Immersed cooling liquid and preparation method thereof
By introducing modification additives A and B into the immersed coolant, the problem of easy failure of small molecule additives is solved, and the thermal conductivity, corrosion inhibition, oxidation and flame retardant properties of the coolant are improved. It is suitable for data centers efficient cooling requirements.
Patent Information
- Application Number
- CN202411462115.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-18
- Publication Date
- 2025-01-17
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Small molecule additives such as corrosion inhibitors, antioxidants and flame retardants used in existing immersion coolants have problems such as small molecules, poor compatibility with base oil, and easy migration and failure in long-term use, resulting in the cooling fluid being Corrosion resistance, oxidation resistance and flame retardancy during storage and use cannot be guaranteed, and the high surfactivity of high insulating thermal fillers leads to poor heat dissipation.
Modification additive A and additive B, which introduces benzotriazole and alkane long chains into the highly thermally conductive insulating filler. Additive B is a hyperbranched macromolecule containing hindered phenol and DOPO, through specific chemistry The reaction process forms substances with stability and good dispersion, improving the thermal conductivity, corrosion resistance, oxidation resistance and flame retardant properties of the coolant.
It improves the thermal conductivity, corrosion resistance, oxidation resistance and flame retardancy of the coolant, extends its service life, and shows excellent performance in the high temperature and high radiation environment of the data center.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of cooling liquids, and in particular to an immersion cooling liquid and a preparation method thereof. Background Art
[0002] Data centers (DCs) include servers, switches, storage devices, racks, etc. They are physical places for data exchange and storage, and are also the most important infrastructure for the information industry. The temperature control system of a data center must ensure that the information interaction system (ICT) equipment operates stably at the optimal temperature. When the instantaneous heat exceeds the critical temperature, thermal protection will be triggered, shortening the life of the processor. Therefore, data centers require an external cooling system to ensure that the heat generated by ICT equipment is removed and hot spots are quickly eliminated. The air cooling traditionally used in data centers has high requirements for ambient temperature, air quality, etc., and the energy consumption of air cooling is higher than that of liquid cooling, so liquid cooling technology has entered the stage of alternative applications.
[0003] Liquid cooling is mainly divided into cold plate type, spray type and immersion type. Cold plate liquid cooling is to fit the cold plate filled with coolant tightly with the CPU and other heat dissipation devices to achieve local precision cooling, but because the heat is dissipated through the metal cold plate, traditional air cooling equipment such as air conditioners are still needed; spray liquid cooling is to spray the coolant directly onto the heat-generating components, and then recover the coolant after heat exchange. This method has uneven flow of the spray plate and is difficult to deal with problems such as instantaneous heat; immersion liquid cooling is to completely immerse the electronic heat-generating equipment in the coolant. After the coolant takes away the heat, it is cooled through an outdoor cooling tower for recycling. Compared with cold plate and spray types, immersion liquid cooling has higher thermal conductivity and heat uniformity.
[0004] In the prior art, an immersion coolant used in cooling of data centers is obtained by adding high-insulation thermal conductive fillers, functional additives, etc. to base oil for mixing. The added functional additives include corrosion inhibitors, antioxidants, flame retardants, defoamers and other additives. Adding functional additives can prevent the use of coolants from being adversely affected by the corrosion of electronic heating equipment made of metal materials, the degradation of the thermal oxidation performance of the immersion liquid, and the potential fire hazard caused by the combustion of the base oil, thereby obtaining an immersion coolant with more stable performance and longer service life. However, corrosion inhibitors such as benzotriazole, antioxidants such as hindered phenols, and phosphorus-containing flame retardants such as DOPO all have problems such as small molecules, poor compatibility with base oils, and easy migration failure after long-term use, and cannot guarantee the corrosion inhibition, oxidation resistance and flame retardancy of the coolant during storage and use. In addition, inorganic nanoparticles such as nano-alumina, nano-aluminum nitride and nano-boron nitride, which are usually included in high-insulation thermal conductive fillers, have high surface activity, are easy to agglomerate and cannot effectively dissipate heat, and fail to make the coolant play an effective cooling role.
[0005] Therefore, a suitable modification method is needed to improve the above-mentioned problems existing in the use of small molecule additives such as corrosion inhibitors, antioxidants, flame retardants and high-insulation thermal conductive fillers, so as to obtain immersion coolants with better performance, expand their application scope, and thus obtain good application prospects. Summary of the invention
[0006] In order to solve the above technical problems, the present invention provides an immersion cooling liquid and a preparation method thereof.
[0007] The purpose of the present invention can be achieved through the following technical solutions: An immersion coolant comprises the following raw materials in parts by weight: 90-100 parts of base oil, 7-9 parts of additive A, 4.5-5.5 parts of additive B, and 0.5-1.0 parts of defoaming agent; The base oil is one of mineral oil and vegetable oil; the defoaming agent is one of methyl silicone oil, ethyl silicone oil and acrylate; The preparation of the immersion cooling liquid comprises the following steps: The base oil, additive A and 2 / 3 of the total mass of the defoamer are stirred and mixed at room temperature and a speed of 200-300 r / min for 2-2.5 hours, and then the additive B and the remaining defoamer are added and stirred and mixed at room temperature and a speed of 100-200 r / min for 1-1.5 hours to obtain the immersion coolant.
