Oxahydrofluoroether compound for coolant and preparation method therefor, coolant composition and use thereof

Abstract

Provided in the present application are an oxahydrofluoroether compound for a coolant and a preparation method therefor, a coolant composition and the use thereof. The oxahydrofluoroether compound is a compound as represented by formula (1), wherein R1 and R2 are both selected from perfluoroalkyl groups; R3 is selected from CnF2n+1; and m is an integer of 0 to 4, and n is a positive integer. The oxahydrofluoroether compound has the characteristics of a high boiling point, a low pour point, high volume resistivity, relatively low viscosity at -60°C, a relatively low GWP100 value, high chemical stability, good thermal stability and high temperature-control accuracy.

Description

An oxahydrofluoroether compound for use as a coolant, its preparation method, coolant composition and its application. Technical Field

[0001] This application relates to the field of refrigerant technology, and in particular to an oxahydrofluoroether compound for use as a coolant, a method for preparing the same, a coolant composition and its application. Background Technology

[0002] Semiconductor manufacturing generally includes wafer fabrication, chip fabrication, and post-packaging. Chip fabrication further includes steps such as oxide layer growth, photolithography, etching, cleaning and drying, thin film growth, and ion implantation. Throughout the semiconductor manufacturing process, many steps require temperature management, such as etching, thin film growth, and post-packaging. With the continuous development of semiconductor technology and increasing environmental awareness, higher requirements are being placed on the coolants used in semiconductor manufacturing, such as requiring a volume resistivity greater than 10⁻⁶. ^ 11Ω·cm, Global Warming Potential (GWP 100) < 100, Pour Point of Coolant < -60℃, Low Viscosity, Good Chemical Stability, etc.

[0003] Commonly used semiconductor process coolants include: water-ethylene glycol, perfluorotripropylamine, perfluoropolyether, and hydrofluoroether. While water-ethylene glycol has a low GWP value, its pour point is >-60℃ and its viscosity is high, thus it does not meet the requirements. Perfluorotripropylamine (e.g., 3M)... TM Fluorinert TM FC-3283) and perfluoropolyethers (such as Solvey) Although their pour points meet the requirements, their GWP values ​​are all greater than 8000, which does not meet the requirements; traditionally used hydrofluoroethers, such as 3M produced by 3M... TM NOVEC TM The boiling point of 7200 is only 76℃, making it suitable only for low-temperature temperature control and not for high-temperature temperature control. Furthermore, its volume resistivity is only 10. ^ 8Ω·cm cannot meet the usage requirements; for example, 3M TM NOVEC TM The volume resistivity of 7500 is only 10. ^ 8 Ω·cm is insufficient to meet the requirements; for example, hydrofluoroether HCF2CF2CF2CF2CH2OCF2CF2H has a -CF2H group in its structure, which easily removes HF under high heat conditions for a long time, thus producing acidity and failing to meet the requirements. At a low temperature of -60℃, its viscosity is too high, which also fails to meet the requirements. Summary of the Invention

[0004] In view of the problems of high viscosity, low volume resistivity and high pour point of coolants used in existing semiconductor manufacturing processes at low temperatures, this application provides an oxahydrofluoroether compound for use as a coolant, its preparation method, coolant composition and its application.

[0005] On one hand, this application provides an oxafluoroether compound for use as a coolant, said oxafluoroether compound being a compound of Formula 1:

[0006] R1 and R2 are both selected from perfluoroalkyl groups; R3 is selected from C n F 2n+1 ;

[0007] m is an integer from 0 to 4, and n is a positive integer.

[0008] Preferably, n is a positive integer from 1 to 6, R1 is selected from perfluoroalkyl groups having 1 to 4 carbon atoms, and R2 is selected from perfluoroalkyl groups having 1 to 4 carbon atoms.

[0009] Preferably, the oxafluoroether compound has a boiling point of 120–220°C, a pour point < -100°C, and a volume resistivity > 10. ^ 11Ω·cm;

[0010] The GWP100 of the oxahydrofluoroether compound is <100;

[0011] At -60°C, the kinematic viscosity of the oxafluoroether compound is <20 cSt.

[0012] Secondly, this application provides a method for preparing the above-mentioned oxafluoroether compound for coolant, comprising the following steps:

[0013] A fluorinated acyl fluoride compound is synthesized by adding potassium fluoride and a phase transfer catalyst to a fluorinated acyl fluoride compound and an alkylating agent under the action of potassium fluoride and the phase transfer catalyst.

[0014] The fluorine-containing acyl fluorine compounds include those shown in Formula 2.

[0015] R4 and R5 are both selected from perfluoroalkyl groups; R6 is selected from C6. n F 2n+1 ;

[0016] m is an integer from 0 to 4, and n is a positive integer.

[0017] Preferably, the synthesis of the oxahydrofluoroether compound by reacting a fluorine-containing acyl fluoride compound and an alkylating agent in the presence of potassium fluoride and a phase transfer catalyst includes the following steps:

[0018] A fluorine-containing acyl fluoride compound, potassium fluoride, a phase transfer catalyst, an alkylating agent, and a solvent are mixed evenly and reacted at 50–60°C for 20–30 h. After the reaction is completed, post-treatment is performed to obtain the oxahydrofluoride compound.

