Composition, preparation method and application thereof, and electronic cooling liquid

Abstract

The invention relates to the field of cooling liquid, in particular to a composition, a preparation method and application thereof and electronic cooling liquid. The composition is prepared from a hexafluoropropylene oligomer, perfluorocyclohexane, fluoropyridine and an antioxidant. The composition has the advantages of high stability, low viscosity, high thermal conductivity and low cost, and can be used as an electronic cooling liquid.

Description

Technical Field

[0001] The present invention relates to the field of coolant, and particularly to a composition, a preparation method and uses thereof, and an electronic coolant. Background Art

[0002] Currently, due to their low dielectric constants and good heat transfer properties, hexafluoropropylene dimers and trimers have been reported as fluorinated heat transfer fluids. When hexafluoropropylene dimers and trimers are used in immersion-type electronic coolants, it is found that they will show souring phenomenon after running continuously for a long time at a certain temperature, seriously corroding the materials in the application environment, which brings serious consequences to the objects of immersion cooling; for example, hexafluoropropylene dimer will show souring phenomenon after running continuously at 50°C for 100 hours; similar situations have also been found in the application process of hexafluoropropylene trimer. In the prior art, hydrofluorocyclopentane is selected to inhibit the souring of hexafluoropropylene oligomers. However, hydrofluorocyclopentane is flammable and explosive, and at the same time its chemical properties are relatively active, and it is easy to react with other substances in the environment, which may cause it to gradually decompose or deteriorate during use, thus affecting its effect of inhibiting souring. Therefore, there is an urgent need to provide an electronic coolant with high stability. Summary of the Invention

[0003] The present invention aims to solve at least one of the technical problems in the related art to a certain extent. For this reason, the present invention provides a composition, a preparation method and uses thereof, and an electronic coolant. The composition has high stability, low viscosity, high thermal conductivity and low cost, and can be used as an electronic coolant.

[0004] For this reason, in the first aspect of the present invention, a composition is provided, which includes hexafluoropropylene oligomer, perfluorocyclohexane, fluoropyridine and an antioxidant.

[0005] The composition has excellent cooling performance, long-term stability and thermal stability. Using it as an electronic coolant can avoid the souring phenomenon during long-term operation under high-temperature conditions, and ensure the long-term stable operation of the system. At the same time, the composition uses specific fluorinated liquids and additives, and has excellent insulation performance. Using it as an electronic coolant can achieve a breakdown voltage ≥ 42 kV at 25°C, which is much higher than that of traditional coolants (24 kV), and can effectively prevent current flow and ensure the safe operation of electronic devices. The composition also has high thermal conductivity, can quickly absorb and conduct the heat generated by the battery, effectively reduce the battery temperature, prevent the battery from overheating and oxidative damage, and extend the service life of the battery. In addition, the composition has excellent chemical stability and long service life, reduces the replacement frequency and maintenance cost, and saves operating expenses.

[0006] According to an embodiment of the present invention, the mass ratio of the hexafluoropropylene oligomer in the composition is 65-85%, the mass ratio of the perfluorocyclohexane is 10-20%, the mass ratio of the fluoropyridine is 1-10%, and the mass ratio of the antioxidant is 1-5%.

[0007] According to an embodiment of the present invention, the hexafluoropropylene oligomer includes at least one of E-perfluoro-4-methyl-2-pentene, Z-perfluoro-4-methyl-2-pentene, perfluoro-2-methyl-2-pentene, E-perfluoro-2,4-dimethyl-3-heptene, Z-perfluoro-2,4-dimethyl-3-heptene, perfluoro-4-methyl-3-isopropyl-2-pentene, or perfluoro-2,4-dimethyl-3-ethyl-2-pentene.

[0008] According to an embodiment of the present invention, the fluoropyridine includes at least one of 2-fluoropyridine, 4-fluoropyridine, 3,4-difluoropyridine, 2,4-difluoropyridine, 2,5-difluoropyridine, 2,3-difluoropyridine, 2,6-difluoropyridine, 3,4,5-trifluoropyridine, 2,3,4-trifluoropyridine, 2,3,6-trifluoropyridine, 2,4,5-trifluoropyridine, 2,4,6-trifluoropyridine, 2,3,4,5-tetrafluoropyridine, or pentafluoropyridine.

[0009] According to an embodiment of the present invention, the antioxidant includes at least one of butylated hydroxyanisole, dibutylhydroxytoluene, or tert-butylhydroquinone.

[0010] The second aspect of the present invention provides a preparation method of the composition described in the first aspect, including mixing the hexafluoropropylene oligomer, perfluorocyclohexane, fluoropyridine, and antioxidant, and stirring to obtain the composition.

