Synthesis process of perfluoroester, composition of perfluoroester and application of composition

Abstract

The invention discloses a synthesis process of perfluoroester, a composition of the perfluoroester and application of the composition, and relates to the technical field of fluorination processes. The synthesis process of the perfluoroester comprises the following steps: adding reactants alcohol and triethylamine into a reaction kettle, starting stirring and reducing the temperature; introducing perfluoroisobutyryl fluoride by adopting a gas phase pipe, and controlling the reaction temperature in the gas introduction process; after feeding is completed, stirring is conducted for 30-50 min; and after the reaction is finished, completely discharging mother liquor in the kettle, adding water with the same volume for washing, standing for layering, and taking subnatant to obtain a product. The synthesis process provided by the invention is simple, few in by-products, green, environment-friendly and easy to industrialize. Besides, the obtained perfluoroester is combined with auxiliary materials to obtain the flash-point-free incombustible composition, and the composition can be applied to the fields of cleaning agents, fire extinguishing agents, cooling liquid and the like and has wide development prospects.

Description

Technical Field

[0001] The present application relates to the field of fluorination process technology, and in particular to a synthesis process of perfluoroester, a composition thereof and an application of the composition. Background Art

[0002] With the rapid advancement of science and technology, electronic products are increasingly developing towards a highly integrated direction, which has put forward unprecedented requirements for the cleanliness of products. Historically, the electronics industry has widely relied on CFC cleaning agents, but they have been banned by the international community due to their damage to the ozone layer and aggravation of the greenhouse effect. Subsequently, HCFC, as its substitute, was used briefly as a transitional solution, but it contains chlorine, so it is not a long-term solution.

[0003] At present, the cleaning industry is moving towards chlorine-free cleaning agents. Among them, the Novec hydrofluoroether solvent series launched by the foreign giant 3M Company has demonstrated excellent application performance and environmental protection characteristics with its unique structure mainly composed of C, F, and O elements, and has occupied an important position in the fields of chip semiconductors, data centers, and energy storage. However, this technological achievement has encountered a double attack from foreign product patent barriers and international trade tensions, resulting in the dual pressure of high prices and sales monopoly in the domestic market, posing a severe challenge to emerging industries such as domestic chip semiconductors, energy storage, and artificial intelligence.

[0004] In this context, domestic scientific research forces have actively responded and are committed to developing new fluorinated liquids to break the monopoly of 3M's Novec hydrofluoroether. It is driven by such demand that perfluoroester products have come into being and have become a highly anticipated alternative option. Perfluoroester products can not only effectively overcome the defects of existing technologies, such as high costs and supply monopoly problems, but also show strong market competitiveness with their unique chemical properties, such as higher stability, lower environmental impact, and excellent performance comparable to Novec hydrofluoroether. More importantly, the localization process of perfluoroesters is expected to break the foreign technology monopoly, reduce production costs, and provide strong support for the rapid development of emerging domestic science and technology industries.

[0005] However, although the emergence of perfluoroester products provides a possible solution to existing problems, the production process of perfluoroester products still faces certain challenges. The complexity of the production process, the difficulty in obtaining raw materials, and the low production efficiency all affect the large-scale production and cost control of the products, thereby limiting their application and promotion in a wider range of fields. Summary of the invention

[0006] In order to provide a new synthesis process from perfluoroisobutyryl fluoride to perfluoro ester, the present application provides a synthesis process of perfluoro ester, a composition thereof and an application of the composition.

[0007] The present application provides a synthesis process of perfluoroester, which adopts the following technical scheme: A synthesis process of perfluoroester comprises the following steps: S1. Add the reactants alcohol and triethylamine to the reactor, start stirring and lower the temperature; S2. Use a gas phase tube to introduce perfluoroisobutyryl fluoride, and control the reaction temperature during the ventilation process; after the feeding is completed, stir for 30-50 minutes; S3. Increase the temperature and keep it warm. After the reaction is completed, release all the mother liquor in the kettle, add an equal volume of water for washing, let it stand and separate into layers, take the lower layer liquid, and obtain the product.

