CN110066295B - Preparation method of pentafluoroethoxy cyclotriphosphazene - Google Patents
Preparation method of pentafluoroethoxy cyclotriphosphazene Download PDFInfo
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- CN110066295B CN110066295B CN201910350650.1A CN201910350650A CN110066295B CN 110066295 B CN110066295 B CN 110066295B CN 201910350650 A CN201910350650 A CN 201910350650A CN 110066295 B CN110066295 B CN 110066295B
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
Abstract
The invention relates to the field of organic chemistry, in particular to a preparation method of pentafluoroethoxy cyclotriphosphazene. The invention provides a preparation method of pentafluoroethoxy cyclotriphosphazene, which comprises the following steps: 1) fluorination reaction: reacting hexachlorocyclotriphosphazene with hydrogen fluoride in the presence of a catalyst to prepare hexachlorocyclotriphosphazene; 2) and (3) etherification reaction: reacting hexachlorocyclotriphosphazene with sodium alkoxide to prepare pentafluoroethoxycyclotriphosphazene. The preparation method of pentafluoroethoxy cyclotriphosphazene provided by the invention has the advantages of simple reaction steps and reasonable cost, and is suitable for large-scale industrialization.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a preparation method of pentafluoroethoxy cyclotriphosphazene.
Background
The lithium ion battery has the advantages of large energy density, wide working temperature range, small self-discharge, no memory effect, excellent cycle performance, quick charge and discharge, high charging efficiency, long service life and the like, and is widely used in modern production and life, particularly in the fields of new energy automobiles, electronic equipment and the like. However, lithium batteries are also susceptible to internal thermal runaway, which leads to battery ignition and even explosion, and therefore, it is generally necessary to add a suitable flame retardant, so that the safety of the battery can be significantly improved. The cyclotriphosphazene is not easy to open the ring due to the special molecular structure of the cyclotriphosphazene, has excellent thermal stability, and simultaneously, because the phosphorus and the nitrogen have synergistic effect, the compound containing the cyclotriphosphazene can absorb heat in the high-temperature degradation process, generate phosphate, metaphosphate and polyphosphate, form a non-volatile protective film on the surface, and release CO2、NH3、N2And the like, thereby achieving the flame-retardant effect. Pentafluoroethoxycyclotriphosphazene isOne such flame retardant additive.
The existing technical scheme for preparing pentafluoroethoxy cyclotriphosphazene is to take hexachlorocyclotriphosphazene as a raw material. The method provided by the patent CN102702268A is that hexachlorocyclotriphosphazene is firstly substituted by ethoxy and then fluorinated, but the activity of a P-Cl bond is high, so that the mono-ethoxy substitution reaction of hexachlorocyclotriphosphazene is difficult to control in a mono-substituted state, and the method has low yield and difficult and complicated purification. Patents CN104558045A, CN105732718A, WO2016165310a1 and the like provide solutions of perfluorination and then ethoxy substitution, but in the first step of fluorination, fluorine salts such as potassium fluoride, sodium fluoride and the like are selected for reaction under the action of a catalyst, and because a large amount of solids exist in the system, the requirement on the stirring effect of reaction equipment is high, and because the chloride generated by the reaction can occlude the fluorine salts, the fluorine salts need to be greatly excessive to complete the fluorination reaction, so a large amount of inorganic solid wastes are generated, and adverse effects are caused to the environment; the fluoridation reaction temperature of the fluorine salt such as potassium fluoride, sodium fluoride and the like is high, the reaction time is long, and a large amount of energy is consumed; in addition, because the intermediate hexafluorocyclotriphosphazene has a lower boiling point and is very volatile, the escape of the hexafluorocyclotriphosphazene is easily caused by the conventional reaction method and purification method, so that the yield is greatly reduced.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a method for preparing pentafluoroethoxycyclotriphosphazene, which solves the problems of the prior art.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing pentafluoroethoxycyclotriphosphazene, comprising:
1) fluorination reaction: reacting hexachlorocyclotriphosphazene with hydrogen fluoride in the presence of a catalyst to prepare hexachlorocyclotriphosphazene;
2) and (3) etherification reaction: reacting hexachlorocyclotriphosphazene with sodium alkoxide to prepare pentafluoroethoxycyclotriphosphazene.
In some embodiments of the invention, the catalyst is selected from lewis acids in the fluorination reaction.
