Ultralow-density fluoropolyether electronic cooling liquid and preparation method thereof

Abstract

The invention provides a preparation method of ultralow-density fluoropolyether electronic cooling liquid, ultralow-density fluoropolyether comprises a first structure and / or a second structure, and the preparation method comprises the following steps: adding a metal cyanide catalyst into a reaction kettle; adding fluorine-containing alkylene oxide under the condition of nitrogen, and adding a main chain unit and / or a fragment unit into the reaction kettle; wherein the main chain unit is a fluorine-containing alkylene oxide end-capping reagent and comprises alkyl alcohol or alkoxy alcohol, the fragment unit comprises cyclohexene oxide or fluorine-containing cyclohexene oxide, the fluoropolyether with the first structure is generated through the main chain unit, the fluoropolyether with the second structure is generated through the fragment unit, and the low-density polyether is prepared through preset conditions. Through a preset preparation scheme, the cost is low, the yield is high, separation treatment is simple and easy, and the prepared electronic cooling liquid has the characteristics of quantitative characteristic, low density, high thermal conductivity, high fluidity and the like.

Description

Technical Field

[0001] The present application relates to the field of chemical technology, and in particular to an ultra-low density fluoropolyether electronic coolant and a preparation method thereof. Background Art

[0002] Continuous breakthroughs in high-performance electronic devices and new energy technologies have greatly improved human living conditions. However, electronic components generate a lot of heat during operation. If the heat cannot be dissipated in time, it will directly affect their performance and life. Traditional hydrocarbon or silane heat sinks are widely used because of their low prices, but the proportion of CH in hydrocarbon or silane compounds is extremely high, which is very flammable, and the GWP index of some alkanes is high. Fluoropolyether, as a new type of cooling medium, contains fluorine in its chemical structure, making it non-flammable. It has good thermal stability, chemical corrosion resistance and environmental protection performance, which effectively prevents equipment from overheating and ensures its good working condition.

[0003] In the application of electronic coolants, fluoropolyethers have high thermal conductivity and can efficiently dissipate the heat transferred from electronic components to maintain the normal operating temperature of the equipment. Due to its good chemical stability, PFPE (perfluoropolyether) is not easy to decompose in extreme environments, so it can be used for a long time without degradation or pollution. PFPE's low toxicity and environmental protection prevent it from releasing harmful substances, which is in line with the modern concept of sustainable development. Against the background of the rise of cloud computing and big data, the heat dissipation problem of data centers has become more and more serious. Traditional air or liquid cooling systems often cannot meet the needs of high-power consumption equipment. The application of PFPE coolant can effectively reduce the operating temperature of computer servers and other equipment and improve overall energy efficiency.

[0004] With the popularity of electric vehicles, thermal management of battery packs has become one of the key technologies. Fluoropolyethers have good thermal conductivity and dielectric properties, which are very suitable for battery cooling systems of electric vehicles and can improve the safety and service life of battery packs. In special laboratories and extreme environments, fluoropolyether electronic coolants play an irreplaceable role. However, fluoropolyether electronic coolants still face some challenges. Enhancing the thermal conductivity and fluidity of fluoropolyethers is an important direction for future research. In addition, as the research and development of electronic products develops towards higher performance and smaller size, the performance requirements for cooling materials will become more stringent. Reducing the density of coolants can reduce the weight of the overall equipment and improve the integration and efficiency of the equipment. Some electronic coolant products have excellent thermal conductivity and electrical insulation, which are suitable for data centers, high-performance computers, aerospace and other fields, but the high price and high density and heavy weight limit the wide application and application scenarios of the above commercial products. Summary of the invention

[0005] In view of the above problems, the present application is proposed to provide an ultra-low density fluoropolyether electronic coolant and a preparation method thereof that overcomes the above problems or at least partially solves the above problems, comprising:

[0006] A method for preparing an ultra-low density fluoropolyether electronic coolant, wherein the ultra-low density fluoropolyether comprises a first structure and / or a second structure, comprising the steps of:

[0007] adding a metal cyanide catalyst into a reaction kettle;

[0008] Adding fluorinated alkylene oxide under nitrogen conditions, and adding a main chain unit and / or a fragment unit to the reaction kettle; wherein the main chain unit is a fluorinated alkylene oxide end-capping agent, including an alkyl alcohol or an alkoxy alcohol, and the fragment unit includes cyclohexene oxide or fluorinated cyclohexene oxide, and the fluoropolyether of the first structure is generated through the main chain unit, and the fluoropolyether of the second structure is generated through the fragment unit;

[0009] The reactor is heated to 100-150° C. and maintained at 100-150° C. for 4-10 hours to obtain an ultra-low density fluoropolyether; wherein the structural formula of the fluoropolyether of the first structure is:

[0010]

[0011] The structural formula of the fluoropolyether of the second structure is:

[0012]

[0013] A low-density fluoropolyether electronic coolant is configured by using the fluoropolyether of the first structure and / or the fluoropolyether of the second structure.