[0008] By adopting the above technical scheme, the present application uses perfluoroisobutyryl fluoride as a raw material to carry out esterification reaction with alcohols to generate a series of perfluoroesters. The synthesis process is simple, the cost of reactants is low, the reaction conditions are easy to control, there are few by-products, it is green and environmentally friendly, and it is easy to industrialize.

[0009] Preferably, the reactant alcohol is one of a monohydric alcohol, a dihydric alcohol and a polyhydric alcohol.

[0010] Preferably, the reactant alcohol is one of methanol, ethanol, trifluoroethanol, ethylene glycol and propylene glycol.

[0011] Preferably, the reaction temperature in S2 is -10-10°C.

[0012] Preferably, the elevated temperature in S3 is 40-70° C., and the insulation time is 3-12 h.

[0013] The present application provides a perfluoroester composition, which adopts the following technical solution: A perfluoroester composition comprises a binary azeotropic composition and a ternary azeotropic composition.

[0014] By adopting the above technical scheme, the present application combines perfluoroester with a series of auxiliary materials to obtain perfluoroester-containing compositions. These compositions have a low azeotropic point, no flash point and are non-flammable, and can be applied to cleaning agents, fire protection, liquid cooling and other fields.

[0015] Preferably, the binary azeotropic composition raw material comprises 11-80% perfluoroester and 20-89% auxiliary material A by volume; the auxiliary material A is one of methanol, ethanol, perfluoroheptanone, perfluoroisobutyl methyl ether, perfluoroisobutyl ethyl ether, and hexafluoropropylene trimer.

[0016] Preferably, the ternary azeotropic composition raw material comprises 37-69% perfluoroester, 21-25% auxiliary material B, and 10-38% auxiliary material C by volume; the auxiliary material B is one of methanol and ethanol; the auxiliary material C is one of dimethyl carbonate, diethyl carbonate, and perfluoroisobutyl ether.

[0017] The present application provides a synthesis process of a perfluoroester, a composition thereof and an application of the composition using the following technical scheme: Preferably, an application of a perfluoroester composition is characterized in that the perfluoroester composition is used in the fields of cleaning agents, fire protection, and liquid cooling.

[0018] By adopting the above technical scheme, the field of cleaning agents includes but is not limited to chip cleaning, semiconductor cleaning, aerospace cleaning, and high-voltage live cleaning; the field of fire protection includes but is not limited to data center fire protection, energy storage fire protection, power station fire protection, etc.; the field of liquid cooling includes but is not limited to data center cooling, energy storage cooling, etc.

[0019] In summary, the present application includes at least one of the following beneficial technical effects: 1. The present application uses perfluoroisobutyryl fluoride as a raw material to react with alcohols for esterification to generate a series of perfluoroesters. The synthesis process is simple, the cost of reactants is low, the reaction conditions are easy to control, there are few by-products, it is green and environmentally friendly, and it is easy to industrialize; 2. The present application combines perfluoroester with a series of auxiliary materials to obtain perfluoroester-containing compositions. These compositions have a low azeotropic point, no flash point and are non-flammable. They can be applied to cleaning agents, fire fighting, liquid cooling and other fields, and have broad development prospects. DETAILED DESCRIPTION

[0020] The present application is further described in detail below with reference to the embodiments. Example

[0021] Example 1 The synthesis of methyl perfluoroisobutyrate, the reaction formula is as follows: The preparation steps are as follows: S1. Add 1 kg of methanol and 1.2 kg of triethylamine into a 10 L autoclave, start stirring and cool to -10 ° C; S2. Slowly introduce 4.73 kg of perfluoroisobutyryl fluoride through a gas phase tube. During the ventilation process, the reaction temperature is controlled between -10 and 10 ° C. When the temperature exceeds the limit, close the air inlet pipe at any time. After the feeding is completed, stir for 30 minutes; S3. Raise the temperature to 40 ° C and keep warm for 3 hours; after the reaction is completed, the mother liquor in the kettle is completely discharged, an equal volume of water is added for washing, the layers are allowed to stand, and the lower layer is removed to obtain the product; The obtained product was subjected to GC-MS detection and analysis. The purity of the product methyl perfluoroisobutyrate obtained in this example was 93.5%, and the yield was 93.9%, which shows that the preparation method of perfluoroester provided in this application can not only obtain a product with higher purity, but also has a higher yield.