[0008] The preparation of the auxiliary agent A comprises the following steps: Step A1: adding a high thermal conductive insulating filler to ethanol, ultrasonically dispersing for 30-40 minutes to obtain a solution a, then adding oleic acid to the ethanol, stirring at 50-60° C. for 20-30 minutes to obtain a solution b, adding the solution b to the solution a, reflux stirring at 75-85° C. for 1-1.5 hours, and then filtering, drying, and grinding to obtain a modified filler; Furthermore, the dosage ratio of the high thermal conductive insulating filler to ethanol is 10 g: 30-40 mL, the dosage ratio of oleic acid to ethanol is 0.1 mol: 60-70 mL, the dosage ratio of solution a to solution b is 40-50 mL: 65-75 mL, the volume fraction of ethanol is 95%, and the high thermal conductive insulating filler is one of nano-alumina, nano-silicon nitride, and nano-boron nitride; During the reaction of step A1, oleic acid is used to wet-modify the high thermal conductivity insulating filler to obtain a modified filler having a long alkane chain with unsaturated double bonds on the surface; Step A2: Add the modified filler to dichloromethane, add 3-chloroperoxybenzoic acid under stirring, and react at room temperature for 4-5 hours to obtain an epoxy product; in a protective gas atmosphere, add 2H-benzotriazole-2-butyric acid to ethyl acetate, heat to 40-50° C., add pyridine, add the epoxy product under stirring, continue to stir and react for 8-10 hours, then heat to 100-110° C., reflux and stir for 1-2 hours to obtain a hydroxyl product; Further, the usage ratio of the modified filler, dichloromethane and 3-chloroperoxybenzoic acid is 5-7 g: 50-60 mL: 20-22 g; the usage ratio of 2H-benzotriazole-2-butyric acid, ethyl acetate, pyridine and epoxy product is 23-25 g: 110-120 mL: 0.1-0.2 mol: 25-27 g; During the reaction of step A2, the unsaturated carbon-carbon double bonds in the modified filler are oxidized to epoxy groups to obtain epoxy products; the carboxyl group of 2H-benzotriazole-2-butyric acid reacts with the epoxy group of the epoxy product to generate a hydroxyl product containing benzotriazole; Step A3: adding the hydroxyl product and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 1, then adding lauroyl chloride to dimethyl sulfoxide to obtain a mixed solution 2, adding the mixed solution 2 dropwise to the mixed solution 1 under an ice-water bath, then heating to 40-45° C., reacting at a constant temperature for 8-10 hours, and distilling under reduced pressure to obtain an auxiliary agent A; Further, the usage ratio of the hydroxyl product, potassium carbonate and dimethyl sulfoxide is 28-30 g: 0.01-0.02 mol: 65-75 mL; the usage ratio of lauroyl chloride and dimethyl sulfoxide is 23-25 g: 55-65 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 70-80 mL: 60-70 mL; During the reaction of step A3, the hydroxyl product reacts with lauroyl chloride to generate an esterification product containing a high thermal conductive insulating filler, benzotriazole and a long alkane chain, namely, auxiliary agent A.
[0009] The preparation of the auxiliary agent B comprises the following steps: Step B1: 1,3-oleyl-2-elaidyl glyceride is added to dichloromethane, and 3-chloroperoxybenzoic acid is added under stirring, and the mixture is stirred at room temperature for 4-5 hours to obtain the epoxy product 1; in a protective gas atmosphere, a carboxylic acid containing a hindered phenol is added to ethyl acetate, the temperature is raised to 45-55° C., pyridine is added, stirring is started, and the epoxy product 1 is added, the mixture is stirred for 9-11 hours, and then the temperature is raised to 110-120° C., and the mixture is refluxed with stirring for 1-1.5 hours to obtain the hydroxyl product 1; Further, the dosage ratio of 1,3-oleyl-2-elaidyl glycerol ester, dichloromethane, and 3-chloroperoxybenzoic acid is 0.1 mol: 210-230 mL: 0.3-0.4 mol; the dosage ratio of the carboxylic acid containing hindered phenol, ethyl acetate, pyridine, and epoxidation product 1 is 0.3-0.4 mol: 200-220 mL: 10-13 g: 27-30 g, and the carboxylic acid containing hindered phenol is one of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, and 3,5-di-tert-butyl-4-hydroxybenzoic acid; During the reaction of step B1, the unsaturated carbon-carbon double bond in 1,3-oleyl-2-elaidyl glycerol is oxidized to an epoxy group to obtain an epoxy product 1; the carboxyl group of the carboxylic acid containing hindered phenol reacts with the epoxy group of the epoxy product to generate a hydroxyl product 1 containing hindered phenol; Step B2: Add the carboxylic acid containing DOPO to DMF, add dichlorothionyl under stirring, and reflux and stir at 50-55° C. for 4-5 hours to obtain an acyl chloride product; add an alcohol containing an unsaturated double bond and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 3, and then add the acyl chloride product to dimethyl sulfoxide to obtain a mixed solution 4, and add the mixed solution 4 dropwise to the mixed solution 3 under an ice-water bath, then heat to 40-50° C., react at a constant temperature for 7-9 hours, and distill under reduced pressure to obtain a DOPO product containing a carbon-carbon double bond; Further, the carboxylic acid containing DOPO is [(6-oxo-6H-dibenzo[C,E][1,2]oxaphosphorin-6-yl)methyl]succinic acid, and the amount ratio of the carboxylic acid containing DOPO, DMF, and dichlorothionyl is 0.1-0.15 mol: 100-120 mL: 0.2-0.3 mol; the alcohol containing an unsaturated double bond is one of 8-nonene-1-ol, 9-decene-1-ol, and (Z)-8-dodecene-1-ol, and the amount ratio of the alcohol containing an unsaturated double bond, potassium carbonate, and dimethyl sulfoxide is 0.2-0.25 mol: 0.01-0.02 mol: 70-80 mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide is 40-42 g: 90-100 mL; the amount ratio of the mixed solution 3 and the mixed solution 4 is 80-90 mL: 100-110 mL; During the reaction of step B2, the carboxylic acid containing DOPO reacts with thionyl chloride to generate an acyl chloride product; the