[0019] Preferably, the post-processing to obtain the oxafluoroether compound after the reaction includes the following steps:

[0020] After the synthesis reaction is completed, an alkaline solution is added, and the mixture is kept at 55-60°C for 40-60 minutes. After the heat treatment is completed, the mixture is separated into liquids. The lower liquid is then distilled to obtain the oxahydrofluoroether compound.

[0021] The solvent includes one or more of acetonitrile, dimethylformamide, N-methylpyrrolidone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, anhydrous diethylene glycol dimethyl ether, and isosorbide dimethyl ether.

[0022] Preferably, the molar ratio of the fluorinated acyl fluoride compound, potassium fluoride, alkylating agent, and phase transfer catalyst is (1.5–3):(1.5–3):(1.5–3):(0.005–0.015).

[0023] The alkylating agent includes alkyl sulfate;

[0024] The phase transfer catalyst includes one or more of tetrabutylammonium chloride, tetrabutylammonium fluoride, trioctylmethylammonium chloride, and tetradecyldimethylbenzylammonium chloride.

[0025] Thirdly, this application provides a coolant composition comprising the oxafluoroether compound for coolant described above or the oxafluoroether compound prepared by the method described above for preparing the oxafluoroether compound for coolant.

[0026] Preferably, the coolant composition further includes a fluorinated compound, which includes one or more of perfluoropolyethers, hydrofluoroether compounds, perfluoroalkylamines, perfluoroolefins, and hydrofluoroolefins;

[0027] In the coolant composition, the mass ratio of the oxafluoroether compound to the fluorinated compound is (70–99.9):(30–0.1);

[0028] The boiling point of the coolant composition is 120–220°C, and the GWP100 of the coolant composition is <100.

[0029] At -60°C, the kinematic viscosity of the coolant composition is <20 cSt.

[0030] Thirdly, this application provides an application of the above-described oxafluoroether compound for coolant or the above-described coolant composition in the semiconductor, data center, or medical fields.

[0031] The oxafluoroether compound provided in this application has the following characteristics: high boiling point, low pour point, high volume resistivity, low viscosity at -60°C, low GWP100 value, high chemical stability, good thermal stability, and high temperature control accuracy. When used as a coolant, the oxafluoroether compound provided in this application exhibits a wide temperature range and can be used over a broad temperature range, meeting the requirements of coolants in semiconductor manufacturing processes. Attached Figure Description

[0032] Figure 1 is a GC-MS image of the oxahydrofluoroether prepared in Example 2 of this application. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0034] To illustrate the technical solution of this application, specific embodiments are described below.

[0035] In a first aspect, this application provides an oxafluoroether compound for use as a coolant, said oxafluoroether compound being a compound of Formula 1:

[0036] R1 and R2 are both selected from perfluoroalkyl groups; R3 is selected from C n F 2n+1 ;

[0037] m is an integer from 0 to 4, and n is a positive integer.

[0038] Specifically, m can take the values ​​0, 1, 2, 3, or 4. R1 and R2 are both selected from perfluoroalkyl groups, and R3 is selected from C... n F 2n+1 It is also a perfluoroalkyl group.

[0039] Perfluoroalkyl compounds are alkyl groups in which all hydrogen atoms are replaced by fluorine atoms. Perfluoroalkyl compounds include perfluoro linear alkyl groups and perfluoro branched alkyl groups. Perfluoro linear alkyl groups are unbranched alkyl groups in which all hydrogen atoms are replaced by fluorine atoms, such as perfluoromethyl, perfluoroethyl, and perfluoropropyl. Perfluoro branched alkyl groups are branched alkyl groups in which all hydrogen atoms are replaced by fluorine atoms, such as perfluoroisobutyl.

[0040] The oxafluoroether compound provided in this application has the following characteristics: high boiling point, low pour point, high volume resistivity, low viscosity at -60°C, low GWP100 value, high chemical stability, good thermal stability, and high temperature control accuracy. When used as a coolant, the oxafluoroether compound provided in this application exhibits a wide temperature range and can be used over a broad temperature range, meeting the requirements of coolants in semiconductor manufacturing processes.

[0041] If m is greater than 4, the resulting compound may have a high pour point, a low boiling point, and a narrow temperature range. Using this compound as a coolant will result in low cooling efficiency, or high viscosity at -60℃, which will affect the flow rate of the coolant and reduce cooling efficiency.

[0042] In some preferred embodiments, n is a positive integer from 1 to 6, R1 is selected from perfluoroalkyl groups having 1 to 4 carbon atoms, and R2 is selected from perfluoroalkyl groups having 1 to 4 carbon atoms.

[0043] Specifically, n is a positive integer from 1 to 6, and the value of n can be 1, 2, 3, 4, 5 or 6; then the corresponding R3 is selected from perfluoroalkyl groups with 1 to 6 carbon atoms, such as perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluoroisobutyl, etc.

[0044] Specifically, n is in the range of 1 to 6, and the carbon atoms of R1 and R2 are selected from the above range. The compound shown in Formula 1 has the characteristics of lower viscosity, higher boiling point, lower pour point and higher volume resistivity at -60℃ temperature. It has the characteristics of high chemical stability, good thermal stability and high temperature control accuracy.

[0045] In some embodiments, the boiling point of the oxafluoroether compound is 120–220°C.