[0022] Example 2 The synthesis of methyl perfluoroisobutyrate, the preparation steps are as follows: S1. Add 1 kg of methanol and 1.2 kg of triethylamine into a 10 L autoclave, start stirring and cool to -10 ° C; S2. Slowly introduce 4.73 kg of perfluoroisobutyryl fluoride through a gas phase tube. During the ventilation process, the reaction temperature is controlled between -10 and 10 ° C. When the temperature exceeds the limit, close the air inlet pipe at any time. After the feeding is completed, stir for 40 minutes; S3. Raise the temperature to 50 ° C and keep warm for 5 hours; after the reaction is completed, the mother liquor in the kettle is completely discharged, an equal volume of water is added for washing, the layers are allowed to stand, and the lower layer is removed to obtain the product; The obtained product was subjected to GC-MS detection and analysis. The purity of the product methyl perfluoroisobutyrate obtained in this example was 94.5%, and the yield was 94.3%.

[0023] Example 3 The synthesis of methyl perfluoroisobutyrate, the preparation steps are as follows: S1. Add 1 kg of methanol and 1.2 kg of triethylamine into a 10 L autoclave, start stirring and cool to -10 ° C; S2. Slowly introduce 4.73 kg of perfluoroisobutyryl fluoride through a gas phase tube. During the ventilation process, the reaction temperature is controlled between -10 and 10 ° C. When the temperature exceeds the limit, close the air inlet pipe at any time. After the feeding is completed, stir for 50 minutes; S3. Raise the temperature to 70 ° C and keep warm for 12 hours; after the reaction is completed, the mother liquor in the kettle is completely discharged, an equal volume of water is added for washing, the layers are allowed to stand, and the lower layer is removed to obtain the product; The obtained product was subjected to GC-MS detection and analysis. The purity of the product of methyl perfluoroisobutyrate obtained in this embodiment was 91.6%, and the yield was 89.7%.

[0024] Example 4 The synthesis of ethyl perfluoroisobutyrate, the reaction formula is as follows: The preparation steps are as follows: S1. Add 1.68 kg of ethanol and 1.2 kg of triethylamine to a 10 L autoclave, start stirring and cool to -10 ° C; S2. Slowly introduce 4.55 kg of perfluoroisobutyryl fluoride through a gas phase tube. During the ventilation process, the reaction temperature is controlled between -10 and 10 ° C. When the temperature exceeds the limit, close the air inlet pipe at any time. After the feeding is completed, stir for 30 minutes; S3. Raise the temperature to 50 ° C and keep warm for 5 hours; after the reaction is completed, the mother liquor in the kettle is completely discharged, an equal volume of water is added for washing, the layers are allowed to stand, and the lower layer is removed to obtain the product; The obtained product was subjected to GC-MS detection and analysis. The purity of the product ethyl perfluoroisobutyrate obtained in this example was 91.4%, and the yield was 87.66%.

[0025] Example 5 The synthesis of trifluoroethyl perfluoroisobutyrate, the reaction formula is as follows: The preparation steps are as follows: S1. Add 3.9 kg of trifluoroethanol and 1.2 kg of triethylamine into a 10 L autoclave, start stirring and cool to -10 ° C; S2. Slowly introduce 4.81 kg of perfluoroisobutyryl fluoride through a gas phase tube. During the ventilation process, the reaction temperature is controlled between -10 and 10 ° C. When the temperature exceeds the limit, close the air inlet pipe at any time. After the feeding is completed, stir for 30 minutes; S3. Raise the temperature to 50 ° C and keep warm for 5 hours; after the reaction is completed, the mother liquor in the kettle is completely discharged, an equal volume of water is added for washing, the layers are allowed to stand, and the lower layer is removed to obtain the product; The obtained product was subjected to GC-MS detection and analysis. The purity of the product trifluoroethyl perfluoroisobutyrate obtained in this example was 94.2%, and the yield was 73.2%.