acyl chloride product then reacts with an alcohol containing an unsaturated double bond to obtain a DOPO product containing a carbon-carbon double bond; Step B3: Add the DOPO product containing a carbon-carbon double bond to dichloromethane, add 3-chloroperoxybenzoic acid while stirring, and react at room temperature for 4-5 hours to obtain a DOPO product containing an epoxy group; add the DOPO product containing an epoxy group and the hydroxyl product 1 to methanol, start stirring, and then add trimethylamine, reflux and stir at 110-120° C. for 6-7 hours to obtain an additive B; Further, the usage ratio of the DOPO product containing a carbon-carbon double bond, dichloromethane, and 3-chloroperoxybenzoic acid is 63-65 g: 140-150 mL: 0.25-0.3 mol; the usage ratio of the DOPO product containing an epoxy group, the hydroxyl product 1, methanol, and trimethylamine is 66-68 g: 32-35 g: 220-230 mL: 0.02-0.03 mol; During the reaction of step B3, the unsaturated carbon-carbon double bonds of the DOPO product containing carbon-carbon double bonds are oxidized into epoxy groups to obtain a DOPO product containing epoxy groups; the epoxy groups of the DOPO product containing epoxy groups then react with the hydroxyl groups of the hydroxyl product 1 to generate an auxiliary agent B containing hindered phenol and DOPO and having a hyperbranched macromolecular structure.
[0010] Beneficial effects of the invention: The invention discloses an immersion coolant, comprising raw materials such as base oil, additive A, additive B and defoamer. In the process of synthesizing additive A and additive B, biodegradable reactants such as oleic acid, lauroyl chloride and 1,3-oleyl-2-elaidyl glyceride are used, thereby improving the environmental friendliness of the immersion coolant.
[0011] The synthesized auxiliary agent A is prepared by modifying a high thermal conductivity insulating filler through a reaction, and introducing benzotriazole and a long alkane chain onto the surface of the high thermal conductivity insulating filler. After benzotriazole is loaded on the high thermal conductivity insulating filler, it is not easy to migrate and fail. After the surface of the high thermal conductivity insulating filler is modified, the agglomeration phenomenon is improved. At the same time, the long alkane chain is introduced, so that the auxiliary agent A is more evenly dispersed in the coolant with mineral oil and vegetable oil as the base oil, and the thermal conductivity and heat dissipation of the base oil are improved; in the auxiliary agent A, benzotriazole can form a stable covalent bond and coordination bond with the metal and be adsorbed on the metal surface, and the long alkane chain forms a tight protective film on the metal surface, which effectively isolates the metal from contact with corrosive media such as water and oxygen, and delays metal corrosion; the addition of auxiliary agent A makes the coolant have better thermal conductivity and heat dissipation and better corrosion inhibition.
[0012] The synthesized additive B is a substance with a hyperbranched macromolecular structure containing hindered phenol, DOPO and long alkane chains. After the macromolecule is formed, hindered phenol and DOPO are not easy to migrate and fail, and the introduction of long alkane chains enhances the compatibility with the base oil, so that additive B can be more evenly dispersed in the coolant. Hindered phenol can quickly terminate the oxidative degradation reaction chain to avoid oxidative degradation of the base oil and extend the service life of the coolant. The DOPO structure can produce phosphorus-containing derivatives that cover the surface during combustion, isolate the transfer of combustible gas and heat, and prevent the combustion from continuing. The addition of additive B improves the antioxidant and flame retardancy of the coolant. DETAILED DESCRIPTION
[0013] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0014] Example 1 An auxiliary agent A, the preparation of which comprises the following steps: Step A1: adding a high thermal conductive insulating filler to ethanol, ultrasonically dispersing for 30 minutes to obtain solution a, then adding oleic acid to ethanol, stirring at 50°C for 20 minutes to obtain solution b, adding solution b to solution a, refluxing and stirring at 75°C for 1 hour, filtering, drying and grinding to obtain a modified filler; the amount ratio of the high thermal conductive insulating filler to ethanol is 10g:30mL, the amount ratio of oleic acid to ethanol is 0.1mol:60mL, the amount ratio of solution a to solution b is 40mL:65mL, the volume fraction of ethanol is 95%, and the high thermal conductive insulating filler is nano-alumina; Step A2: Add the modified filler to dichloromethane, add 3-chloroperoxybenzoic acid under stirring, and react at room temperature for 4 hours to obtain an epoxy product; in a nitrogen atmosphere, add 2H-benzotriazole-2-butyric acid to ethyl acetate, heat to 40°C, add pyridine, add the epoxy product under stirring, continue to react with stirring for 8 hours, then heat to 100°C, reflux and stir for 1 hour to obtain a hydroxyl product; the amount ratio of the modified filler, dichloromethane and 3-chloroperoxybenzoic acid is 5g:50mL:20g; the amount ratio of 2H-benzotriazole-2-butyric acid, ethyl acetate, pyridine and epoxy product is 23g:110mL:0.1mol:25g; Step A3: Add the hydroxyl product and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 1, then add lauroyl chloride to dimethyl sulfoxide to obtain a mixed solution 2, add the mixed solution 2 dropwise to the mixed solution 1 under an ice-water bath, then raise the temperature to 40°C, react at a constant temperature for 8 hours, and distill under reduced pressure to obtain an auxiliary agent A; the amount ratio of the hydroxyl product, potassium carbonate and dimethyl sulfoxide is 28g:0.01mol:65mL; the amount ratio of lauroyl chloride and dimethyl sulfoxide is 23g:55mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 70mL:60mL.