[0046] Specifically, the oxafluoroether compound provided in this application has a high boiling point. When used as a coolant composition in semiconductor manufacturing processes, it will not boil within the operating temperature range, ensuring thermal stability during the process and high temperature control accuracy. The high-boiling-point coolant has low volatility, reducing potential environmental impact.

[0047] In some embodiments, the pour point of the oxafluoroether compound is <-100°C.

[0048] Specifically, the pour point is the temperature at which a liquid loses its fluidity and begins to solidify at low temperatures. A low pour point means that the coolant can remain liquid and flow normally at lower temperatures. Low-pour-point oxafluoroether compounds, when used as coolant compositions in semiconductor manufacturing processes, can be used at lower temperature environments, maintaining the required heat exchange efficiency in semiconductor processes, thus helping to improve heat exchange efficiency and reduce energy consumption.

[0049] In some embodiments, the volume resistivity of the oxafluoroether compound is >10. ^ 11Ω·cm.

[0050] Specifically, the volume resistivity of oxafluoroether compounds is >10. ^ With a resistivity of 11 Ω·cm, it is suitable for semiconductor applications requiring high electrical insulation. The high volume resistivity also provides better chemical and thermal stability, which helps to improve the safety and reliability of equipment in semiconductor manufacturing processes.

[0051] In some embodiments, the GWP100 of the oxafluoroether compound is less than 100.

[0052] Specifically, GWP100 refers to how many times greater the potential impact of a compound on global warming is compared to carbon dioxide over a 100-year timeframe. For example, GWP100<100 means that over a 100-year timeframe, the potential impact of oxafluoroether compounds on global warming is less than 100 times that of carbon dioxide.

[0053] Oxafluoroethers have low GWP values, low potential impact on global warming, and meet stringent environmental requirements.

[0054] In some embodiments, the kinematic viscosity of the oxafluoroether compound is <20 cSt at -60°C.

[0055] Specifically, at -60℃, the kinematic viscosity of the oxafluoroether compound is <20cSt. The low viscosity allows the coolant to have better fluidity at low temperatures, improves heat exchange efficiency, has a more uniform cooling effect, and increases the cooling rate, making it very suitable for applications with high heat exchange requirements at low temperatures.

[0056] In some preferred embodiments, the kinematic viscosity of the oxafluoroether compound is <15 cSt at -60°C.

[0057] Secondly, this application provides a method for preparing the above-mentioned oxafluoroether compound for coolant, comprising the following steps:

[0058] A fluorinated acyl fluoride compound is synthesized by adding potassium fluoride and a phase transfer catalyst to a fluorinated acyl fluoride compound and an alkylating agent under the action of potassium fluoride and a phase transfer catalyst.

[0059] The fluorine-containing acyl fluorine compounds include those shown in Formula 2.

[0060] R4 and R5 are both selected from perfluoroalkyl groups; R6 is selected from C6. n F 2n+1 ;

[0061] m is an integer from 0 to 4, and n is a positive integer.

[0062] Specifically, the value of m can be 0, 1, 2, 3, or 4. R6 is selected from C. n F 2n+1 R6 is selected from perfluoroalkyl groups, and both R4 and R5 are selected from perfluoroalkyl groups. Perfluoroalkyl groups are alkyl groups in which all hydrogen atoms are replaced by fluorine atoms. Perfluoroalkyl groups include perfluoro linear alkyl groups or perfluoro branched alkyl groups. Perfluoro linear alkyl groups are alkyl groups without branches, where all hydrogen atoms are replaced by fluorine atoms. Examples of perfluoro linear alkyl groups include perfluoromethyl, perfluoroethyl, and perfluoropropyl. Perfluoro branched alkyl groups are alkyl groups containing branches, where all hydrogen atoms are replaced by fluorine atoms. Examples of perfluoro branched alkyl groups include perfluoroisobutyl.

[0063] The method for preparing oxafluoroether compounds for coolants provided in this application involves reacting a fluorine-containing acyl fluoride compound, an alkylating agent, and potassium fluoride in the presence of a phase transfer catalyst to synthesize the oxafluoroether compound. The preparation process is simple and low in cost.

[0064] In some preferred embodiments, in the compound shown in Formula 2, R4 is selected from perfluoroalkyl groups having 1 to 4 carbon atoms; R5 is selected from perfluoroalkyl groups having 1 to 4 carbon atoms; m is an integer from 1 to 4; and n is an integer from 1 to 6.

[0065] Specifically, perfluoroalkyl groups with 1 to 4 atoms include perfluoromethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl.

[0066] In some embodiments, the synthesis of the oxahydrofluoroether compound by reacting a fluorine-containing acyl fluoride compound and an alkylating agent in the presence of potassium fluoride and a phase transfer catalyst includes the following steps:

[0067] A fluorine-containing acyl fluoride compound, potassium fluoride, a phase transfer catalyst, an alkylating agent, and a solvent are mixed evenly and reacted at 50–60°C for 20–30 h. After the reaction is completed, post-treatment is performed to obtain the oxahydrofluoride compound.

[0068] Specifically, the synthesis reaction temperature is 50–60℃. A lower reaction temperature results in lower preparation costs. If the synthesis temperature is below 50℃, the reaction rate is too slow, making synthesis difficult. If the temperature is above 60℃, side reactions occur, generating more impurities and increasing preparation costs. The specific reaction temperature can be 50℃, 52℃, 54℃, 55℃, 57℃, 59℃, 60℃, etc., as long as the reaction temperature is within the 50–60℃ range.

