Process for the preparation of a pentafluorocyclotriphosphazene derivative
By reacting trimethylsiloxypentafluorocyclotriphosphazene with hydroxyl compounds and combining this with distillation technology, the problems of complex steps and low purity in the synthesis of pentafluorocyclotriphosphazene derivatives have been solved, resulting in a preparation method with high conversion rate and high purity, suitable for industrial production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ZHANGJIAGANG GUOTAI HUARONG NEW CHEM MATERIALS CO LTD
- Filing Date
- 2024-12-04
- Publication Date
- 2026-06-05
AI Technical Summary
Existing methods for synthesizing pentafluorocyclic triphosphazene derivatives are complex, have difficult-to-control reaction conditions, low conversion rates and purity, and are difficult to purify.
The pentafluorocyclotriphosphazene derivative was synthesized using trimethylsiloxypentafluorocyclotriphosphazene and hydroxyl compounds as raw materials under mild reaction conditions, and post-processing was carried out by distillation.
It achieves easily controllable reaction conditions, 100% conversion rate, and high purity, making it suitable for industrial production.
Smart Images
Figure CN122145520A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of compound synthesis technology, specifically to the synthesis of pentafluorocyclic triphosphazene derivatives. Background Technology
[0002] Phosphazene compounds can be used as flame retardants in lithium battery electrolytes. Other functional groups, however, can provide different enhancing effects. For example, alkenyl groups protect the negative electrode and improve cycle performance; alkyne-containing compounds exhibit good high-temperature performance and high-voltage resistance; and cyanoethoxy groups suppress gas production and improve high-voltage withstand capability.
[0003] Compounds that combine phosphazene with different functional groups have the combined effects of both, and can reduce the amount used and save costs when used as electrolyte additives.
[0004] Generally, pentafluorocyclotriphosphazene derivatives are obtained by reacting hexafluorocyclotriphosphazene with hydroxyl compounds in the presence of an acid-binding agent. However, this method can result in the formation of multi-substituted compounds during synthesis, which increases the difficulty of purification and reduces the yield. Summary of the Invention
[0005] The technical problem to be solved by the present invention is to provide a method for preparing pentafluorocyclic triphosphazene derivatives, which has simple steps, mild and easy-to-control reaction conditions, high conversion rate and high purity.
[0006] To solve the above problems, the technical solution adopted in this invention is: a method for preparing a pentafluorocyclic triphosphazene derivative, comprising reacting trimethylsiloxypentafluorocyclic triphosphazene with a hydroxyl compound as raw material, followed by post-processing to obtain the product; the general structural formula of methylsiloxypentafluorocyclic triphosphazene is general formula one, and the structure of general formula one is as follows: ; The structural formula of the pentafluorocyclic triphosphazene derivative is general formula two, and the structure of general formula two is as follows: , In general formula II, R represents one of alkyl, alkenyl, alkynyl, epoxyalkyl, and cyanoalkyl.
[0007] Furthermore, in the aforementioned method for preparing a pentafluorocyclic triphosphazene derivative, the hydroxyl compound includes methanol, ethanol, n-propanol, isopropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol, allyl alcohol, propynyl alcohol, 3-hydroxypropionitrile, ethylene glycol, propylene glycol, glycerol, and diethyl hydroxymethylphosphonate.
[0008] Furthermore, in the aforementioned method for preparing a pentafluorocyclotriphosphazene derivative, the molar ratio of trimethylsiloxypentafluorocyclotriphosphazene to the hydroxyl group in the hydroxyl compound is 1:1.2 to 1:2.
[0009] Furthermore, in the aforementioned method for preparing a pentafluorocyclic triphosphazene derivative, the reaction time is 1 to 10 hours.
[0010] Furthermore, in the aforementioned method for preparing a pentafluorocyclic triphosphazene derivative, the reaction temperature is controlled at 25~50℃.
[0011] Furthermore, in the aforementioned method for preparing a pentafluorocyclic triphosphazene derivative, the post-treatment involves distillation.
[0012] The advantages of this invention are: the reaction of trimethylsiloxypentafluorocyclotriphosphazene with hydroxyl compounds to prepare pentafluorocyclotriphosphazene derivatives is mild, easy to control, has a conversion rate of 100%, is easy to purify, and is suitable for industrial production. Attached Figure Description
[0013] Figure 1 This is the MS spectrum of the product obtained in Example 1.
[0014] Figure 2 This is the carbon NMR spectrum of the product obtained in Example 5. Detailed Implementation
[0015] The preparation method of a pentafluorocyclic triphosphazene derivative of the present invention will be described in detail below through specific embodiments.
[0016] Example 1: In a 1000 mL three-necked flask equipped with an electric stirrer, reflux condenser, and thermometer, 320 g of trimethylsiloxypentafluorocyclotriphosphazene and 150 g of 2,2,2-trifluoroethanol were added; the temperature was raised to 50 °C, and the mixture was stirred for 2 hours; after the reaction was completed, trimethylsiloxypentafluorocyclotriphosphazene was completely converted to 2,2,2-trifluoroethoxypentafluorocyclotriphosphazene. The reaction solution was distilled to obtain 230 g of product with a purity of over 99.5%. The conversion rate of trimethylsiloxypentafluorocyclotriphosphazene was 100%, and the overall molar yield of 2,2,2-trifluoroethoxypentafluorocyclotriphosphazene was 70%. See the MS chromatogram of the product. Figure 1 .
[0017] The reaction diagram of Example 1 is shown below: .