In some embodiments of the invention, the fluorination reactionWherein the catalyst is selected from SbCl5、TiCl4、SnCl4、MoCl5、FeCl3、NiCl2、MnCl2、BiCl3One or more of the above.
In some embodiments of the invention, the fluorination reaction is carried out in the presence of a solvent selected from organic solvents.
In some embodiments of the present invention, the solvent in the fluorination reaction is selected from aromatic hydrocarbon solvents.
In some embodiments of the present invention, the solvent in the fluorination reaction is selected from one or more of benzotrifluoride, p-chlorotrifluoromethylene, 3, 4-dichlorobenzotrifluoride, m-benzotrifluoride, and p-benzotrifluoride.
In some embodiments of the present invention, the reaction temperature in the fluorination reaction is 0 to 60 ℃.
In some embodiments of the present invention, the reaction temperature in the fluorination reaction is 10 to 40 ℃.
In some embodiments of the present invention, the reaction temperature in the fluorination reaction is 20 to 30 ℃.
In some embodiments of the present invention, in the fluorination reaction, the molar ratio of hydrogen fluoride to hexachlorocyclotriphosphazene is 6 to 15: 1.
in some embodiments of the present invention, in the fluorination reaction, the molar ratio of hydrogen fluoride to hexachlorocyclotriphosphazene is 6.5 to 10: 1.
in some embodiments of the present invention, in the fluorination reaction, the molar ratio of hydrogen fluoride to hexachlorocyclotriphosphazene is 7 to 8: 1.
in some embodiments of the present invention, in the fluorination reaction, hexachlorocyclotriphosphazene, a solvent and a catalyst are mixed, and hydrogen fluoride is introduced to carry out the reaction.
In some embodiments of the present invention, the fluorination reaction further comprises: distillation to provide hexafluorocyclotriphosphazene.
In some embodiments of the invention, the etherification reaction is carried out in the presence of a solvent.
In some embodiments of the invention, the sodium alkoxide in the etherification reaction is selected from sodium ethoxide.
In some embodiments of the present invention, the etherification reaction is carried out at a reaction temperature of-30 to 30 ℃.
In some embodiments of the present invention, the etherification reaction is carried out at a reaction temperature of-15 to 10 ℃.
In some embodiments of the invention, in the etherification reaction, the molar ratio of sodium alkoxide to hexafluorocyclotriphosphazene is 0.5-2: 1.
in some embodiments of the present invention, in the etherification reaction, the molar ratio of sodium alkoxide to hexafluorocyclotriphosphazene is 0.7 to 1.2: 1.
in some embodiments of the invention, the solvent in the etherification reaction is selected from aprotic polar solvents.
In some embodiments of the invention, the solvent in the etherification reaction is selected from one or more of tetrahydrofuran, methyltetrahydrofuran, diethyl ether, isopropyl ether, methyl tert-butyl ether, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate.
In some embodiments of the present invention, the etherification reaction further comprises: distillation and/or rectification to provide pentafluoroethoxycyclotriphosphazene.
Drawings
FIG. 1 shows the mass spectrum of hexafluorocyclotriphosphazene in example 1 of the present invention;
FIG. 2 shows a 19F NMR spectrum of hexafluorocyclotriphosphazene of example 1 of the present invention;
FIG. 3 shows a 31P NMR spectrum of hexafluorocyclotriphosphazene in example 1 of the present invention;
FIG. 4 shows a mass spectrum of pentafluoroethoxycyclotriphosphazene in example 1 of the present invention;
FIG. 5 shows a 1H NMR spectrum of pentafluoroethoxycyclotriphosphazene of example 1 of the present invention;
FIG. 6 shows a 13C NMR spectrum of pentafluoroethoxycyclotriphosphazene of example 1 of the present invention;
FIG. 7 shows a pentafluoroethoxycyclotriphosphazene 19F NMR spectrum of example 1 of the present invention;
FIG. 8 shows a spectrum of a pentafluoroethoxycyclotriphosphazene 31P NMR spectrum according to example 1 of the present invention.
Detailed Description
The inventor of the invention provides a novel preparation method of pentafluoroethoxy cyclotriphosphazene through a great deal of research, and the preparation method has the advantages of low cost, less pollution, high yield and the like, is a more economic and efficient preparation method of pentafluoroethoxy cyclotriphosphazene, and completes the invention on the basis.