[0069] In some embodiments, the post-processing to obtain the oxafluoroether compound after the reaction includes the following steps:

[0070] After the reaction is complete, an alkaline solution is added, and the mixture is kept at 55-60°C for 40-60 minutes. After the temperature is maintained, the mixture is separated into layers. The lower liquid is then distilled to obtain the oxafluoroether compound.

[0071] Specifically, after the reaction is complete, an alkaline solution is added, and the mixture is kept at 55–60°C for 40–60 minutes. This is mainly used to remove unreacted potassium fluoride, alkylating reagents, and byproducts generated from the reaction of potassium fluoride and alkylating reagents. After the incubation period, the mixture is separated. The liquid mixture containing the alkaline solution is in the upper layer, and the generated compound, oxafluoroether, is in the lower layer. The upper and lower liquids are separated, and the lower liquid is then distilled to obtain the oxafluoroether compound.

[0072] In some embodiments, the alkaline solution includes potassium hydroxide.

[0073] Potassium hydroxide is used as the alkali solution to prevent the introduction of new impurity ions.

[0074] In some embodiments, the solvent includes one or more of acetonitrile, dimethylformamide, N-methylpyrrolidone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, anhydrous diethylene glycol dimethyl ether, and isosorbide dimethyl ether.

[0075] In some embodiments, the solvent comprises tetraethylene glycol dimethyl ether and isosorbide dimethyl ether, wherein the molar ratio of the tetraethylene glycol dimethyl ether to the isosorbide dimethyl ether is (1-2):(1-2).

[0076] The solvent serves to dissolve the fluorinated acyl fluoride compounds and alkylating agents in the reactants.

[0077] In some embodiments, the molar ratio of the fluorinated acyl fluoride compound, potassium fluoride, alkylating agent, and phase transfer catalyst is (1.5–3):(1.5–3):(1.5–3):(0.005–0.015).

[0078] Specifically, before the synthesis reaction, if the amount of fluorine-containing acyl fluoride compound added is 1.5–3 mol, the amount of potassium fluoride added is 1.5–3 mol, the amount of alkylating agent added is 1.5–3 mol, and the amount of phase transfer catalyst added is 0.005–0.015 mol.

[0079] In some embodiments, the alkylating agent comprises alkyl sulfate.

[0080] In some preferred embodiments, the alkyl sulfate includes one or more of dimethyl sulfate, diethyl sulfate, dipropyl sulfate, and diisopropyl sulfate.

[0081] In some preferred embodiments, the alkylating agent includes dimethyl sulfate.

[0082] In some embodiments, the phase transfer catalyst preferably includes one or a mixture of tetrabutylammonium chloride, tetrabutylammonium fluoride, trioctylmethylammonium chloride, and tetradecyldimethylbenzylammonium chloride.

[0083] In some preferred embodiments, the phase transfer catalyst comprises tetrabutylammonium fluoride and tetrabutylammonium chloride, wherein the molar ratio of tetrabutylammonium fluoride to tetrabutylammonium chloride is (1-2):(1-2).

[0084] Specifically, the phase transfer catalyst uses tetrabutylammonium fluoride and tetrabutylammonium chloride in a molar ratio of (1-2):(1-2), which helps to transfer the reactant potassium fluoride from the aqueous phase to the organic phase in which the reaction can occur, thereby accelerating the reaction rate of the heterogeneous system and promoting the reaction to occur.

[0085] Thirdly, this application provides a coolant composition comprising the oxafluoroether compound for coolant described above or the oxafluoroether compound prepared by the method described above for preparing the oxafluoroether compound for coolant.

[0086] The coolant composition includes an oxafluoroether compound, resulting in a coolant composition with a high boiling point, low pour point, and wide temperature range, allowing for use over a broad temperature range. The coolant composition also exhibits high volume resistivity, making it suitable for semiconductor applications requiring high electrical insulation. Furthermore, the coolant composition has extremely low kinematic viscosity at -60°C, making it ideal for applications with high heat exchange requirements at low temperatures. The coolant composition also features high temperature control accuracy, a low GWP 100 value, meeting stringent environmental requirements, and good chemical and thermal stability, without affecting semiconductor fabrication and meeting the coolant requirements in semiconductor manufacturing processes.

[0087] In some embodiments, the coolant composition further includes a fluorinated compound, which includes one or more of perfluoropolyethers, hydrofluoroethers, perfluoroalkylamines, perfluoroolefins, and hydrofluoroolefins.

[0088] Specifically, fluorinated compounds are also commonly used coolants. Coolant compositions obtained by mixing fluorinated compounds with oxafluoroether compounds have the characteristics of high boiling point, low pour point, high volume resistivity, low viscosity, high temperature control accuracy, low GWP100 value, and good chemical stability, which meet the requirements for coolant use in semiconductor manufacturing processes.

[0089] Perfluoroalkylamines include perfluorotripropylamine, perfluorotributylamine, etc.