[0015] Example 2 An auxiliary agent A, the preparation of which comprises the following steps: Step A1: adding a high thermal conductive insulating filler to ethanol, ultrasonically dispersing for 35 minutes to obtain solution a, then adding oleic acid to ethanol, stirring at 55°C for 25 minutes to obtain solution b, adding solution b to solution a, reflux stirring at 80°C for 1.3 hours, and then filtering, drying, and grinding to obtain a modified filler; the amount ratio of the high thermal conductive insulating filler to ethanol is 10g:35mL, the amount ratio of oleic acid to ethanol is 0.1mol:65mL, the amount ratio of solution a to solution b is 45mL:70mL, the volume fraction of ethanol is 95%, and the high thermal conductive insulating filler is nano silicon nitride; Step A2: Add the modified filler to dichloromethane, add 3-chloroperoxybenzoic acid under stirring, and react at room temperature for 4.5 hours to obtain an epoxy product; in a protective gas atmosphere, add 2H-benzotriazole-2-butyric acid to ethyl acetate, heat to 45°C, add pyridine, add the epoxy product under stirring, continue to stir and react for 9 hours, then heat to 105°C, reflux and stir for 1.5 hours to obtain a hydroxyl product; the amount ratio of the modified filler, dichloromethane and 3-chloroperoxybenzoic acid is 6g:55mL:21g; the amount ratio of 2H-benzotriazole-2-butyric acid, ethyl acetate, pyridine and epoxy product is 24g:115mL:0.15mol:26g; Step A3: Add the hydroxyl product and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 1, then add lauroyl chloride to dimethyl sulfoxide to obtain a mixed solution 2, add the mixed solution 2 dropwise to the mixed solution 1 under an ice-water bath, then heat to 43°C, react at a constant temperature for 9 hours, and distill under reduced pressure to obtain an auxiliary agent A; the amount ratio of the hydroxyl product, potassium carbonate and dimethyl sulfoxide is 29g:0.015mol:70mL; the amount ratio of lauroyl chloride and dimethyl sulfoxide is 24g:60mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 75mL:65mL.
[0016] Example 3 An auxiliary agent A, the preparation of which comprises the following steps: Step A1: adding a high thermal conductive insulating filler to ethanol, ultrasonically dispersing for 40 minutes to obtain solution a, then adding oleic acid to ethanol, stirring at 60°C for 30 minutes to obtain solution b, adding solution b to solution a, reflux stirring at 85°C for 1.5 hours, and then filtering, drying, and grinding to obtain a modified filler; the amount ratio of the high thermal conductive insulating filler to ethanol is 10g:40mL, the amount ratio of oleic acid to ethanol is 0.1mol:70mL, the amount ratio of solution a to solution b is 50mL:75mL, the volume fraction of ethanol is 95%, and the high thermal conductive insulating filler is nano boron nitride; Step A2: Add the modified filler to dichloromethane, add 3-chloroperoxybenzoic acid under stirring, and react at room temperature for 5 hours to obtain an epoxy product; in a protective gas atmosphere, add 2H-benzotriazole-2-butyric acid to ethyl acetate, heat to 50°C, add pyridine, add the epoxy product under stirring, continue to stir and react for 10 hours, then heat to 110°C, reflux and stir for 2 hours to obtain a hydroxyl product; the amount ratio of the modified filler, dichloromethane and 3-chloroperoxybenzoic acid is 7g:60mL:22g; the amount ratio of 2H-benzotriazole-2-butyric acid, ethyl acetate, pyridine and epoxy product is 25g:120mL:0.2mol:27g; Step A3: Add the hydroxyl product and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 1, then add lauroyl chloride to dimethyl sulfoxide to obtain a mixed solution 2, add the mixed solution 2 dropwise to the mixed solution 1 under an ice-water bath, then heat to 45°C, react at a constant temperature for 10 hours, and distill under reduced pressure to obtain an auxiliary agent A; the amount ratio of the hydroxyl product, potassium carbonate and dimethyl sulfoxide is 30g:0.02mol:75mL; the amount ratio of lauroyl chloride and dimethyl sulfoxide is 25g:65mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 80mL:70mL.