The first aspect of the invention provides a preparation method of pentafluoroethoxy cyclotriphosphazene, which comprises the following steps:
1) fluorination reaction: reacting hexachlorocyclotriphosphazene with hydrogen fluoride in the presence of a catalyst to prepare hexachlorocyclotriphosphazene;
2) and (3) etherification reaction: reacting hexachlorocyclotriphosphazene with sodium alkoxide to prepare pentafluoroethoxycyclotriphosphazene.
The preparation method of pentafluoroethoxy cyclotriphosphazene provided by the invention can comprise the following steps: reacting hexachlorocyclotriphosphazene with sodium alkoxide to prepare pentafluoroethoxycyclotriphosphazene, wherein the reaction equation is as follows:
in the etherification reaction provided by the present invention, the reaction may be performed in the presence of a solvent, which is usually selected from aprotic polar solvents and is usually a good solvent of the reaction system, for example, in the etherification reaction, the solvent may be selected from one or more combinations including but not limited to tetrahydrofuran, methyltetrahydrofuran, diethyl ether, isopropyl ether, methyl tert-butyl ether, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, etc., for another example, the amount of the solvent used in the etherification reaction may be 2 to 10 times the mass of hexafluorocyclotriphosphazene.
In the etherification reaction provided by the invention, the etherification reaction is specifically Williamson synthesis, and a target product is mainly prepared by the action of sodium alkoxide and a halogenated compound, wherein the sodium alkoxide can be specifically sodium ethoxide and the like, the dosage of the sodium alkoxide can be generally matched with hexafluorocyclotriphosphazene, and for example, the molar ratio of the sodium alkoxide to the hexafluorocyclotriphosphazene can be 0.5-2: 1, preferably 0.7 to 1.2: 1.
in the etherification reaction provided by the present invention, the etherification reaction is usually performed at a low temperature, for example, the etherification reaction may be performed at a temperature of-30 to 30 ℃, and the preferred reaction temperature may be-15 to 10 ℃. The reaction time can be adjusted by those skilled in the art according to the reaction progress, for example, the reaction progress of the etherification reaction can be judged by methods such as TLC and chromatography, and for example, the reaction time of the etherification reaction can be 3 to 10 hours.
In the etherification reaction provided by the present invention, a person skilled in the art may select a suitable method to perform post-treatment on the product of the etherification reaction, for example, the etherification reaction may further include: distillation and/or rectification to provide pentafluoroethoxycyclotriphosphazene. After the etherification reaction is completed, the reaction system may be distilled and/or rectified to provide a pentafluoroethoxycyclotriphosphazene product of suitable purity. In a preferred embodiment of the present invention, the reaction system may be filtered to remove some impurities prior to distillation and/or rectification.
The preparation method of pentafluoroethoxy cyclotriphosphazene provided by the invention can comprise a fluorination reaction: fluorinating hexachlorocyclotriphosphazene in the presence of a catalyst to prepare hexachlorocyclotriphosphazene, wherein the reaction equation is as follows:
in the fluorination reaction provided by the invention, the catalyst is usually Lewis acid, and specifically can include but is not limited to SbCl5、TiCl4、SnCl4、MoCl5、FeCl3、NiCl2、MnCl2、BiCl3And the like. In a preferred embodiment of the invention, the catalyst used in the fluorination reaction is selected from FeCl3、MoCl5、SbCl5One or more of the above. The amount of catalyst used in the fluorination reaction is generally a catalytic amount, for example, the weight ratio of catalyst to hexachlorocyclotriphosphazene may be 0.001 to 0.05: 1, preferably 0.01 to 0.03: 1.
in the fluorination reaction provided by the present invention, the reaction can be performed in the presence of a solvent, the solvent used in the fluorination reaction is usually selected from organic solvents and is usually a good solvent of the reaction system, so that the reactants are mixed sufficiently and a certain concentration is ensured to allow the reaction to proceed smoothly, for example, the solvent can be selected from aromatic hydrocarbon solvents and the like, preferably halogenated aromatic hydrocarbon solvents and the like, and specifically, the solvent can be one or a combination of more of trifluorotoluene, p-chlorotrifluoromethane, 3, 4-dichlorotrifluorotoluene, m-ditrifluoromethane, p-ditrifluoromethane and the like, and in a preferred embodiment of the present invention, the solvent used in the fluorination reaction is selected from one or a combination of more of trifluorotoluene, p-chlorotrifluoromethane and the like. For another example, in the fluorination reaction, the weight ratio of the solvent to the hexachlorocyclotriphosphazene may be 1 to 10: 1, preferably 2 to 5: 1.