[0090] Perfluoroolefins include hexafluoropropylene dimer, hexafluoropropylene trimer, hexafluoropropylene tetramer, 1,3,3,4,4,5,5-heptafluoro-2-(perfluoroprop-2-yl)cyclopent-1-ene, 3,3,4,4,5,5-hexafluoro-1,2-bis(perfluoroprop-2-yl)cyclopent-1-ene, etc.

[0091] Hydrofluoroolefins include E-1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene, etc.

[0092] In some embodiments, hydrofluoroether compounds include NOVEC TM 7200, NOVEC TM 7500, Opteon TM At least one of SF10, HCF2CF2CF2CF2CH2OCF2CF2H.

[0093] Among them, NOVEC TM 7200 is methyl nonafluorobutyl ether (NOVEC) manufactured by 3M. TM 7500 is 2-(trifluoromethyl)-3-ethoxydodecylfluorohexane produced by 3M, Opteon. TM SF10 (Methoxytridecafluoroheptene isomers) was purchased from Chemours' fluorinated liquid tridecafluoroheptene methyl ether.

[0094] In some embodiments, the mass ratio of the oxafluoroether compound to the fluorinated compound in the coolant composition is (70–99.9):(30–0.1).

[0095] Specifically, in the coolant composition, the mass ratio of oxafluoroether compound to fluorine-containing compound is in the range of (70-99.9):(30-0.1). The content of oxafluoroether compound is relatively high, resulting in a coolant composition with a high boiling point, low pour point, high volume resistivity, low viscosity at -60°C, low GWP100 value, high chemical stability, and high temperature control accuracy.

[0096] Specifically, the mass ratio of the oxafluoroether compound to the fluorinated compound can be 70:30, 80:20, 90:10, 91:9, 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, 98:2, 99:1, or 99.9:0.1, as long as the mass ratio of the oxafluoroether compound to the fluorinated compound is within the range of (70 to 99.9): (30 to 0.1).

[0097] In some preferred embodiments, the mass ratio of the oxafluoroether compound to the fluorinated compound is (90–99.9):(0.1–10).

[0098] It contains a high content of oxafluoroether compounds, resulting in a coolant composition with a high boiling point, high stability, and high temperature control accuracy.

[0099] In some embodiments, the boiling point of the coolant composition is 120–220°C.

[0100] Specifically, the boiling point of the prepared coolant composition is in the range of 120 to 220°C. It has a high boiling point and can be applied to high temperatures above 120°C. It also has high temperature control accuracy and high thermal stability.

[0101] In some embodiments, the GWP100 of the coolant composition is less than 100.

[0102] The coolant composition has a low GWP100 value, a low potential impact on global warming, and meets stringent environmental requirements.

[0103] In some embodiments, the kinematic viscosity of the coolant composition is <20 cSt at -60°C.

[0104] Specifically, the kinematic viscosity of the coolant composition is <20 cSt. The low viscosity allows the coolant to have better fluidity at low temperatures, improves heat exchange efficiency, provides a more uniform cooling effect, and increases the cooling rate, making it very suitable for applications with high heat exchange requirements at low temperatures.

[0105] In some embodiments, the kinematic viscosity of the coolant composition is <15 cSt at -60°C.

[0106] Fourthly, this application provides an application of the above-described oxafluoroether compound for coolant or the above-described coolant composition in the semiconductor field, data center field, or medical field.

[0107] The coolant composition provided in this application is mainly used in the semiconductor, data center, or medical fields. The coolant has the characteristics of high boiling point, low pour point, high volume resistivity, low viscosity, high temperature control accuracy, low GWP100 value, and good chemical stability. When applied in the semiconductor field, it can be used to ensure the dissipation of a large amount of heat in high-density electronic equipment environments while maintaining precise temperature control. It can also perform constant temperature cooling to ensure stable operation.

[0108] In some embodiments, the application of the coolant composition in the semiconductor field includes the following steps: in the semiconductor front-end process, helium carries away the heat of the process, the heat-carrying helium exchanges heat with the coolant composition to achieve cooling, and the coolant composition after heat exchange is circulated for cooling; the operating temperature range of the coolant composition in the semiconductor front-end process is a minimum temperature ≤ -60°C and a maximum temperature ≥ 90°C.

[0109] In some embodiments, the application of the coolant composition in the semiconductor field includes the following steps: in semiconductor back-end processes, for chip reliability testing, and for high and low temperature cycling of the coolant composition; in semiconductor front-end processes, the operating temperature range of the coolant composition is a minimum temperature ≤ -60°C and a maximum temperature ≥ 120°C.

[0110] The present application will be further illustrated by the following examples.

[0111] Example 1

[0112] Preparation of CF3OCF(CF3)CF2OCF(CF3)CF2OCH3:

[0113] 1) Raw material: Fluorine-containing acyl fluorine compound with the structural formula: CF3OCF(CF3)CF2OCF(CF3)COF

[0114] 2.2 mol of a fluorinated acyl fluoride compound, 2.5 mol of tetraethylene glycol dimethyl ether, 2.8 mol of potassium fluoride, 0.009 mol of tetrabutylammonium chloride (a phase transfer catalyst), and 2.5 mol of dimethyl sulfate were added to a 2 L autoclave. The mixture was stirred at 400 rpm while the temperature was raised to 55 °C and maintained at 55 °C for 27 hours to carry out the synthesis reaction. After 27 hours of synthesis, 300 g of a 45% potassium hydroxide aqueous solution was added, and the temperature was raised to 60 °C and maintained at 60 °C for 50 minutes. The mixture was then separated using a separatory funnel, and the lower layer was distilled to obtain the target product. The obtained target product was distilled to obtain CF3OCF(CF3)CF2OCF(CF3)CF2OCH3 with a purity of 99.8% and a yield of 96.8%.