[0017] Example 4 An auxiliary agent B, the preparation of which comprises the following steps: Step B1: 1,3-oleic acid-2-elaidic acid glyceride is added to dichloromethane, and 3-chloroperoxybenzoic acid is added under stirring, and the mixture is stirred at room temperature for 4 hours to obtain the epoxy product 1; in a nitrogen atmosphere, a carboxylic acid containing a hindered phenol is added to ethyl acetate, the temperature is raised to 45°C, pyridine is added, stirring is started, and the epoxy product 1 is added, stirring is carried out for 9 hours, and then the temperature is raised to 110°C, and refluxed with stirring for 1 hour to obtain the hydroxyl product 1; the dosage ratio of 1,3-oleic acid-2-elaidic acid glyceride, dichloromethane, and 3-chloroperoxybenzoic acid is 0.1 mol: 210 mL: 0.3 mol; the dosage ratio of the carboxylic acid containing a hindered phenol, ethyl acetate, pyridine, and the epoxy product 1 is 0.3 mol: 200 mL: 10 g: 27 g, and the carboxylic acid containing a hindered phenol is 3,5-di-tert-butyl-4-hydroxybenzoic acid; Step B2: Add the carboxylic acid containing DOPO to DMF, add dichlorothionyl under stirring, and reflux and stir at 50°C for 4 hours to obtain an acid chloride product; add an alcohol containing an unsaturated double bond and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 3, and then add the acid chloride product to dimethyl sulfoxide to obtain a mixed solution 4. In an ice-water bath, add the mixed solution 4 dropwise to the mixed solution 3, then heat to 40°C, react at a constant temperature for 7 hours, and distill under reduced pressure to obtain a DOPO product containing a carbon-carbon double bond; the carboxylic acid containing DOPO is [(6-oxo-6H-dibenzo[ C,E][1,2]oxaphosphorin-6-yl)methyl]succinic acid, carboxylic acid containing DOPO, DMF, and dichlorothionyl are used in a ratio of 0.1 mol: 100 mL: 0.2 mol; the alcohol containing an unsaturated double bond is 8-nonen-1-ol, and the alcohol containing an unsaturated double bond, potassium carbonate, and dimethyl sulfoxide are used in a ratio of 0.2 mol: 0.01 mol: 70 mL; the ratio of the acyl chloride product and dimethyl sulfoxide is 40 g: 90 mL; the ratio of mixed solution 3 and mixed solution 4 is 80 mL: 100 mL; Step B3: Add the DOPO product containing a carbon-carbon double bond to dichloromethane, add 3-chloroperbenzoic acid while stirring, and react at room temperature for 4 hours to obtain a DOPO product containing an epoxy group; add the DOPO product containing an epoxy group and the hydroxyl product 1 to methanol, start stirring, and then add trimethylamine, reflux and react at 110°C with stirring for 6 hours to obtain auxiliary agent B; the amount ratio of the DOPO product containing a carbon-carbon double bond, dichloromethane, and 3-chloroperbenzoic acid is 63g:140mL:0.25mol; the amount ratio of the DOPO product containing an epoxy group, the hydroxyl product 1, methanol, and trimethylamine is 66g:32g:220mL:0.02mol.
[0018] Example 5 An auxiliary agent B, the preparation of which comprises the following steps: Step B1: 1,3-oleic acid-2-elaidic acid glyceride is added to dichloromethane, and 3-chloroperoxybenzoic acid is added under stirring, and the mixture is stirred at room temperature for 4.5 hours to obtain an epoxy product 1; in a nitrogen atmosphere, a carboxylic acid containing a hindered phenol is added to ethyl acetate, the temperature is raised to 50° C., pyridine is added, stirring is started, and then the epoxy product 1 is added, the mixture is stirred for 10 hours, and then the temperature is raised to 115° C., and the mixture is refluxed and stirred for 1.3 hours to obtain a hydroxyl product 1; the amount ratio of 1,3-oleic acid-2-elaidic acid glyceride, dichloromethane, and 3-chloroperoxybenzoic acid is 0.1 mol: 220 mL: 0.35 mol; the amount ratio of the carboxylic acid containing a hindered phenol, ethyl acetate, pyridine, and the epoxy product 1 is 0.35 mol: 210 mL: 11.5 g: 28.5 g, and the carboxylic acid containing a hindered phenol is 3,5-di-tert-butyl-4-hydroxyphenylacetic acid; Step B2: Add the carboxylic acid containing DOPO to DMF, add dichlorothionyl under stirring, and reflux and stir at 53°C for 4.5 hours to obtain an acid chloride product; add an alcohol containing an unsaturated double bond and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 3, and then add the acid chloride product to dimethyl sulfoxide to obtain a mixed solution 4. In an ice-water bath, add the mixed solution 4 dropwise to the mixed solution 3, then heat to 45°C, react at a constant temperature for 8 hours, and distill under reduced pressure to obtain a DOPO product containing a carbon-carbon double bond; the carboxylic acid containing DOPO is [(6-oxo-6H-dibenzo[C ,E][1,2]oxyphosphorin-6-yl)methyl]succinic acid, carboxylic acid containing DOPO, DMF, and dichlorothionyl are used in a ratio of 0.13mol:110mL:0.25mol; the alcohol containing an unsaturated double bond is 9-decene-1-ol, the alcohol containing an unsaturated double bond, potassium carbonate, and dimethyl sulfoxide are used in a ratio of 0.23mol:0.015mol:75mL; the ratio of the acyl chloride product and dimethyl sulfoxide is 41g:95mL; the ratio of mixed solution 3 and mixed solution 4 is 85mL:105mL; Step B3: Add the DOPO product containing a carbon-carbon double bond to dichloromethane, add 3-chloroperbenzoic acid while stirring, and react at room temperature with stirring for 4.5 hours to obtain a DOPO product containing an epoxy group; add the DOPO product containing an epoxy group and the hydroxyl product 1 to methanol, start stirring, and then add trimethylamine, reflux and stir at 115°C for 6.5 hours to obtain auxiliary agent B; the amount ratio of the DOPO product containing a carbon-carbon double bond, dichloromethane, and 3-chloroperbenzoic acid is 64g:145mL:0.28mol; the amount ratio of the DOPO product containing an epoxy group, the hydroxyl product 1, methanol, and trimethylamine is 67g:33.5g:225mL:0.025mol.