in the fluorination reaction provided by the present invention, the reaction may be carried out in the presence of a fluorinating agent, which may be selected from nucleophilic fluorinating agents in general, and hydrogen fluoride in particular. The amount of hydrogen fluoride used is usually in excess relative to the amount of hexachlorocyclotriphosphazene so as to completely replace the chlorine in the molecule of hexachlorocyclotriphosphazene with fluorine, and the amount of hydrogen fluoride used is at least 6 times (molar ratio) the amount of hexachlorocyclotriphosphazene, and when the amount of hydrogen fluoride is less than 6 equivalents, hexachlorocyclotriphosphazene tends not to be completely converted to hexachlorocyclotriphosphazene, resulting in a yield loss, for example, the molar ratio of hydrogen fluoride to hexachlorocyclotriphosphazene is 6 to 15: 1, preferably 6.5 to 10: 1, more preferably 7 to 8: 1. when the fluorination reagent is a gas, the hexachlorocyclotriphosphazene, the solvent and the catalyst can be mixed, and the fluorination reagent is introduced into the reaction system, so that the fluorination reagent is introduced into the reaction system for reaction. Generally, when hydrogen fluoride is introduced, temperature control measures may be taken to keep the temperature of the reaction system stable, and for example, a method such as cooling in a water bath may be employed.
In the fluorination reaction provided by the present invention, the fluorination reaction is usually performed at normal temperature or at a heating temperature, for example, the fluorination reaction may be performed at a temperature of 0 to 60 ℃, preferably at a temperature of 10 to 40 ℃, and more preferably at a temperature of 20 to 30 ℃. When the reaction temperature is lower than 0 ℃, the solubility of hexachlorocyclotriphosphazene in the solvent is relatively low, the solvent needs to be fully used by increasing the amount of the solvent, for example, 8 times or more of the solvent relative to the weight of hexachlorocyclotriphosphazene may need to be used, and the reaction may be slow, so that the production period needs to be prolonged, which means that the solvent consumption is large and the reaction efficiency is low, therefore, the method is not preferred; when the reaction temperature is higher than 60 ℃, although the reaction proceeds faster, there is a possibility that product escape may be caused, resulting in a loss of yield. The reaction time can be adjusted by those skilled in the art according to the reaction progress, for example, the reaction progress of the fluorination reaction can be judged by TLC, chromatography, etc., and for example, the reaction time of the fluorination reaction can be 5 to 24 hours, preferably not less than 6 hours. When the reaction time is short, the fluorination reaction is not easily completed, and there may be a case where the desired yield cannot be achieved, and the reaction time may usually be not more than 24 hours from the viewpoint of the conversion rate, the yield and the like. In one embodiment of the present invention, it takes 6-10 hours for the chlorine atoms in the molecule to be completely replaced at 20-30 ℃.
In the fluorination reaction provided by the present invention, a person skilled in the art can select a suitable method for post-treating the product of the fluorination reaction, for example, the fluorination reaction may further include: distillation to provide hexafluorocyclotriphosphazene. After the fluorination reaction is completed, the reaction system may be subjected to distillation to provide hexafluorocyclotriphosphazene of suitable purity as an intermediate product. For example, atmospheric distillation, atmospheric rectification, etc. may be employed, and the distillation temperature may be 55 to 100 ℃. Before distillation, the system may be cooled and purged to remove hydrogen fluoride and the like remaining in the system as much as possible. In one embodiment of the invention, the system is cooled to below 20 ℃ and purged with nitrogen for 1-2 hours prior to distillation.