[0115] Example 2

[0116] This embodiment is largely the same as Example 1, except that the fluorine-containing acyl fluoride compound has the structural formula CF3CF2OCF(CF3)CF2OCF(CF3)COF, and the synthesis reaction temperature is different, as detailed below. In Example 2, the temperature was raised to 50°C while stirring at 400 rpm, and maintained at 50°C for 30 hours for the synthesis reaction. After 30 hours, 300g of a 45% potassium hydroxide aqueous solution was added, and the temperature was raised to 55°C and maintained at 55°C for 50 minutes. Then, the mixture was separated using a separatory funnel, and the lower layer was distilled to obtain the target product. The target product obtained after distillation was CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH3, with a purity of 99.8% and a yield of 96.2%.

[0117] Example 3

[0118] This embodiment is the same as Example 1 in most steps, except that the fluorine-containing acyl fluoride compound has the structural formula CF3CF2CF2CF2CF2CF2OCF(CF3)COF, and the target product obtained after distillation is CF3CF2CF2CF2CF2CF2OCF(CF3)CF2OCH3. The purity of the product is 99.8% and the yield is 96.8%.

[0119] Example 4

[0120] This embodiment is largely the same as Example 1, except that the fluorine-containing acyl fluoride compound has the structural formula: CF3CF2CF2CF2CF2CF2O(CF(CF2CF2CF2CF3)CF2O)4CF(CF3)COF, and the synthesis reaction temperature is different, as detailed below. In Example 3, the temperature was raised to 60°C while stirring at 400 rpm, and maintained at 60°C for 30 hours for the synthesis reaction. After 30 hours, 300g of a 45% potassium hydroxide aqueous solution was added, and the temperature was raised to 57°C. This temperature was maintained for 60 minutes, and then the mixture was separated using a separatory funnel. The lower layer was then distilled to obtain the target product. The target product obtained after distillation was CF3CF2CF2CF2CF2CF2O(CF(CF2CF2CF2CF2CF3)CF2O)4CF(CF3)CF2OCH3, with a purity of 98.2% and a yield of 90.1%.

[0121] Example 5

[0122] This embodiment is the same as Example 1 in most steps, except that the fluorine-containing acyl fluorine compound has the structural formula CF3O(CF(CF3)CF2O)2CF(CF3)COF, and the target product obtained after distillation is CF3O(CF(CF3)CF2O)2CF(CF3)CF2OCH3. The purity of the product is 99.4% and the yield is 95.7%.

[0123] Example 6

[0124] This embodiment is the same as Example 1 in most steps, except that the fluorine-containing acyl fluorine compound has the structural formula CF3O(CF(CF3)CF2O)3CF(CF3)COF, and the target product obtained after distillation is CF3O(CF(CF3)CF2O)3CF(CF3)CF2OCH3. The purity of the product is 99.1% and the yield is 94.9%.

[0125] Comparative Examples 1-5

[0126] Comparative Examples 1-5 used commercially available coolant products. The specific types of coolant used are as follows: Comparative Example 1 used perfluorotripropylamine, Comparative Example 2 used perfluoropolyether, and Comparative Example 3 used NOVEC. TM 7500, Comparative Example 4 is Opteon TM SF10, Comparative Example 5 is HCF2CF2CF2CF2CH2OCF2CF2H.

[0127] Performance testing

[0128] 1) Physical property testing of oxafluoroether compounds

[0129] The oxafluoroether compounds prepared in the above embodiments and the coolants of the comparative examples were tested for boiling point, pour point, kinematic viscosity at -60°C, volume resistivity, and GWP. The test results are recorded in Table 1.

[0130] 2) Physical property testing of the coolant composition

[0131] Proportioning: The mass content of the oxahydrofluoroether compound in the cooling composition is 95%, and the mass content of the fluorine-containing compound is 5%.

[0132] The oxahydrofluoric ether compounds and the fluorine-containing compound NOVEC prepared in Examples 1-3 were used. TM The cooling compositions formed by the combination of 7500 are respectively designated as coolant composition 1, coolant composition 2, and coolant composition 3. The boiling point, pour point, kinematic viscosity at -60℃, volume resistivity, and GWP of these cooling compositions were tested and compared with those of Comparative Examples 1-5. The test results are recorded in Table 2.

[0133] 3) Proportioning: The mass content of the oxahydrofluoroether compound in the cooling composition is 95%, and the mass content of the fluorine-containing compound is 5%.

[0134] The oxahydrofluoroether compounds prepared in Examples 1-3, the oxahydrofluoroether compounds prepared in Examples 1-3 (95% by mass), and the fluorine-containing compound NOVEC were compared. TM The cooling composition formed by combining 7500 (5% by mass) and the commercially available coolant products (Comparative Examples 1-5) were placed in a semiconductor temperature control device (Chiller, brand: SMC, model: HRZ010-WS-F) to test the time required for them to change from -20℃ to 90℃ and then back to -20℃ under no-load (no heat source) conditions. The test results are shown in Table 3.