[0026] Example 6 The synthesis of ethylene diperfluoroisobutyrate and ethylene monoperfluoroisobutyrate monool is as follows: The preparation steps are as follows: S1. 500 g of ethylene glycol and 212.1 g of triethylamine were added to a 10 L autoclave, stirred and cooled to -10 ° C; S2. Slowly introduce 4.48 kg of perfluoroisobutyryl fluoride through a gas phase tube. During the ventilation process, the reaction temperature is controlled between -10 and 10 ° C. When the temperature exceeds the limit, close the air inlet pipe at any time. After the feeding is completed, stir for 30 minutes; S3. Raise the temperature to 70 ° C and keep warm for 12 hours; after the reaction, the mother liquor in the kettle is completely discharged, an equal volume of water is added for washing, the layers are allowed to stand, the lower layer is removed, and the product is obtained by vacuum distillation; The obtained product was subjected to GC-MS detection and analysis. The purity of the product perfluoroisobutyric acid ethylene glycol obtained in this example was 99.2%, and the yield was 23.0%; the purity of perfluoroisobutyric acid ethyl monoester monoalcohol was 99.4%, and the yield was 42.6%.

[0027] Example 7 The synthesis of perfluoroisobutyric acid propylene glycol, perfluoroisobutyric acid ethylene glycol and perfluoroisobutyric acid propylene glycol, the reaction formula is as follows: The preparation steps are as follows: S1. 370 g of propylene glycol and 212.1 g of triethylamine were added to a 10 L autoclave, stirred and cooled to -10 ° C; S2. Slowly introduce 4.36 kg of perfluoroisobutyryl fluoride through a gas phase tube. During the ventilation process, the reaction temperature is controlled between -10 and 10 ° C. When the temperature exceeds the limit, close the air inlet pipe at any time. After the feeding is completed, stir for 30 minutes; S3. Raise the temperature to 70 ° C and keep warm for 12 hours; after the reaction, the mother liquor in the kettle is completely discharged, an equal volume of water is added for washing, the layers are allowed to stand, the lower layer is removed, and the product is obtained by vacuum distillation; The obtained products were subjected to GC-MS detection and analysis. The purity of the perfluoroisobutyric acid propylene glycol obtained in this example was 99.3%, and the yield was 8.6%; the purity of the perfluoroisobutyric acid propylene glycol monool was 99.4%, and the yield was 18.3%; the purity of the perfluoroisobutyric acid propylene monoester diol was 99.4%, and the yield was 35.6%.

[0028] Embodiment 8-14 The perfluoroester obtained in Examples 1-7 was combined with auxiliary material A to obtain a binary azeotropic composition. The raw materials and proportions are shown in Table 1: Table 1 Raw material composition of Examples 8-14 Perfluorinated esters and ratios Auxiliary material A and proportion Example 8 Methyl perfluoroisobutyrate 80% Methanol 20% Example 9 Methyl perfluoroisobutyrate 65% Ethanol 35% Example 10 Methyl perfluoroisobutyrate 27% Perfluoroheptanone 73% Embodiment 11 Methyl perfluoroisobutyrate 55% Perfluoroisobutyl methyl ether 45% Example 12 Methyl perfluoroisobutyrate 35% Perfluoroisobutyl ether 65% Embodiment 13 Ethyl perfluoroisobutyrate 11% Perfluoroheptanone 89% Embodiment 14 Ethyl perfluoroisobutyrate 11% Hexafluoropropylene trimer 89% Examples 15-17 The perfluoroester obtained in Examples 1-7 was combined with auxiliary material A to obtain a binary azeotropic composition. The raw materials and proportions are shown in Table 2: Table 2 Raw material composition of Examples 15-17 Perfluorinated esters and ratios Auxiliary material B and proportion Auxiliary material C and proportion Embodiment 15 Methyl perfluoroisobutyrate 69% Methanol 21% Dimethyl carbonate 10% Example 16 Ethyl perfluoroisobutyrate 64% Ethanol 24% Diethyl carbonate 12% Embodiment 17 Methyl perfluoroisobutyrate 37% Ethanol 25% 7200 38％ Performance testing 1. The azeotropic point of the perfluoroester composition obtained in Examples 8-17 was tested by distillation, and the flash point was tested by an open cup flash point tester. The results are shown in Table 3.