[0019] Example 6 An auxiliary agent B, the preparation of which comprises the following steps: Step B1: 1,3-oleic acid-2-elaidic acid glyceride is added to dichloromethane, and 3-chloroperoxybenzoic acid is added under stirring, and the mixture is stirred at room temperature for 5 hours to obtain an epoxy product 1; in a protective gas atmosphere, a carboxylic acid containing a hindered phenol is added to ethyl acetate, the temperature is raised to 55° C., pyridine is added, stirring is started, and then the epoxy product 1 is added, and the mixture is stirred for 11 hours, and then the temperature is raised to 120° C., and the mixture is refluxed and stirred for 1.5 hours to obtain a hydroxyl product 1; the amount ratio of 1,3-oleic acid-2-elaidic acid glyceride, dichloromethane, and 3-chloroperoxybenzoic acid is 0.1 mol: 230 mL: 0.4 mol; the amount ratio of the carboxylic acid containing a hindered phenol, ethyl acetate, pyridine, and the epoxy product 1 is 0.4 mol: 220 mL: 13 g: 30 g, and the carboxylic acid containing a hindered phenol is 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid; Step B2: Add the carboxylic acid containing DOPO to DMF, add dichlorothionyl under stirring, and reflux and stir at 55°C for 5 hours to obtain an acyl chloride product; add an alcohol containing an unsaturated double bond and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 3, and then add the acyl chloride product to dimethyl sulfoxide to obtain a mixed solution 4. In an ice-water bath, add the mixed solution 4 dropwise to the mixed solution 3, then heat to 50°C, react at a constant temperature for 9 hours, and distill under reduced pressure to obtain a DOPO product containing a carbon-carbon double bond; the carboxylic acid containing DOPO is [(6-oxo-6H-dibenzo[C,E] [1,2] oxaphosphorin-6-yl)methyl] succinic acid, carboxylic acid containing DOPO, DMF, and dichlorothionyl are used in a ratio of 0.15 mol: 120 mL: 0.3 mol; the alcohol containing an unsaturated double bond is (Z)-8-dodecene-1-ol, the alcohol containing an unsaturated double bond, potassium carbonate, and dimethyl sulfoxide are used in a ratio of 0.25 mol: 0.02 mol: 80 mL; the acid chloride product and dimethyl sulfoxide are used in a ratio of 42 g: 100 mL; the ratio of mixed solution 3 and mixed solution 4 is 90 mL: 110 mL; Step B3: Add the DOPO product containing a carbon-carbon double bond to dichloromethane, add 3-chloroperbenzoic acid while stirring, and react at room temperature with stirring for 5 hours to obtain a DOPO product containing an epoxy group; add the DOPO product containing an epoxy group and the hydroxyl product 1 to methanol, start stirring, and then add trimethylamine, reflux and stir at 120°C for 7 hours to obtain auxiliary agent B; the amount ratio of the DOPO product containing a carbon-carbon double bond, dichloromethane, and 3-chloroperbenzoic acid is 65g:150mL:0.3mol; the amount ratio of the DOPO product containing an epoxy group, the hydroxyl product 1, methanol, and trimethylamine is 68g:35g:230mL:0.03mol.
[0020] Example 7 An immersion coolant comprises the following raw materials in parts by weight: 90 parts of base oil, 7 parts of auxiliary agent A, 4.5 parts of auxiliary agent B, and 0.5 parts of defoaming agent; the base oil is white oil; the defoaming agent is methyl silicone oil; The preparation of the immersion cooling liquid comprises the following steps: The base oil, the auxiliary agent A obtained in Example 1 and 2 / 3 of the total mass of the defoamer were stirred and mixed at room temperature and a speed of 200 r / min for 2 hours, and then the auxiliary agent B obtained in Example 4 and the remaining defoamer were added and stirred and mixed at room temperature and a speed of 100 r / min for 1 hour to obtain an immersion coolant.
[0021] Example 8 An immersion coolant comprises the following raw materials in parts by weight: 95 parts of base oil, 8 parts of auxiliary agent A, 5.0 parts of auxiliary agent B, and 0.8 parts of defoaming agent; the base oil is soybean oil; the defoaming agent is acrylate defoaming agent RP-6030; The preparation of the immersion cooling liquid comprises the following steps: The base oil, the auxiliary agent A obtained in Example 2 and 2 / 3 of the total mass of the defoamer were stirred and mixed at room temperature and a speed of 250 r / min for 2.3 hours, and then the auxiliary agent B obtained in Example 5 and the remaining defoamer were added and stirred and mixed at room temperature and a speed of 150 r / min for 1.3 hours to obtain an immersion coolant.
[0022] Example 9 An immersion coolant comprises the following raw materials in parts by weight: 100 parts of base oil, 9 parts of auxiliary agent A, 5.5 parts of auxiliary agent B, and 1.0 part of defoaming agent; the base oil is white oil; the defoaming agent is ethyl silicone oil; The preparation of the immersion cooling liquid comprises the following steps: The base oil, the auxiliary agent A obtained in Example 3 and 2 / 3 of the total mass of the defoamer were stirred and mixed at room temperature and a speed of 300 r / min for 2.5 hours, and then the auxiliary agent B obtained in Example 6 and the remaining defoamer were added and stirred and mixed at room temperature and a speed of 200 r / min for 1.5 hours to obtain an immersion coolant.