[0014] Furthermore, the structural formulas of the alkyl alcohol and the alkoxy alcohol are

[0015] R2-OH

[0016] Wherein, R2 in the structural formula is C1-C20 straight chain alkane, C1-C20 branched chain alkane,

[0017] R3 is a C1-C10 straight chain alkane or a C1-C10 branched chain alkane.

[0018] Furthermore, the molar ratio of the fluorinated alkylene oxide to the main chain unit is 10-30:1.

[0019] Furthermore, the structural formulas of the cyclohexene oxide and the fluorine-containing cyclohexene oxide are:

[0020]

[0021] Wherein, R4 in the structural formula is H or F.

[0022] Furthermore, the molar ratio of the fluorinated alkylene oxide to the fragment unit is 1-10:1.

[0023] Furthermore, the metal cyanide catalyst is a mixture of at least one double metal cyanide compound and at least one rare earth compound.

[0024] Furthermore, the addition amount of the metal cyanide catalyst is 50-100 ppm based on the weight of the product.

[0025] Furthermore, the structural formula of the fluorinated alkylene oxide is:

[0026]

[0027] Wherein, R1 in the structural formula is a C1-C10 fluorinated straight-chain alkane or a C1-C10 fluorinated branched-chain alkane.

[0028] Furthermore, the step of reacting at a temperature of 100-150° C. for 4-10 hours to obtain a low-density fluoropolyether further comprises:

[0029] The reactor is heated to 100-150°C and maintained at 100-150°C for 4-10 hours;

[0030] Add an excess amount of fluorinated alkylene oxide into the reactor and react at a temperature of 100-150° C. for 2-5 hours;

[0031] The product was filtered, and the filtrate was washed with methanol to obtain a low-density fluoropolyether.

[0032] A low-density fluoropolyether electronic coolant, wherein the ultra-low-density fluoropolyether electronic coolant is prepared by any of the preparation methods described above, and the structure of the fluoropolyether contained in the ultra-low-density fluoropolyether electronic coolant is:

[0033]

[0034] and / or,

[0035]

[0036] This application has the following advantages:

[0037] In the embodiments of the present application, in view of the shortcomings of the prior art electronic coolant having a high density, which makes the overall weight of the device high, and having a high production cost and is difficult to commercialize, the present application provides a method for preparing an ultra-low density fluoropolyether electronic coolant, wherein the ultra-low density fluoropolyether comprises a first structure and / or a second structure, and comprises the steps of: adding a metal cyanide catalyst to a reaction kettle; adding a fluorinated alkylene oxide under nitrogen conditions, and adding a main chain unit and / or a fragment unit to the reaction kettle; wherein the main chain unit is a fluorinated alkylene oxide capping unit; The end agent includes an alkyl alcohol or an alkoxy alcohol, the fragment unit includes cyclohexene oxide or fluorinated cyclohexene oxide, the fluoropolyether of the first structure is generated through the main chain unit, and the fluoropolyether of the second structure is generated through the fragment unit; the reactor is heated to 100-150°C, and the temperature of 100-150°C is maintained for 4-10 hours to obtain an ultra-low density fluoropolyether; the low-density fluoropolyether electronic coolant is configured through the fluoropolyether of the first structure and / or the fluoropolyether of the second structure, and a low-density fluoropolyether is prepared through preset conditions. Through the preset preparation scheme, the cost is low and the yield is high, it is simple and easy to separate and process, and the prepared electronic coolant has quantitative characteristics, low density, high thermal conductivity and high fluidity. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the technical solution of the present application, the drawings required for use in the description of the present application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0039] Figure 1 It is a flow chart of the steps of a method for preparing an ultra-low density fluoropolyether electronic coolant provided in one embodiment of the present application. DETAILED DESCRIPTION

[0040] In order to make the objects, features and advantages of the present application more obvious and understandable, the present application is further described in detail below in conjunction with the accompanying drawings and specific implementation methods. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present application.

[0041] By analyzing the prior art, the inventors found that the electronic coolants produced by the prior art have a high density and cannot be adapted to high-performance small-volume electronic devices. In addition, the production cost is high and is only suitable for cutting-edge technology fields, which limits the application fields and scenarios of commercial products.