[0011] According to an embodiment of the present invention, the stirring speed is 300-800 rpm.

[0012] According to an embodiment of the present invention, the stirring time is 30-60 min.

[0013] The third aspect of the present invention provides the use of the composition described in the first aspect or the composition obtained by the preparation method described in the second aspect as an electronic coolant.

[0014] The fourth aspect of the present invention provides an electronic coolant, including the composition described in the first aspect or the composition obtained by the preparation method described in the second aspect. Thus, the electronic coolant has all the advantages of the foregoing composition, which will not be elaborated here.

[0015] The beneficial effects of the present invention compared with the prior art:

[0016] (1) The composition provided by the present invention uses hexafluoropropylene oligomer and perfluorocyclohexane as the basic components, and adds fluoropyridine and antioxidant. The multi-components act synergistically to achieve excellent cooling performance and long-term stability.

[0017] (2) This composition has excellent thermal stability. When used as an electronic coolant, it can operate for a long time under high-temperature conditions without acid reflux, ensuring the long-term stable operation of the system.

[0018] (3) This composition has excellent insulation performance. When used as an electronic coolant, the breakdown voltage at 25 °C can reach ≥42 kV, which is much higher than that of traditional coolants (24 kV). It can effectively prevent current flow and ensure the safe operation of electronic devices.

[0019] (4) This composition has high thermal conductivity. When used as an electronic coolant, it can quickly absorb and conduct the heat generated by the battery, effectively reduce the battery temperature, prevent the battery from overheating and oxidative damage, and extend the service life of the battery.

[0020] (5) This composition has excellent chemical stability and long-life characteristics, reducing the replacement frequency and maintenance cost, and saving operating expenses.

[0021] Additional aspects and advantages of the present invention will be given in part in the following description, become apparent in part from the following description, or be understood through the practice of the present invention. Detailed Description of the Invention

[0022] The embodiments of the present invention will be described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as a limitation of the present invention.

[0023] It should be noted that the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of such features. Further, in the description of the present invention, unless otherwise stated, the meaning of "plurality" is two or more.

[0024] In the ranges disclosed herein, the endpoints and any value are not limited to the exact range or value. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and a single point value, and between single point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0025] To facilitate a better understanding of the present invention, certain technical and scientific terms are specifically defined below. Unless otherwise clearly defined elsewhere in this document, all other technical and scientific terms used herein shall have the meanings commonly understood by those of ordinary skill in the art to which the present invention pertains.

[0026] As used herein, the term "comprising" or "including" is an open-ended expression, meaning it includes the content specified in the present invention but does not exclude other aspects.

[0027] According to an embodiment of the present invention, a first aspect of the present invention provides a composition, which comprises a hexafluoropropylene oligomer, perfluorocyclohexane, fluoropyridine, and an antioxidant.

[0028] Among them, the hexafluoropropylene oligomer has extremely high stability, insulation, and excellent thermal conductivity, and the preparation process is mature; perfluorocyclohexane has extremely high chemical inertness, can withstand high-temperature environments, is not easily decomposed or deteriorated at high temperatures, and also has good electrical insulation and low surface tension. By adding it, the stability of the composition can be synergistically increased; fluoropyridine and the antioxidant further improve the properties such as the stability of the composition. Specifically, fluoropyridine can capture the free acidic groups in the hexafluoropropylene oligomer through van der Waals forces similar to hydrogen bonds, thereby inhibiting its deterioration and acid reflux, improving the stability of the composition. At the same time, fluoropyridine is usually used as a component of the electrolyte, and adding it to the composition can improve its compatibility with materials such as batteries.

[0029] According to an embodiment of the present invention, the composition consists of a hexafluoropropylene oligomer, perfluorocyclohexane, fluoropyridine, and an antioxidant.

[0030] According to an embodiment of the present invention, the mass ratio of the hexafluoropropylene oligomer in the composition is 65 - 85%, the mass ratio of the perfluorocyclohexane is 10 - 20%, the mass ratio of the fluoropyridine is 1 - 10%, and the mass ratio of the antioxidant is 1 - 5%; wherein, the mass percentage of the composition is calculated based on 100%.

[0031] According to specific embodiments of the present invention, the mass proportion of the hexafluoropropylene oligomer in the composition is 65-85%. As some specific examples, the mass proportion of the hexafluoropropylene oligomer can be 65%, 70%, 75%, 80%, 85%, etc.; the mass proportion of perfluorocyclohexane is 10-20%. As some specific examples, the mass proportion of perfluorocyclohexane can be 10%, 12%, 14%, 16%, 18%, 20%, etc.; the mass proportion of fluoropyridine is 1-10%. As some specific examples, the mass proportion of fluoropyridine can be 1%, 2%, 4%, 6%, 8%, 10%, etc.; the mass proportion of the antioxidant is 1-5%. As some specific examples, the mass proportion of the antioxidant can be 1%, 2%, 3%, 4%, 5%, etc.