[0029] The specific test results are as follows: Table 3 Azeotropic point and flash point of the perfluoroester compositions obtained in Examples 8-17 It can be seen from the test results in Table 3 that the perfluoroester composition provided in the present application has a low azeotropic point and no flash point, which indicates that the perfluoroester composition provided in the present application has the characteristics of no flash point and non-flammable.

[0030] 2. Cleaning effect test (1) According to GB / T 11134-1989 "Determination of the value of kauri resin butanol in hydrocarbon solvents", the KB values ​​of the perfluoroesters and perfluoroester compositions obtained in Examples 1-17 were tested; the results are shown in Table 4.

[0031] (2) The perfluoroester and perfluoroester composition obtained in Examples 1-17 were added to a round-bottom flask respectively, and a blank sample was added as a control. A PCB board coated with a certain amount of solder paste was weighed and placed in the round-bottom flask. The heating temperature was controlled. After reaching the boiling point or azeotropic point, the liquid was boiled for a certain period of time and then the heating was stopped. The PCB board was taken out and the fluorinated liquid composition was dried. The PCB board was weighed again and the solder paste residue was observed. The removal rate of the solder paste was calculated. The results are shown in Table 4.

[0032] The specific test results are as follows: Table 4 Product KB value and solder paste removal rate It can be seen from the test results in Table 4 that the KB value of perfluoroester is about 10-15, and the KB values ​​between the perfluoroester compositions vary greatly, with the lowest reaching 1.6 and the maximum reaching 23.1; combined with its non-flammable and flash-free properties, the perfluoroesters and perfluoroester compositions provided in the present application, such as methyl perfluoroisobutyrate, ethyl perfluoroisobutyrate, ethylene difluoroisobutyrate, Example 11 and Example 12, can be used in chip cleaning and other fields; for example, the KB values ​​of Example 8, Example 15 and Example 16 reach about 20, which can be used for moderate cleaning, such as precision engine cleaning, oil pipeline oil pollution and other scenes.

[0033] 3. Fire extinguishing effect test Fire extinguishing experiment: (1) At room temperature, add fuel to the fuel cup, adjust the lifting platform to adjust the fuel liquid level to 1 mm below the edge of the fuel cup; set the air feed temperature to 90°C, the oil bath temperature for heating the liquid to be tested to 130°C, and the constant temperature box temperature to 50°C; after all experimental conditions are stable, turn on the air pump and adjust the pressure reducing valve, and adjust the air flow rate to 30L / min by adjusting the flow meter; (2) Ignite the n-heptane in the fuel cup and pre-burn for 60-120 seconds. Observe the temperature of the air entering the burner mixing chamber. The test can be started only when the temperature is higher than 50°C to prevent the fire extinguishing agent from cooling down. Start to introduce the compound solvent into the oil bath pipeline. The oil bath temperature is set to 130°C to completely vaporize the compound solvent. Gradually increase the flow rate of the compound solvent until the flame is extinguished within 1 minute at this flow rate. Record the fire extinguishing agent flow rate and fire extinguishing time. Increasing the speed of the peristaltic pump will increase the concentration of the fire extinguishing agent. During operation, be careful not to increase this increase by more than 2% of the previous concentration. (3) Record the peristaltic pump speed corresponding to the flame extinguishing, the mixed gas temperature during the fire extinguishing and other data; repeat the test three times each time; if the flame can be extinguished two times, the fire extinguishing concentration corresponding to the speed is taken as the minimum fire extinguishing concentration; Calculation method of fire extinguishing concentration: The volume percentage concentration C of the fire extinguishing agent can be calculated according to the following formula: Where: --volume percentage concentration of fire extinguishing agent, %; V air ---Volume flow rate of air, L / min; V ext ---Volume flow rate of fire extinguishing agent, L / min; The air flow rate displayed on the rotor flowmeter is the air flow rate at room temperature. The air flow rate at room temperature and the temperature of the fire extinguishing agent / air mixture in the diffuser should be tested first to convert the volume. The conversion formula is as follows: V air Room---the air volume flow rate at room temperature is the air flow rate measured by the rotor flowmeter, L / min; ρ air Room---Dry air density at room temperature, Kg / m 3 ; ρ air Diffuser---Density of dry air at the temperature in the diffuser, Kg / m 3 ; The formula obtained by linear regression of the peristaltic pump is the mass flow rate of the fire extinguishing agent. To convert it into the volume flow rate at the temperature in the diffuser, the formula is as follows: V ext =m 室 ×s 扩 V ext ---Volume flow rate of fire extinguishing agent in the diffuser, L / min; m 室 ---Mass flow rate of the liquid to be measured at room temperature; s 扩 ---Specific volume of fire extinguishing agent at the temperature in the diffuser; The results are shown in Table 5.