[0135] The flow rate used above was set to 20L / min at 60Hz, and the heat source power was 0KW.

[0136] The oxahydrofluoroether compound (95% by mass) and the fluorinated compound NOVEC prepared in Examples 1-3 TM The cooling compositions formed by combining 7500 (5% by mass) are respectively recorded as coolant composition 1, coolant composition 2, and coolant composition 3.

[0137] 4) The oxafluoroether compounds prepared in Examples 1-3, the oxafluoroether compounds prepared in Examples 1-3 (95% by mass), and the fluorine-containing compound NOVEC TM The cooling composition formed by combining 7500 (5% by mass) and 500g each of commercially available coolant products (Comparative Examples 1-5) were heated under reflux at 100°C for 1000h. The changes in fluoride ion concentration before and after the experiment were tested for each coolant product. The test results are shown in Table 4.

[0138] The oxahydrofluoroether compound (95% by mass) and the fluorinated compound NOVEC prepared in Examples 1-3 TM The cooling compositions formed by combining 7500 (5% by mass) are respectively recorded as composition 1, composition 2, and composition 3.

[0139] 5) The oxahydrofluoroether compound (95% by mass) and the fluorinated compound NOVEC prepared in Example 1 TM The cooling composition formed by combining 7500 (5% by mass) was placed in a sealed container with samples of different materials, and then immersed in a 90℃ constant temperature oven for 12000h. The mass and volume changes of the samples before and after the experiment were tested, and the test results are shown in Table 5.

[0140] The boiling point was tested according to GB / T616, the pour point according to ASTM D97, the viscosity according to ASTM D7042, the volume resistivity according to GB / T5654, and the GWP100 was tested according to the Climate Change 2013-IPCC (Year 100) regulations.

[0141] Table 1

[0142] Figure 1 shows the GC-MS image of the oxafluoroether prepared in Example 2. Comparing Examples 1-6 and Comparative Examples 1-5, the compounds prepared in Examples 1-3 conform to the oxafluoroether compound shown in Formula 1, with a boiling point of 120℃ to 220℃ and a pour point less than -100℃. This high boiling point and low pour point provide an extremely wide temperature range (the difference between the boiling point and the pour point), enabling use over a wide temperature range. For boiling points above 120℃, it is particularly suitable for high-temperature temperature control applications. The oxafluoroether compounds prepared in Examples 1-3 have a viscosity of less than 20 cSt at -60℃, exhibiting extremely low viscosity, making them ideal for applications with high heat exchange requirements at low temperatures, thus improving cooling efficiency. The volume resistivity of the oxafluoroether compounds prepared in Examples 1-6 is all >10. ^ With a resistivity of 11 Ω·cm, it is suitable for semiconductor applications requiring high electrical insulation. The product's GWP100 is less than 100, meeting stringent environmental requirements. A comparison of Examples 1-6 shows that when m is in the range of 0–1 and n is in the range of 1–3, the prepared oxafluoroether compounds exhibit high boiling points, lower pour points, and a wider temperature range. They also possess high volume resistivity, low viscosity at -60°C, and low GWP100 values, resulting in higher chemical stability, better thermal stability, and better temperature control as a coolant.

[0143] Table 2

[0144] As shown in Table 2, comparing Comparative Examples 1-5 and Coolant Combinations 1-3, Coolant Combinations 1-3 have boiling points in the range of 120–220℃ and pour points < -100℃. The high boiling point and low pour point of these compositions demonstrate a very wide temperature range (the difference between boiling point and pour point), proving their applicability to a wider range of operating conditions. Coolant Combinations 1-3 all have boiling points above 120℃, making them particularly suitable for high-temperature temperature control applications. At -60℃, their kinematic viscosity is <20 cSt, indicating extremely low viscosity, making them ideal for applications with high heat exchange requirements at low temperatures. The volume resistivity of Coolant Combinations 1-3 is >10⁻⁶. ^With a strength of 11 Ω·cm, it is suitable for semiconductor applications requiring high electrical insulation; the GWP100 of coolant compositions 1-3 is all <100, meeting stringent environmental requirements.

[0145] Table 3

[0146] As shown in Table 3, compared with Comparative Examples 1-2, 5 and Examples 1-3, the oxafluoroether prepared in Examples 1-3 and the coolant composition formed by the combination of oxafluoroether and fluorinated compounds prepared in Examples 1-3 have a kinematic viscosity of less than 20 cSt at -60°C. Due to its ultra-low viscosity, it can reach the specified temperature faster under the same flow rate and initial temperature in the same equipment, indicating better heat exchange capacity. In actual semiconductor manufacturing processes, it can achieve more precise temperature control. Similarly, it can achieve more precise temperature control when used as a refrigerant in medical fields. Although Comparative Examples 3 and 4 require shorter times, Comparative Example 3 has a low volume resistivity, making it unsuitable for applications requiring high electrical insulation, and its high GWP value does not meet environmental requirements. Comparative Example 4 has a high pour point and a small temperature range, making it unsuitable for use under conditions with a wide temperature range.