[0042] Reference Figure 1, showing a flow chart of the steps of a method for preparing an ultra-low density fluoropolyether electronic coolant provided in one embodiment of the present application:

[0043] The ultra-low density fluoropolyether in the preparation method includes a first structure and / or a second structure, and includes the steps of:

[0044] S110, adding a metal cyanide catalyst into the reaction kettle;

[0045] S120, adding fluorinated alkylene oxide under nitrogen conditions, and adding main chain units and / or fragment units to the reactor; wherein the main chain units are fluorinated alkylene oxide end-capping agents, including alkyl alcohols or alkoxy alcohols, and the fragment units include cyclohexene oxide or fluorinated cyclohexene oxide, and the fluoropolyether of the first structure is generated through the main chain units, and the fluoropolyether of the second structure is generated through the fragment units;

[0046] S130, heating the reactor to 100-150° C. and maintaining the temperature at 100-150° C. for 4-10 hours to obtain an ultra-low density fluoropolyether; wherein the structural formula of the fluoropolyether of the first structure is:

[0047] The structural formula of the fluoropolyether of the second structure is:

[0048]

[0049] S140. Prepare a low-density fluoropolyether electronic coolant using the fluoropolyether of the first structure and / or the fluoropolyether of the second structure.

[0050] In an embodiment of the present application, in view of the shortcomings of the prior art that the electronic coolant has a high density, resulting in a high overall weight of the equipment, and a high production cost and difficulty in commercialization, the present application provides a method for preparing an ultra-low density fluoropolyether electronic coolant, wherein the ultra-low density fluoropolyether includes a first structure and / or a second structure, and comprises the steps of: adding a metal cyanide catalyst to a reactor; adding a fluorinated alkylene oxide under nitrogen conditions, and adding a main chain unit and / or a fragment unit to the reactor; wherein the main chain unit is a fluorinated alkylene oxide capping agent, including an alkyl alcohol or an alkoxy alcohol, and the fragment unit includes cyclohexene oxide or fluorinated cyclohexene oxide, the fluoropolyether of the first structure is generated by the main chain unit, and the fluoropolyether of the second structure is generated by the fragment unit; the reactor is heated to 100-150°C, and the temperature is maintained at 100-150°C for 4-10h to obtain an ultra-low density fluoropolyether; a low-density fluoropolyether electronic coolant is configured by the ultra-low density fluoropolyether, and a low-density is prepared by preset conditions. Through the preset preparation scheme, the cost is low and the yield is high. It is simple and easy to separate and process. The prepared electronic coolant has quantitative characteristics, low density, high thermal conductivity and high fluidity.

[0051] Next, a method for preparing an ultra-low density fluoropolyether electronic coolant in this exemplary embodiment will be further described.

[0052] As described in step S110, a metal cyanide catalyst is added into the reaction kettle.

[0053] In one embodiment of the present application, the metal cyanide catalyst is a mixture of at least one double metal cyanide compound and at least one rare earth compound.

[0054] As an example, the at least one double metal cyanide compound and the at least one rare earth compound may be Co[Fe(CN)3]3·2ZnCl2·3LaCl3 and Ni[Fe(CN)3]2·5ZnCl2·2CeCl3, etc.

[0055] In one embodiment of the present application, the added amount of the metal cyanide catalyst is 50-100 ppm based on the weight of the product.

[0056] As described in step S120, fluorinated alkylene oxide is added under nitrogen conditions, and main chain units and / or fragment units are added to the reactor; wherein the main chain units are fluorinated alkylene oxide end-capping agents, including alkyl alcohols or alkoxy alcohols, and the fragment units include cyclohexene oxide or fluorinated cyclohexene oxide, and the fluoropolyether of the first structure is generated by the main chain units, and the fluoropolyether of the second structure is generated by the fragment units.

[0057] In one embodiment of the present application, the structural formula of the fluorinated alkylene oxide is:

[0058]

[0059] Among them, R1 in the structural formula is C1-C 10 Fluorinated straight chain alkanes or C1-C 10 Fluorinated branched alkanes.

[0060] In one embodiment of the present application, the main chain unit includes an alkyl alcohol or an alkoxy alcohol, and the general structural formula is:

[0061] R2-OH

[0062]

[0063] C1-C 10 Straight chain alkanes or C1-C 10 Branched chain alkanes.