[0034] The specific test results are as follows: Table 5 Fire extinguishing concentration test results It can be seen from the test results in Table 5 that the perfluoroester and perfluoroester composition provided in the present application have good fire extinguishing effects. Among them, the effects of ethylene glycol perfluoroisobutyrate and Example 14 in the fire extinguishing experiment are better than the current mainstream fire extinguishing agent perfluorohexanone, indicating that the application scenarios of such compositions can be expanded to the field of fire protection, and at the same time have fire extinguishing properties in other fields such as the use of electrolytes.

[0035] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed. However, as long as it is within the scope of the claims of the present application, it shall be protected by the patent law.

Claims

1. A synthesis process for perfluoroester, characterized in that: The following steps are involved: S1. Add the reactants alcohol and triethylamine to the reactor, start stirring and lower the temperature; S2. Use a gas phase tube to pass perfluoroisobutyryl fluoride, and control the reaction temperature during the ventilation process; after the feeding is completed, stir for 30-50 minutes; S3. Raise the temperature and keep it warm. After the reaction is completed, release all the mother liquor in the kettle, add an equal volume of water for washing, let it stand and separate into layers, take the lower layer liquid to obtain the product.

2. A process for synthesizing perfluoroester according to claim 1, characterized in that: The reactant alcohol is one of monohydric alcohol, dihydric alcohol and polyhydric alcohol.

3. A process for synthesizing perfluoroester according to claim 2, characterized in that: The reactant alcohol is one of methanol, ethanol, trifluoroethanol, ethylene glycol and propylene glycol.

4. A process for synthesizing perfluoroester according to claim 1, characterized in that: The reaction temperature in S2 is -10-10°C.

5. A process for synthesizing perfluoroester according to claim 1, characterized in that: The elevated temperature in S3 is 40-70° C., and the insulation time is 3-12 hours.

6. A perfluoroester composition, characterized in that: The composition includes a binary azeotropic composition and a ternary azeotropic composition.

7. A perfluoroester composition according to claim 6, characterized in that: The binary azeotropic composition raw material comprises 11-80% perfluoroester and 20-89% auxiliary material A by volume; the auxiliary material A is one of methanol, ethanol, perfluoroheptanone, perfluoroisobutyl methyl ether, perfluoroisobutyl ethyl ether and hexafluoropropylene trimer.

8. A composition according to claim 6, characterized in that: The raw materials of the ternary azeotropic composition include 37-69% perfluoroester, 21-25% auxiliary material B, and 10-38% auxiliary material C by volume; the auxiliary material B is one of methanol and ethanol; the auxiliary material C is one of dimethyl carbonate, diethyl carbonate, and perfluoroisobutyl ether.

9. Use of a perfluoroester composition according to any one of claims 6 to 8, characterized in that: The perfluoroester composition is used in the fields of cleaning agents, fire protection, and liquid cooling.

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