[0032] According to specific embodiments of the present invention, the type of the hexafluoropropylene oligomer is not particularly limited and includes but is not limited to at least one of E-perfluoro-4-methyl-2-pentene, Z-perfluoro-4-methyl-2-pentene, perfluoro-2-methyl-2-pentene, E-perfluoro-2,4-dimethyl-3-heptene, Z-perfluoro-2,4-dimethyl-3-heptene, perfluoro-4-methyl-3-isopropyl-2-pentene or perfluoro-2,4-dimethyl-3-ethyl-2-pentene.

[0033] According to specific embodiments of the present invention, the type of the fluoropyridine is not particularly limited and includes but is not limited to at least one of 2-fluoropyridine, 4-fluoropyridine, 3,4-difluoropyridine, 2,4-difluoropyridine, 2,5-difluoropyridine, 2,3-difluoropyridine, 2,6-difluoropyridine, 3,4,5-trifluoropyridine, 2,3,4-trifluoropyridine, 2,3,6-trifluoropyridine, 2,4,5-trifluoropyridine, 2,4,6-trifluoropyridine, 2,3,4,5-tetrafluoropyridine or pentafluoropyridine.

[0034] According to specific embodiments of the present invention, the type of the antioxidant is not particularly limited and includes but is not limited to at least one of butylated hydroxyanisole (BHA), dibutylhydroxytoluene (BHT) or tert-butylhydroquinone (TBHQ).

[0035] According to an embodiment of the present invention, a second aspect of the present invention provides a preparation method of the composition described in the first aspect, including mixing the hexafluoropropylene oligomer, perfluorocyclohexane, fluoropyridine and antioxidant, and stirring to obtain the composition.

[0036] According to specific embodiments of the present invention, the parameters in the stirring treatment are not particularly limited. The stirring speed can be 300 - 800 rpm. As some specific examples, the stirring speed can be 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm, etc.; the stirring time can be 30 - 60 min. As some specific examples, the stirring time can be 30 min, 40 min, 50 min, 60 min, etc.

[0037] According to specific embodiments of the present invention, the preparation method further includes: pre-cooling the hexafluoropropylene oligomer, perfluorocyclohexane, fluoropyridine, and antioxidant, and then mixing, stirring, and filtering to obtain the composition. Cooling the raw materials can improve the mixing uniformity, and at the same time, the filtering process can remove unreacted impurities and agglomerated nanoparticles.

[0038] According to an embodiment of the present invention, a third aspect of the present invention provides the use of the composition described in the first aspect or the composition obtained by the preparation method described in the second aspect as an electronic coolant. This can avoid the phenomenon of acid reflux under the condition of long-term operation at high temperature of the electronic coolant, ensure the long-term operation of the system, and improve the safety and stability of the equipment.

[0039] According to an embodiment of the present invention, a fourth aspect of the present invention provides an electronic coolant, which includes the composition described in the first aspect or the composition obtained by the preparation method described in the second aspect. Thus, this electronic coolant has all the advantages of the foregoing composition, which will not be elaborated here.

[0040] Next, the solutions of the present invention will be explained in conjunction with embodiments. Those skilled in the art will understand that the following embodiments are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those not specified in the embodiments regarding specific technologies or conditions, they shall be carried out according to the technologies or conditions described in the literature in this field or according to the product specifications. For reagents or instruments not indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0041] Example 1

[0042] 75 parts of E-perfluoro-2,4-dimethyl-3-heptene, 5 parts of pentafluoropyridine, 17 parts of perfluorocyclohexane, and 3 parts of BHA were placed in an environment at 5°C for pre-cooling treatment. Then, the raw materials were added to a reaction kettle, the speed of the stirrer was set at 600 rpm, and stirred for 30 min. After stirring, the mixture was filtered through a microporous filter to remove unreacted impurities and agglomerated nanoparticles, obtaining the composition.

[0043] Examples 2-10 and Comparative Examples 1-6 are different from Example 1 only in the types and mass fractions of raw materials, as specifically shown in Table 1. The physical and chemical properties of the compositions obtained in each example and comparative example were tested to obtain Table 2.

[0044] Table 1

[0045]

[0046] In the table, "-" indicates none.