[0147] Table 4

[0148] As shown in Table 4, compared with Comparative Examples 4-5 and Examples 1-3, the oxafluoroether prepared in Examples 1-3, and the coolant compositions prepared in Examples 1-3 and those containing fluorine compounds, all exhibit good thermal stability. After heating at 100°C for 1000 hours, the fluoride ion concentration remained essentially unchanged. Although Comparative Examples 1-3 showed good thermal stability, Comparative Example 3 had a low volume resistivity, making it unsuitable for applications requiring high electrical insulation. Comparative Examples 1-2 had high GWP values, failing to meet environmental protection requirements.

[0149] Table 5

[0150] As can be seen from Table 5, the cooling combination formed by the combination of oxafluoroether compound and fluorine-containing compound provided in this application has a volume change rate of <±5% and a mass change rate of <±5% after immersing the cooling composition and various materials at 90℃ for 12000h. This indicates that the cooling combination formed by the combination of oxafluoroether compound and fluorine-containing compound provided in this application has good compatibility with various components, good chemical stability, and can meet the usage requirements.

[0151] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit it. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application, and should all be included within the protection scope of this application.

Claims

1. An oxazolium hydrofluoroether compound for a coolant, characterized by, The oxazaborolidine compound is a compound represented by formula 1: wherein R1and R2are each selected from perfluoroalkyl groups; R3is selected from C n F 2n+1 ; m is an integer from 0 to 4, and n is a positive integer.

2. The oxazolide compound for coolant according to claim 1, characterized by, n is a positive integer from 1 to 6, and R1 is selected from perfluoroalkyl groups having 1 to 4 carbon atoms, and R2 is selected from perfluoroalkyl groups having 1 to 4 carbon atoms.

3. The oxazolide compound for coolant according to claim 1, characterized by, The boiling point of the oxazohydrofluoroether compound is 120-220°C, the pour point is <-100°C, and the volume resistivity is >10 ^ 11 ohm-cm; The GWP100 of the oxazohydrofluoroether compound is less than 100. The kinematic viscosity of the oxazohydrofluoroether compound at -60℃ is less than 20 cSt.

4. A process for the preparation of oxazohydrofluoroether compounds for coolants according to claim 1, characterized in that, The method comprises the following steps: The fluorine-containing acyl fluoride compound and the alkylating agent are added with potassium fluoride and a phase transfer catalyst, and the fluorine-containing acyl fluoride compound and the alkylating agent are reacted under the action of potassium fluoride and the phase transfer catalyst to synthesize the oxazohydrofluoroether compound, The fluorine-containing acyl fluoride compound includes a compound represented by Formula 2, wherein R4and R5are each selected from perfluoroalkyl; R6is selected from C n F 2n+1 ; m is an integer from 0 to 4, and n is a positive integer.

5. The method for preparing the oxafluoroether compound according to claim 4, characterized in that, The fluorine-containing acyl fluoride compound and the alkylating agent are reacted under the action of potassium fluoride and the phase transfer catalyst to synthesize the oxazohydrofluoroether compound, which comprises the following steps: The fluorine-containing acyl fluoride compound, potassium fluoride, the phase transfer catalyst, the alkylating agent and the solvent are uniformly mixed, and the reaction is carried out at a temperature of 50-60℃ for 20-30 hours, and after the reaction is completed, the oxazohydrofluoroether compound is obtained after post-treatment.

6. The method for preparing the oxafluoroether compound according to claim 5, characterized in that, The method for obtaining the oxazohydrofluoroether compound after the reaction is completed comprises the following steps: After the reaction is completed, the alkali solution is added, and the temperature is kept at 55-60℃ for 40-60 minutes, then the liquid is separated, and the lower liquid is rectified to obtain the oxazohydrofluoroether compound; The solvent comprises one or more of acetonitrile, dimethylformamide, N-methylpyrrolidone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, anhydrous diethylene glycol dimethyl ether and isosorbide dimethyl ether.

7. The method for preparing the oxafluoroether compound according to claim 4, characterized in that, The molar ratio of the fluorine-containing acyl fluoride compound, potassium fluoride, the alkylating agent and the phase transfer catalyst is (1.5-3):(1.5-3):(1.5-3):(0.005-0.015). The alkylating agent comprises an alkyl sulfate. The phase transfer catalyst comprises one or more of tetrabutylammonium chloride, tetrabutylammonium fluoride, trioctylmethylammonium chloride and tetradecyldimethylbenzylammonium chloride.

8. A coolant composition characterized in that, The oxazohydrofluoroether compound for a coolant as claimed in claim 1.

9. A coolant composition characterized in that, The oxazohydrofluoroether compound prepared by the method as claimed in claim 4.

10. The coolant composition of claim 8, wherein The coolant composition further comprises a fluorine-containing compound, and the fluorine-containing compound comprises one or more of a perfluoropolyether, a hydrofluoroether compound, a perfluoroalkylamine, a perfluoroalkene and a hydrofluoroalkene. In the coolant composition, the mass ratio of the oxazohydrofluoroether compound to the fluorine-containing compound is (70-99.9):(30-0.1). The boiling point of the coolant composition is 120-220℃, and the GWP100 of the coolant composition is less than 100, The kinematic viscosity of the coolant composition at -60℃ is less than 20 cSt.

11. The oxazohydrofluoroether compound for a coolant as claimed in claim 1.

12. The use of the coolant composition as claimed in claim 8 in the field of semiconductors, data centers or medical treatment.

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