The preparation method of pentafluoroethoxycyclotriphosphazene provided by the invention adopts reaction of hexachlorocyclotriphosphazene and a fluorination reagent to obtain a hexafluorocyclotriphosphazene intermediate, the intermediate reacts with sodium alkoxide, and a high-quality pentafluoroethoxycyclotriphosphazene product can be obtained through simple distillation and purification. The preparation method of pentafluoroethoxy cyclotriphosphazene provided by the invention has the advantages of simple reaction steps and reasonable cost, and is suitable for large-scale industrialization.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1
Fluorination reaction
Adding 120g of hexachlorocyclotriphosphazene, 360g of benzotrifluoride and 3g of antimony pentachloride into a 1000ml hastelloy reaction kettle with magnetic stirring, starting stirring, introducing 52g of hydrogen fluoride into a reaction system at 20-30 ℃, obviously releasing heat in the gas introduction process, cooling in a water bath, after about 3h of ventilation, continuing reacting for 5h, introducing nitrogen for 2h to promote excessive hydrogen fluoride to be discharged out of the system, distilling the system at normal pressure, collecting corresponding fractions to obtain 75g of hexachlorocyclotriphosphazene, wherein the HPLC purity is 97.8%, and the mass spectrogram, 19F NMR spectrogram and 31P NMR spectrogram of the product are respectively shown in figures 1, 2 and 3.
Etherification reaction
Adding 60g of hexafluorocyclotriphosphazene and 120g of 1, 4-dioxane into a 250ml three-neck flask with magnetic stirring, starting stirring, cooling to-10-0 ℃, slowly adding 15g of solid sodium ethoxide by using a solid feeder, keeping the temperature at-10-0 ℃ for reaction for 5H after the addition is finished, filtering, and rectifying the filtrate at normal pressure to obtain 55g of product with the HPLC purity of 99.6%, wherein a mass spectrogram, a 1H NMR spectrogram, a 13C NMR spectrogram, a 19F NMR spectrogram and a 31P NMR spectrogram of the product are respectively shown in figures 4, 5, 6, 7 and 8.
Example 2
Fluorination reaction
Adding 100g of hexachlorocyclotriphosphazene, 300g of p-chlorotrifluoromethane and 2g of molybdenum pentachloride into a 1000ml hastelloy reaction kettle with magnetic stirring, starting stirring, introducing 46g of hydrogen fluoride into a reaction system at 20-30 ℃, obviously releasing heat in a gas introduction process, cooling in a water bath, continuing reacting for 4 hours after 3 hours of ventilation, introducing nitrogen for 2 hours to promote excessive hydrogen fluoride to be discharged out of the system, distilling the system at normal pressure, collecting corresponding fractions to obtain 65g of hexachlorocyclotriphosphazene, wherein the HPLC purity is 96.9%.
Etherification reaction
Adding 60g of hexafluorocyclotriphosphazene and 120g of methyl tert-butyl ether into a 250ml three-neck flask with magnetic stirring, starting stirring, cooling to-10-0 ℃, slowly adding 15g of solid sodium ethoxide by using a solid feeder, keeping the temperature at-10-0 ℃ for reaction for 5 hours after the addition is finished, filtering, and rectifying the filtrate at normal pressure to obtain 54g of product with the HPLC purity of 99.5%.
Example 3
Fluorination reaction
Adding 100g of hexachlorocyclotriphosphazene, 300g of benzotrifluoride and 1g of molybdenum pentachloride into a 1000ml hastelloy reaction kettle with magnetic stirring, starting stirring, introducing 57g of hydrogen fluoride into a reaction system at 20-30 ℃, cooling in a water bath in a gas introduction process, continuously reacting for 5h after about 5h of ventilation is finished, introducing nitrogen for 2h to promote excessive hydrogen fluoride to be discharged out of the system, distilling the system at normal pressure, collecting corresponding fractions to obtain 62g of hexafluorocyclotriphosphazene, wherein the HPLC purity is 97.1%.
Etherification reaction
Adding 60g of hexafluorocyclotriphosphazene and 120g of methyl tert-butyl ether into a 250ml three-neck flask with magnetic stirring, starting stirring, cooling to-10-0 ℃, slowly adding 16g of solid sodium ethoxide by using a solid feeder, keeping the temperature at-10-0 ℃ for reaction for 5 hours after the solid feeding is finished, filtering, and rectifying the filtrate at normal pressure to obtain 55g of product with the HPLC purity of 99.6%.
Example 4
Fluorination reaction
Adding 100g of hexachlorocyclotriphosphazene, 400g of benzotrifluoride and 4g of ferric chloride into a 1000ml hastelloy reaction kettle with magnetic stirring, starting stirring, introducing 50g of hydrogen fluoride into a reaction system at 30-40 ℃, cooling by using a water bath when gas is introduced, continuing to react for 10h after about 5h of ventilation is finished, introducing nitrogen for 2h to promote excessive hydrogen fluoride to be discharged out of the system, distilling the system at normal pressure, collecting corresponding fractions to obtain 60g of hexachlorocyclotriphosphazene, wherein the HPLC purity is 95.2%.