[0018] Example 2: In a 1000mL three-necked flask equipped with an electric stirrer, reflux condenser, and thermometer, 320g of trimethylsiloxypentafluorocyclotriphosphazene and 336g of hexafluoroisopropanol were added; the temperature was raised to 40°C, and the mixture was stirred for 4 hours; after the reaction was completed, trimethylsiloxypentafluorocyclotriphosphazene was completely converted to hexafluoroisopropoxypentafluorocyclotriphosphazene. The reaction solution was distilled to obtain 300g of product with a purity of over 99.5%. The conversion rate of trimethylsiloxypentafluorocyclotriphosphazene was 100%, and the overall molar yield of hexafluoroisopropoxypentafluorocyclotriphosphazene was 75%.
[0019] The reaction diagram of Example 2 is shown below: .
[0020] Example 3: In a 1000mL three-necked flask equipped with an electric stirrer, reflux condenser, and thermometer, 320g of trimethylsiloxypentafluorocyclotriphosphazene and 70g of allyl alcohol were added; the mixture was stirred at 25°C for 10 hours; after the reaction was completed, trimethylsiloxypentafluorocyclotriphosphazene was completely converted to allyloxypentafluorocyclotriphosphazene. The reaction solution was distilled to obtain 237g of product with a purity of over 99.5%. The conversion rate of trimethylsiloxypentafluorocyclotriphosphazene was 100%, and the total molar yield of allyloxypentafluorocyclotriphosphazene was 80%.
[0021] The reaction diagram of Example 3 is shown below: .
[0022] Example 4: In a 1000mL three-necked flask equipped with an electric stirrer, reflux condenser, and thermometer, 320g of trimethylsiloxypentafluorocyclotriphosphazene and 68g of propargyl alcohol were added; the temperature was raised to 30°C, and the mixture was stirred for 1 hour; after the reaction was completed, trimethylsiloxypentafluorocyclotriphosphazene was completely converted to propargyloxypentafluorocyclotriphosphazene. The reaction solution was distilled to obtain 228g of product with a purity of over 99.5%. The conversion rate of trimethylsiloxypentafluorocyclotriphosphazene was 100%, and the total molar yield of propargyloxypentafluorocyclotriphosphazene was 80%.
[0023] The reaction diagram of Example 4 is shown below: .
[0024] Example 5: In a 1000mL three-necked flask equipped with an electric stirrer, reflux condenser, and thermometer, 320g of trimethylsiloxypentafluorocyclotriphosphazene and 140g of 3-hydroxypropionitrile were added; the temperature was raised to 30°C, and the mixture was stirred for 1 hour; after the reaction was completed, trimethylsiloxypentafluorocyclotriphosphazene was completely converted to cyanoethoxypentafluorocyclotriphosphazene. The reaction solution was distilled to obtain 210g of product with a purity of over 99.5%. The conversion rate of trimethylsiloxypentafluorocyclotriphosphazene was 100%, and the total molar yield of cyanoethoxypentafluorocyclotriphosphazene was 70%. The carbon NMR spectrum of the product is shown below. Figure 2 As shown.
[0025] The reaction diagram of Example 5 is shown below: .
[0026] Example 6: In a 1000mL three-necked flask equipped with an electric stirrer, reflux condenser, and thermometer, 640g of trimethylsiloxypentafluorocyclotriphosphazene and 62g of ethylene glycol were added; the temperature was raised to 50°C, and the mixture was stirred for 2 hours; after the reaction was completed, trimethylsiloxypentafluorocyclotriphosphazene was completely converted to ethylenedipentafluorocyclotriphosphazene. The reaction solution was distilled to obtain 442g of product with a purity of over 99.5%. The conversion rate of trimethylsiloxypentafluorocyclotriphosphazene was 100%, and the overall molar yield of ethylenedipentafluorocyclotriphosphazene was 85%.
[0027] The reaction diagram of Example 6 is shown below: .
[0028] From the above embodiments, it can be seen that: the method for preparing pentafluorocyclic triphosphazene derivatives according to the present invention involves reacting trimethylsiloxypentafluorocyclic triphosphazene with a hydroxyl compound as raw material to prepare pentafluorocyclic triphosphazene derivatives. The reaction conditions are mild and easy to control, with a conversion rate of 100%, easy purification, high yield, and high purity, making it suitable for industrial production.
Claims
1. A method for preparing a pentafluorocyclic triphosphazene derivative, characterized in that: The product is obtained by reacting trimethylsiloxypentafluorocyclotriphosphazene with a hydroxyl compound as a raw material and then undergoing post-processing. The general structural formula of methylsiloxypentafluorocyclotriphosphazene is Formula 1, and the structure of Formula 1 is as follows: , The structural formula of the pentafluorocyclic triphosphazene derivative is general formula two, and the structure of general formula two is as follows: , In general formula II, R represents one of alkyl, alkenyl, alkynyl, epoxyalkyl, and cyanoalkyl.
2. The method for preparing a pentafluorocyclic triphosphazene derivative according to claim 1, characterized in that: Hydroxyl compounds include methanol, ethanol, n-propanol, isopropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol, allyl alcohol, propynyl alcohol, 3-hydroxypropionitrile, ethylene glycol, propylene glycol, glycerol, and diethyl hydroxymethylphosphonate.
3. The method for preparing a pentafluorocyclic triphosphazene derivative according to claim 1, characterized in that: The molar ratio of trimethylsiloxypentafluorocyclotriphosphazene to the hydroxyl group in the hydroxyl compound is 1:1.2 to 1:
2.
4. The method for preparing a pentafluorocyclic triphosphazene derivative according to claim 1, characterized in that: The reaction time is 1 to 10 hours.
5. The method for preparing a pentafluorocyclic triphosphazene derivative according to claim 1, characterized in that: The reaction temperature is controlled at 25~50℃.
6. The method for preparing a pentafluorocyclic triphosphazene derivative according to claim 1, characterized in that: Post-processing was performed using distillation.