[0047] Table 2

[0048]

[0049] As can be seen from Table 2, the compositions provided in the examples of the present invention have the characteristics of low viscosity, high specific heat capacity, high insulation, etc. compared with commercially available conventional coolants, and have sufficient safety performance. Among them, the breakdown voltage and volume resistivity of the compositions provided in the examples are much greater than those of commercially available immersion coolants Novec 7300 (25 kV, 1011 Ω·cm) and Novec 7500 (25 kV, 108 Ω·cm), and the specific heat capacities of these compositions are all above 1.2 KJ / (kg·°C). Therefore, more effective insulation and heat transfer can be provided. When used in the liquid cooling system of electronic devices, more effective cooling effects can be provided.

[0050] In addition, since the hexafluoropropylene oligomer will decompose and produce acid under high-temperature long-term operation, subsequent aging tests were carried out to test and analyze the changes in purity and acid value before and after aging to evaluate the stability of the composition.

[0051] The aging experiment refers to the group standard T / CI 208-2023. Specifically, 50 mL of the composition was placed in a hydrothermal reaction kettle and heated and aged at 150 °C for 192 h. Then, the changes in the purity and acid value of the composition were tested and compared before and after to evaluate its chemical stability. The results are shown in Table 3.

[0052] Table 3

[0053]

[0054]

[0055] Note: The acid value test standard in the table refers to GB / T 264, and the purity GC test standard refers to GB / T 4946.

[0056] As can be seen from Table 3, the purity of the composition before and after the test using GC (gas chromatography) was measured, and at the same time, the acid value before and after the test was also measured using potentiometric titration. It was found that the change in the purity and acid value of the composition before and after the test was small, that is, the stability was good. By comparing Comparative Examples 1-6, it can be seen that both perfluorocyclohexane and fluoropyridine can improve the stability of hexafluoropropylene oligomer to a certain extent. By comparing the examples and comparative examples, it can be seen that fluoropyridine, perfluorocyclohexane and antioxidant in the composition of the present invention can cooperate with each other to jointly inhibit the pyrolysis of hexafluoropropylene oligomer at high temperature, especially can inhibit its deterioration and acidification, protect the electronic equipment from being corroded by acid, and the purity remains almost unchanged, and excellent and stable heat transfer performance can be maintained. Therefore, the composition of the present invention has excellent stability and long service life, reduces the replacement frequency and maintenance cost, saves the user's operating expenses, can be used for immersion liquid cooling, and provides the possibility for the large-scale use of immersion liquid cooling.

[0057] In the description of this specification, the descriptions with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples", etc. mean that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0058] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A composition, characterized in that Including hexafluoropropylene oligomers, perfluorocyclohexane, fluoropyridine and antioxidants.

2. The composition according to claim 1, characterized in that In the composition, the mass proportion of hexafluoropropylene oligomer is 65-85%, the mass proportion of perfluorocyclohexane is 10-20%, the mass proportion of fluoropyridine is 1-10%, and the mass proportion of antioxidant is 1-5%.

3. The composition according to claim 1, characterized in that The hexafluoropropylene oligomer includes at least one of E-perfluoro-4-methyl-2-pentene, Z-perfluoro-4-methyl-2-pentene, perfluoro-2-methyl-2-pentene, E-perfluoro-2,4-dimethyl-3-heptene, Z-perfluoro-2,4-dimethyl-3-heptene, perfluoro-4-methyl-3-isopropyl-2-pentene or perfluoro-2,4-dimethyl-3-ethyl-2-pentene.

4. The composition according to claim 1, characterized in that The fluoropyridine includes at least one of 2-fluoropyridine, 4-fluoropyridine, 3,4-difluoropyridine, 2,4-difluoropyridine, 2,5-difluoropyridine, 2,3-difluoropyridine, 2,6-difluoropyridine, 3,4,5-trifluoropyridine, 2,3,4-trifluoropyridine, 2,3,6-trifluoropyridine, 2,4,5-trifluoropyridine, 2,4,6-trifluoropyridine, 2,3,4,5-tetrafluoropyridine or pentafluoropyridine.

5. The composition according to claim 1, characterized in that The antioxidant includes at least one of butylated hydroxyanisole, butylated hydroxytoluene or tert-butylhydroquinone.

6. A method for preparing the composition according to any one of claims 1 to 5, characterized in that: The method comprises mixing the hexafluoropropylene oligomer, perfluorocyclohexane, fluoropyridine and an antioxidant, and stirring to obtain the composition.

7. The preparation method according to claim 6, characterized in that: The stirring speed is 300-800 rpm.

8. The preparation method according to claim 6, characterized in that: The stirring time is 30-60 min.

9. Use of the composition according to any one of claims 1 to 5 or the composition obtained by the preparation method according to any one of claims 6 to 8 as an electronic coolant.

10. An electronic coolant, characterized in that: The invention comprises the composition according to any one of claims 1 to 5 or the composition obtained by the preparation method according to any one of claims 6 to 8.

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