Etherification reaction
Adding 58g of hexafluorocyclotriphosphazene and 120g of tetrahydrofuran into a 250ml three-neck flask with magnetic stirring, starting stirring, cooling to-10-0 ℃, slowly adding 15g of solid sodium ethoxide by using a solid feeder, keeping the temperature at-10-0 ℃ for reaction for 5 hours after the addition is finished, filtering, and rectifying the filtrate at normal pressure to obtain 49g of product with the HPLC purity of 99.2%.
Example 5
Fluorination reaction
Adding 100g of hexachlorocyclotriphosphazene, 400g of benzotrifluoride and 5g of titanium tetrachloride into a 1000ml hastelloy reaction kettle with magnetic stirring, starting stirring, introducing 52g of hydrogen fluoride into a reaction system at 40-45 ℃, cooling in a water bath, continuing reacting for 15h after about 5h of ventilation is finished, introducing nitrogen for 2h to promote excessive hydrogen fluoride to be discharged out of the system, distilling the system at normal pressure, collecting corresponding fractions to obtain 44g of hexachlorocyclotriphosphazene, wherein the HPLC purity is 95.5%.
Etherification reaction
Adding 40g of hexafluorocyclotriphosphazene and 100g of tetrahydrofuran into a 250ml three-neck flask with magnetic stirring, starting stirring, cooling to-10-0 ℃, slowly adding 11g of solid sodium ethoxide by using a solid feeder, keeping the temperature at-10-0 ℃ for reaction for 5 hours after the addition is finished, filtering, and rectifying the filtrate at normal pressure to obtain 34g of product with the HPLC purity of 99.1%.
In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (6)
1. A preparation method of pentafluoroethoxy cyclotriphosphazene comprises the following steps:
1) fluorination reaction: reacting hexachlorocyclotriphosphazene with hydrogen fluoride in the presence of a catalyst to prepare hexachlorocyclotriphosphazene;
2) and (3) etherification reaction: reacting hexachlorocyclotriphosphazene with sodium alkoxide to prepare pentafluoroethoxycyclotriphosphazene;
in the fluorination reaction, the reaction is carried out in the presence of a solvent, wherein the solvent is selected from one or more of benzotrifluoride, p-chlorotrifluoromethane, 3, 4-dichlorobenzotrifluoride, m-benzotrifluoride and p-benzotrifluoride;
in the fluorination reaction, the reaction temperature is 20-30 ℃;
the molar ratio of the hydrogen fluoride to the hexachlorocyclotriphosphazene is 7-8;
the catalyst is selected from SbCl5、TiCl4、SnCl4、MoCl5、FeCl3、NiCl2、MnCl2、BiCl3One or more of the above.
2. The method for producing pentafluoroethoxycyclotriphosphazene according to claim 1, wherein in the fluorination reaction, hexachlorocyclotriphosphazene, a solvent and a catalyst are mixed, and hydrogen fluoride is introduced to carry out the reaction;
the fluorination reaction further comprises: distillation to provide hexafluorocyclotriphosphazene.
3. The method for producing pentafluoroethoxycyclotriphosphazene according to claim 1, wherein in the etherification reaction, the reaction is carried out in the presence of a solvent;
the sodium alkoxide is selected from sodium ethoxide;
in the etherification reaction, the reaction temperature is-30 ℃;
in the etherification reaction, the molar ratio of sodium alkoxide to hexafluorocyclotriphosphazene is 0.5-2: 1.
4. the method for producing pentafluoroethoxycyclotriphosphazene according to claim 3, wherein in the etherification reaction, the solvent is selected from aprotic polar solvents;
in the etherification reaction, the reaction temperature is-15-10 ℃;
in the etherification reaction, the molar ratio of sodium alkoxide to hexafluorocyclotriphosphazene is 0.7-1.2: 1.
5. the method of claim 4, wherein the solvent in the etherification reaction is one or more selected from tetrahydrofuran, methyltetrahydrofuran, diethyl ether, isopropyl ether, methyl tert-butyl ether, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate.
6. The method for producing pentafluoroethoxycyclotriphosphazene according to claim 1, wherein the etherification reaction further comprises: distillation and/or rectification to provide pentafluoroethoxycyclotriphosphazene.
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