[0023] Comparative Example 1 Compared with Example 9, the auxiliary agent A is replaced with the modified filler obtained in step A1, that is, benzotriazole is not introduced into the high thermal conductive insulating filler, and the rest is exactly the same as Example 9 to prepare an immersion coolant.
[0024] Comparative Example 2 Compared with Example 9, the oleic acid in step A1 during the preparation of auxiliary agent A is replaced with 2H-benzotriazole-2-butyric acid, and then the substance 1 obtained in step A1 replaces auxiliary agent A, that is, no long alkane chain is introduced into the high thermal conductive insulating filler, and the rest is exactly the same as in Example 9 to obtain an immersion coolant.
[0025] Comparative Example 3 Compared with Example 9, the auxiliary agent B was replaced with 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, and the rest was exactly the same as Example 9 to prepare an immersion coolant.
[0026] Comparative Example 4 Compared with Example 9, the auxiliary agent B was replaced with DOPO, and the rest was exactly the same as Example 9 to prepare an immersion coolant.
[0027] The immersion cooling liquid prepared by the present invention is further tested for its effect, and the test results are as follows.
[0028] The coolants obtained in Examples 7-9 and Comparative Examples 1-4 were placed in a liquid thermal conductivity meter (TC3010 series), heated to 60°C, and tested for thermal conductivity; 1 g of copper and 1 g of iron were placed in the coolants obtained in Examples 7-9 and Comparative Examples 1-4, respectively, and immersed at 60°C for 7 days, and the rust on the surfaces of the copper and iron were observed and recorded. After being wiped dry, the mass increase after immersion was measured; the coolants obtained in Examples 7-9 and Comparative Examples 1-4 were placed in an oven at 80°C for 3 days, and the kinematic viscosity before and after thermal oxidation treatment was measured, and the kinematic viscosity test at 40°C was performed with reference to GB / T265 "Method for Determination of Kinematic Viscosity of Petroleum Products and Calculation of Dynamic Viscosity"; the coolants were placed in a radiant temperature of 50 kW / m 2 The ignition time of the coolant is measured under the radiation intensity of to measure the combustion performance of the coolant caused by the heat generated by the radiation under the radiation conditions of the data center; the results are recorded in Table 1;
[0029] According to the data in Table 1, the immersion coolant of the present invention has excellent thermal conductivity, corrosion inhibition, oxidation resistance and flame retardancy. Comparison of Example 9 with Comparative Example 1 shows that benzotriazole is not introduced into the high thermal conductivity insulating filler, and the corrosion inhibition of the immersion coolant is very poor. Comparison of Example 9 with Comparative Example 2 shows that the substance 1 obtained by introducing benzotriazole into the high thermal conductivity insulating filler but not introducing the long chain of alkane has poor dispersibility in the base oil, and the corrosion inhibition ability of the coolant is weakened. Comparison of Example 9 with Comparative Example 3 shows that the use of small molecule hindered phenols, without the introduction of long alkane chains and DOPO to form a hyperbranched macromolecular structure, the ignition time of the coolant is greatly reduced, the flame retardant performance is greatly weakened, the dispersibility of small molecule hindered phenols in the coolant is weakened, the antioxidant ability of the coolant is slightly weakened, the kinematic viscosity of the coolant is increased after oxidation treatment, and the fluidity of the coolant is weakened, resulting in a weakened cooling effect. Comparison of Example 9 with Comparative Example 4 shows that by using small molecule DOPO and without introducing long alkane chains and hindered phenols to form a hyperbranched macromolecular structure, the antioxidant capacity of the coolant is greatly reduced, and the kinematic viscosity of the coolant increases significantly after oxidation treatment, resulting in a significant weakening of the cooling effect, weakened dispersibility of small molecule DOPO in the coolant, shortened ignition time of the coolant, and weakened flame retardant properties.
[0030] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.
Claims
1. An immersion coolant, characterized in that: The invention comprises the following raw materials in parts by weight: 90-100 parts of base oil, 7-9 parts of auxiliary agent A, 4.5-5.5 parts of auxiliary agent B, and 0.5-1.0 parts of defoaming agent; The preparation of the auxiliary agent A comprises the following steps: Step A1: adding a high thermal conductive insulating filler to ethanol, ultrasonically dispersing for 30-40 minutes to obtain a solution a, then adding oleic acid to the ethanol, stirring at 50-60° C. for 20-30 minutes to obtain a solution b, adding the solution b to the solution a, reflux stirring at 75-85° C. for 1-1.5 hours, and then filtering, drying, and grinding to obtain a modified filler; Step A2: Add the modified filler to dichloromethane, add 3-chloroperoxybenzoic acid under stirring, and react at room temperature for 4-5 hours to obtain an epoxy product; in a protective gas atmosphere, add 2H-benzotriazole-2-butyric acid to ethyl acetate, heat to 40-50° C., add pyridine, add the epoxy product under stirring, continue to stir and react for 8-10 hours, then heat to 100-110° C., reflux and stir for 1-2 hours to obtain a hydroxyl product; Step A3: Add the hydroxyl product and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 1, then add lauroyl chloride to dimethyl sulfoxide to obtain a mixed solution 2, add the mixed solution 2 dropwise to the mixed solution 1 under an ice-water bath, then heat to 40-45° C., react at a constant temperature for 8-10 hours, and distill under reduced pressure to obtain an auxiliary agent A.
2. An immersion cooling liquid according to claim 1, characterized in that: The base oil is one of mineral oil and vegetable oil; the defoaming agent is one of methyl silicone oil, ethyl silicone oil and acrylate.