[0064] The main chain unit corresponds to the first structure of the fluoropolyether, namely

[0065]

[0066] The synthesis route of preparing the fluoropolyether of the first structure by using the main chain unit and the fluoroalkylene oxide is as follows:

[0067]

[0068] In one embodiment of the present application, the molar ratio of the fluorinated alkylene oxide to the main chain unit is 10-30:1.

[0069] In one embodiment of the present application, the fragment unit is cyclohexene oxide or fluorinated cyclohexene oxide.

[0070] The structural formulas of the cyclohexene oxide and the fluorine-containing cyclohexene oxide are:

[0071]

[0072] Wherein, R4 in the structural formula is H or F.

[0073] The second structure of the fluoropolyether corresponding to the segment unit, namely

[0074]

[0075] The synthetic route for preparing the fluoropolyether of the second structure by using the fragment unit and the fluoroalkylene oxide is as follows:

[0076]

[0077] In one embodiment of the present application, the molar ratio of the fluorinated alkylene oxide to the fragment unit is 1-10:1.

[0078] As described in step S130, the reactor is heated to 100-150° C. and maintained at 100-150° C. for 4-10 hours to obtain an ultra-low density fluoropolyether; wherein the structural formula of the fluoropolyether of the first structure is:

[0079]

[0080] The structural formula of the fluoropolyether of the second structure is:

[0081]

[0082] In one embodiment of the present invention, the specific process of "raising the temperature of the reactor to 100-150° C. and maintaining the temperature of 100-150° C. for 4-10 hours to obtain ultra-low density fluoropolyether" in step S130 can be further explained in combination with the following description.

[0083] As described in the following steps, the reactor is heated to 100-150° C. and maintained at 100-150° C. for 4-10 hours;

[0084] As described in the following steps, an excess amount of fluorinated alkylene oxide is added to the reactor, and the reaction is carried out at a temperature of 100-150° C. for 2-5 hours;

[0085] The resultant was filtered and the filtrate was washed with methanol as described in the following steps to obtain a low-density fluoropolyether.

[0086] It should be noted that the addition of excess fluorinated alkylene oxide allows the reactants in the reactor to react completely, and the excess reactants and impurities are subsequently washed away with methanol to ensure that the reactants react completely, facilitate cleaning and improve reaction efficiency.

[0087] As described in step S130, a low-density fluoropolyether electronic coolant is prepared by using the ultra-low-density fluoropolyether.

[0088] In one specific implementation, the preparation of the low-density fluoropolyether of the first structure is:

[0089] Reaction route:

[0090]

[0091] That is, R1 in the general formula is -CF3, R2 is R3 is ethyl.

[0092] Preparation method: Add 5 mg of multi-metal cyanide catalyst Co[Fe(CN)3]3·2ZnCl2·3LaCl3 to a 500 ml glass reactor, evacuate for half an hour, replace with nitrogen three times, add 30 g of fluorinated propylene oxide and 2.69 g of 2-[2-(2-ethoxyethoxy)ethoxy]ethanol to the glass reactor under nitrogen, stir for half an hour to mix evenly, heat to 100 degrees to react for 3 hours, add 20 g of fluorinated propylene oxide, continue to react for 3 hours, and stop the reaction. The reaction product is filtered and washed with methanol to obtain a low-density fluoropolyether of the first structure.

[0093] In one specific implementation, the preparation of the low-density fluoropolyether of the first structure is:

[0094] Reaction route:

[0095]

[0096] That is, in the general formula, R1 is -CF2CF2CF3; R2 is R3 is hexyl.

[0097] Preparation method: Add 5 mg of multi-metal cyanide catalyst Ni[Fe(CN)3]2·5ZnCl2·2CeCl3 to a 500 ml glass reactor, evacuate for half an hour, replace with nitrogen three times, add 30 g of fluorinated epoxypentane and 2.62 g of 2-[2-[2-(2-hexyloxyethoxy)ethoxy]ethoxy]ethanol to the glass reactor under nitrogen, stir for half an hour, heat to 120 degrees for 2 hours, add 20 g of fluorinated epoxypentane, continue to react for 2 hours, and stop the reaction. The reaction product is filtered and washed with methanol to obtain a low-density fluoropolyether of the first structure.

[0098] In one specific implementation, the preparation of the low-density fluoropolyether of the second structure is:

[0099] Reaction route:

[0100]

[0101] Preparation method: Add 5 mg of multi-metal cyanide catalyst Co[Fe(CN)3]3·2ZnCl2·3LaCl3 to a 500 ml glass reactor, evacuate for half an hour, replace with nitrogen three times, add 30 g of fluorinated pentane oxide and 31 g of fluorinated cyclohexane oxide to the glass reactor under nitrogen, stir for half an hour, heat to 120 degrees for 4 hours, and stop the reaction. The reaction product is filtered and washed with methanol to obtain a low-density fluoropolyether of the second structure.

