ethanol and stirred for crystallization. The obtained solid was washed 3 times with an equal mass of deionized water to obtain 450g of crude product, which was then recrystallized twice with 450g of ethyl acetate-n-hexane (mass ratio of 1:0.5). After purification, it was dried at 40°C (1mmHg) to finally obtain 297g of finished product with a purity of 99.5% and a yield of 71%.
[0021] Example 3: After 152g of arabitol and 530g of acrylonitrile were mixed and stirred, the temperature was controlled at 30-35°C, and 120g of a 5% sodium hydroxide aqueous solution was added dropwise at a rate of 0.1g / min. After the reaction was completed, the reaction solution was concentrated to 100°C (1mmHg) without obvious low boiling. The concentrated reaction solution was added to 3800g of isopropanol and stirred for crystallization. The obtained solid was washed 3 times with an equal mass of deionized water to obtain 415g of crude product, which was then recrystallized twice with 623g of ethyl acetate-n-hexane (mass ratio of 1:0.5). After purification, it was dried at 40°C (1mmHg) to finally obtain 259g of finished product with a purity of 99.3% and a yield of 62%.
[0022] Example 4: After 152g of xylitol and 530g of acrylonitrile were mixed and stirred, the temperature was controlled at 45-50°C, and 560g of a 1% potassium hydroxide aqueous solution was added dropwise at a rate of 0.15g / min. After the reaction was completed, the reaction solution was concentrated to 100°C (1mmHg) without obvious low boiling. The concentrated reaction solution was added to 3040g of ethanol and stirred for crystallization. The obtained solid was washed 3 times with an equal mass of deionized water to obtain 420g of crude product, which was then recrystallized twice with 840g of ethyl acetate-n-hexane (mass ratio of 1:0.5). After purification, it was dried at 40°C (1mmHg) to finally obtain 266g of finished product with a purity of 99.5% and a yield of 64%.
[0023] Example 5: After 152g of xylitol and 424g of acrylonitrile were mixed and stirred, the temperature was controlled at 40-45°C, and 120g of a 2% lithium hydroxide aqueous solution was added dropwise at a rate of 0.025g / min. After the reaction was completed, the reaction solution was concentrated to 100°C (1mmHg) without obvious low boiling. The concentrated reaction solution was added to 3800g of isobutanol for stirring and crystallization. The obtained solid was washed 3 times with an equal mass of deionized water to obtain 439g of crude product, which was then recrystallized twice with 439g of ethyl acetate-n-hexane (mass ratio of 1:0.5). After purification, it was dried at 40°C (1mmHg) to finally obtain 270g of finished product with a purity of 99.3% and a yield of 65%.
[0024] Example 6: After 152g of Adonitol and 477g of acrylonitrile were mixed and stirred, the temperature was controlled at 30-35°C, and 740g of a 1.5% calcium hydroxide aqueous solution was added dropwise at a rate of 0.15g / min. After the reaction was completed, the reaction solution was concentrated to 100°C (1mmHg) without obvious low boiling. The concentrated reaction solution was added to 3200g of n-butanol and stirred for crystallization. The obtained solid was washed 3 times with an equal mass of deionized water to obtain 474g of crude product, which was then recrystallized twice with 711g of ethyl acetate-n-hexane (mass ratio of 1:0.5). After purification, it was dried at 40°C (1mmHg) to finally obtain 284g of finished product with a purity of 99.3% and a yield of 68%.
[0025] Example 7: After 152g of arabitol and 371g of acrylonitrile were mixed and stirred, the temperature was controlled at 30-35°C, and 80g of a 5% sodium hydroxide aqueous solution was added dropwise at a rate of 0.05g / min. After the reaction was completed, the reaction solution was concentrated to 100°C (1mmHg) without obvious low boiling. The concentrated reaction solution was added to 3040g of methanol and stirred for crystallization. The obtained solid was washed 3 times with an equal mass of deionized water to obtain 396g of crude product, which was then recrystallized twice with 792g of ethyl acetate-n-hexane (mass ratio of 1:1). After purification, it was dried at 40°C (1mmHg) to finally obtain 257g of finished product with a purity of 99.5% and a yield of 62%.
[0026] The advantages of the present invention obtained from the above embodiments are: a simple process route, fewer steps, low purification difficulty, and the solvents used can be recycled and reused, effectively reducing production costs; the product purity is high, reaching more than 99%, which meets the purity requirements of additives for lithium-ion battery electrolytes.
Claims
1. A method for preparing 1,2,3,4,5-cyanoethoxypentane, comprising the following steps:
1. After mixing and stirring the pentavalent alcohol and acrylonitrile, the temperature is controlled at 30-50°C. The catalyst is an inorganic alkali aqueous solution, which is added dropwise at a rate of 0.025 g / min-0.15 g / min to ensure that the reaction of acrylonitrile is complete.
2. The reaction solution is heated and concentrated to a temperature of 100°C and a pressure of 1 mmHg without obvious low boiling. The concentrated reaction solution is added to alcohol and stirred for crystallization. The obtained solid is washed with deionized water for recrystallization, purified, and dried to obtain the product.
2. A method for preparing 1,2,3,4,5-cyanoethoxypentane according to claim 1, characterized in that: The pentavalent alcohol is selected from one of adonitol, xylitol and arabitol.
3. A method for preparing 1,2,3,4,5-cyanoethoxypentane according to claim 1, characterized in that: The molar ratio of acrylonitrile to pentavalent alcohol is 6-10:
1.
4. The method for preparing 1,2,3,4,5-cyanoethoxypentane according to claim 1, characterized in that: The inorganic alkali aqueous solution is one selected from sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, tetramethylammonium hydroxide aqueous solution, and calcium hydroxide aqueous solution; the ratio of the molar amount of the alkali to the molar amount of the pentavalent alcohol is 0.1 to 0.
2.
5. A method for preparing 1,2,3,4,5-cyanoethoxypentane according to claim 4, characterized in that: The mass fraction of the inorganic alkali aqueous solution is 1 to 5%.
6. The method for preparing 1,2,3,4,5-cyanoethoxypentane according to claim 1, characterized in that: The alcohol used for crystallization after concentration is selected from one of methanol, ethanol, propanol and butanol, and the amount used is 20 to 30 times the mass of the pentavalent alcohol.
7. The method for preparing 1,2,3,4,5-cyanoethoxypentane according to claim 1, characterized in that: The recrystallization uses a mixed solvent, which is a mixed solution of ethyl acetate and n-hexane, with a mixing ratio of 1:0.5-1, and the amount used is 1-2 times the mass of the crystal.
8. The method for preparing 1,2,3,4,5-cyanoethoxypentane according to claim 1, characterized in that: The solid obtained by adding alcohol and stirring for crystallization was washed three times with deionized water.
9. The method for preparing 1,2,3,4,5-cyanoethoxypentane according to claim 1, characterized in that: The mixed solvent was used for recrystallization twice.
10. The method for preparing 1,2,3,4,5-cyanoethoxypentane according to claim 1, characterized in that: After purification, the product was dried at 40°C and 1 mmHg.