3. The immersion cooling liquid according to claim 1, characterized in that: In step A1, the dosage ratio of high thermal conductive insulating filler and ethanol is 10g:30-40mL, the dosage ratio of oleic acid and ethanol is 0.1mol:60-70mL, the dosage ratio of solution a and solution b is 40-50mL:65-75mL, the volume fraction of ethanol is 95%, and the high thermal conductive insulating filler is one of nano-alumina, nano-silicon nitride, and nano-boron nitride.
4. The immersion cooling liquid according to claim 1, characterized in that: In step A2, the usage ratio of the modified filler, dichloromethane and 3-chloroperoxybenzoic acid is 5-7 g: 50-60 mL: 20-22 g; the usage ratio of 2H-benzotriazole-2-butyric acid, ethyl acetate, pyridine and epoxy product is 23-25 g: 110-120 mL: 0.1-0.2 mol: 25-27 g.
5. The immersion cooling liquid according to claim 1, characterized in that: In step A3, the usage ratio of the hydroxyl product, potassium carbonate and dimethyl sulfoxide is 28-30 g: 0.01-0.02 mol: 65-75 mL; the usage ratio of lauroyl chloride and dimethyl sulfoxide is 23-25 g: 55-65 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 70-80 mL: 60-70 mL.
6. The immersion cooling liquid according to claim 1, characterized in that: The preparation of the auxiliary agent B comprises the following steps: Step B1: 1,3-oleyl-2-elaidyl glyceride is added to dichloromethane, and 3-chloroperoxybenzoic acid is added under stirring, and the mixture is stirred at room temperature for 4-5 hours to obtain the epoxy product 1; in a protective gas atmosphere, a carboxylic acid containing a hindered phenol is added to ethyl acetate, the temperature is raised to 45-55° C., pyridine is added, stirring is started, and the epoxy product 1 is added, the mixture is stirred for 9-11 hours, and then the temperature is raised to 110-120° C., and the mixture is refluxed with stirring for 1-1.5 hours to obtain the hydroxyl product 1; Step B2: Add the carboxylic acid containing DOPO to DMF, add dichlorothionyl under stirring, and reflux and stir at 50-55° C. for 4-5 hours to obtain an acyl chloride product; Add an alcohol containing an unsaturated double bond and potassium carbonate to dimethyl sulfoxide to obtain a mixed solution 3, then add the acyl chloride product to dimethyl sulfoxide to obtain a mixed solution 4, dropwise add the mixed solution 4 to the mixed solution 3 under an ice-water bath, then heat to 40-50° C., react at a constant temperature for 7-9 hours, and distill under reduced pressure to obtain a DOPO product containing a carbon-carbon double bond; Step B3: Add the DOPO product containing a carbon-carbon double bond to dichloromethane, add 3-chloroperoxybenzoic acid while stirring, and react with stirring at room temperature for 4-5 hours to obtain a DOPO product containing an epoxy group; add the DOPO product containing an epoxy group and the hydroxyl product 1 to methanol, start stirring, and then add trimethylamine, reflux and stir at 110-120°C for 6-7 hours to obtain additive B.
7. An immersion cooling liquid according to claim 6, characterized in that: In step B1, the usage ratio of 1,3-oleyl-2-elaidyl glyceride, dichloromethane, and 3-chloroperoxybenzoic acid is 0.1 mol: 210-230 mL: 0.3-0.4 mol; the usage ratio of the carboxylic acid containing hindered phenol, ethyl acetate, pyridine, and epoxidation product 1 is 0.3-0.4 mol: 200-220 mL: 10-13 g: 27-30 g, and the carboxylic acid containing hindered phenol is one of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, and 3,5-di-tert-butyl-4-hydroxybenzoic acid.
8. The immersion cooling liquid according to claim 6, characterized in that: In step B2, the carboxylic acid containing DOPO is [(6-oxo-6H-dibenzo[C,E][1,2]oxaphosphorin-6-yl)methyl]succinic acid, and the amount ratio of the carboxylic acid containing DOPO, DMF, and dichlorothionyl is 0.1-0.15 mol:100-120 mL:0.2-0.3 mol; the alcohol containing an unsaturated double bond is one of 8-nonene-1-ol, 9-decene-1-ol, and (Z)-8-dodecene-1-ol, and the amount ratio of the alcohol containing an unsaturated double bond, potassium carbonate, and dimethyl sulfoxide is 0.2-0.25 mol:0.01-0.02 mol:70-80 mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide is 40-42 g:90-100 mL; the amount ratio of the mixed solution 3 and the mixed solution 4 is 80-90 mL:100-110 mL.
9. The immersion cooling liquid according to claim 6, characterized in that: In step B3, the usage ratio of the DOPO product containing a carbon-carbon double bond, dichloromethane, and 3-chloroperbenzoic acid is 63-65 g: 140-150 mL: 0.25-0.3 mol; the usage ratio of the DOPO product containing an epoxy group, the hydroxyl product 1, methanol, and trimethylamine is 66-68 g: 32-35 g: 220-230 mL: 0.02-0.03 mol.
10. A method for preparing the immersion cooling liquid according to any one of claims 1 to 9, characterized in that: The steps include: The base oil, additive A and 2 / 3 of the total mass of the defoamer are stirred and mixed at room temperature and a speed of 200-300 r / min for 2-2.5 hours, and then the additive B and the remaining defoamer are added and stirred and mixed at room temperature and a speed of 100-200 r / min for 1-1.5 hours to obtain the immersion coolant.