[0102] The molecular weight distribution, boiling point, thermal stability, density, thermal conductivity, dielectric constant, and aging performance of the fluoropolyether prepared by this scheme were tested. The product prepared by this scheme method has the advantages of low density, colorless transparency, high dielectric constant, ideal chemical inertness, good thermal conductivity and system matching compatibility, and can be used in various temperature control and heat dissipation systems. The preparation method of this low-density perfluoropolyether is simple, high in yield, and strong in operability, and has good application prospects in the field of electronic coolants.

[0103] The present application also proposes an ultra-low density fluoropolyether electronic coolant, which is prepared by the above-mentioned preparation method. The structure of the fluoropolyether contained in the ultra-low density fluoropolyether electronic coolant is:

[0104]

[0105] and / or,

[0106]

[0107] Although the preferred embodiments of the present application have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the embodiments of the present application.

[0108] Finally, it should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or terminal device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or terminal device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or terminal device including the elements.

[0109] The above is a detailed introduction to an ultra-low density fluoropolyether electronic coolant and a preparation method thereof provided by the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea; at the same time, for a person skilled in the art, according to the idea of ​​the present application, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A method for preparing an ultra-low density fluoropolyether electronic coolant, characterized in that: The ultra-low density fluoropolyether comprises a first structure, and / or a second structure, comprising the steps of: adding a metal cyanide catalyst into a reaction kettle; Adding fluorinated alkylene oxide under nitrogen conditions, and adding a main chain unit and / or a fragment unit to the reaction kettle; wherein the main chain unit is a fluorinated alkylene oxide end-capping agent, including an alkyl alcohol or an alkoxy alcohol, and the fragment unit includes cyclohexene oxide or fluorinated cyclohexene oxide, and the fluoropolyether of the first structure is generated through the main chain unit, and the fluoropolyether of the second structure is generated through the fragment unit; The reactor is heated to 100-150° C. and maintained at 100-150° C. for 4-10 hours to obtain an ultra-low density fluoropolyether; wherein the structural formula of the fluoropolyether of the first structure is: The structural formula of the fluoropolyether of the second structure is: A low-density fluoropolyether electronic coolant is configured by using the fluoropolyether of the first structure and / or the fluoropolyether of the second structure.

2. The preparation method according to claim 1, characterized in that: The structural formula of the alkyl alcohol and the alkoxy alcohol is R2-OH Among them, R2 in the structural formula is C1-C 20 Straight chain alkanes, C1-C 20 Branched chain alkanes, R3 is C1-C 10 Straight chain alkanes or C1-C 10 Branched chain alkanes.

3. The preparation method according to claim 1, characterized in that: The molar ratio of the fluorinated alkylene oxide to the main chain unit is 10-30:

1.

4. The preparation method according to claim 1, characterized in that: The structural formulas of the cyclohexene oxide and the fluorine-containing cyclohexene oxide are: Wherein, R4 in the structural formula is H or F.

5. The preparation method according to claim 1, characterized in that: The molar ratio of the fluorinated alkylene oxide to the fragment unit is 1-10:

1.

6. The preparation method according to claim 1, characterized in that: The metal cyanide catalyst is a mixture of at least one double metal cyanide compound and at least one rare earth compound.

7. The preparation method according to claim 1, characterized in that: The added amount of the metal cyanide catalyst is 50-100 ppm based on the weight of the product.

8. The preparation method according to claim 1, characterized in that: The structural formula of the fluorinated alkylene oxide is: Among them, R1 in the structural formula is C1-C 10 Fluorinated straight chain alkanes or C1-C 10 Fluorinated branched alkanes.

9. The preparation method according to claim 1, characterized in that: The step of reacting at a temperature of 100-150° C. for 4-10 hours to obtain a low-density fluoropolyether further comprises: The reactor is heated to 100-150°C and maintained at 100-150°C for 4-10 hours; Add an excess amount of fluorinated alkylene oxide into the reactor and react at a temperature of 100-150° C. for 2-5 hours; The product was filtered, and the filtrate was washed with methanol to obtain a low-density fluoropolyether.

10. A low-density fluoropolyether electronic coolant, characterized in that: The ultra-low density fluoropolyether electronic coolant is prepared by the preparation method according to any one of claims 1 to 9, and the structure of the fluoropolyether contained in the ultra-low density fluoropolyether electronic coolant is: and / or,

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