Oxa-hydrofluoroether compound as well as synthesis method and application thereof

Abstract

The invention belongs to the technical field of fluorine-containing fine chemical synthesis, and particularly relates to an oxa-hydrofluoroether compound and a synthesis method and application thereof. The invention relates to an oxa-hydrofluoroether compound, the structure of the oxa-hydrofluoroether compound is shown as a formula (1): # imgabs0 #, in which Rf is F or CF3; r is methyl or ethyl; n is an integer from 1 to 3; according to the oxa hydrofluoroether compound disclosed by the invention, oxygen atoms are embedded into a fluorocarbon chain structure, so that fluorine-containing chain segments of hydrofluoroether are more diversified, and the structure is not limited by a perfluorocarbon chain structure any more; according to the oxa-hydrofluoroether compound, oxygen atoms play a role in reducing surface tension, and the more the oxygen atoms are, the lower the surface tension is; compared with other hydrofluoroether solvents, the hydrofluoroether solvent has higher permeability and better cleaning effect; according to the oxa-hydrofluoroether compound, on one hand, oxygen atoms are embedded into a fluorocarbon chain structure, and on the other hand, the fluorocarbon chain contains branched chains, so that the oxa-hydrofluoroether compound is easy to degrade, and the environmental friendliness is improved.

Description

Technical Field

[0001] This application belongs to the technical field of the synthesis of fluorine-containing fine chemicals, and particularly relates to an oxa-hydrofluoroether compound, a synthesis method thereof, and an application thereof. Background Art

[0002] With the rapid development of information technologies such as artificial intelligence, cloud computing, big data, and blockchain, the requirements for the processing performance and integration of data center servers and communication devices are getting higher and higher, leading to a continuous increase in power density. In recent years, the demand for environmentally friendly electronic cleaning agents and fluorinated electronic coolants in this field has shown a high growth trend.

[0003] Hydrofluoroethers are a class of ether compounds containing fluorine, carbon, hydrogen, and oxygen, belonging to partially fluorinated ethers. They are a new generation of substitutes for ozone-depleting substances and have a series of excellent properties such as low viscosity, low freezing point, low surface tension, and good electrochemical stability. Different from chlorofluorocarbons, hydrofluoroether compounds do not contain other halogens except fluorine and basically do not affect the earth's ozone layer. Therefore, the ozone depletion potential value of hydrofluoroether compounds is zero; in addition, hydrofluoroether compounds are more easily degraded in the earth's atmosphere and have a lower global warming potential value (GWP), making them ideal substitutes for chlorofluorocarbon compounds. Hydrofluoroethers have unparalleled advantages over other substitutes for ozone-depleting substances in the fields of the electronics industry, cleaning agents for precision instruments, lubricant diluents, polymerization solvents, leak detection liquids, heat conduction media, electronic coolants, medical anesthetics, etc.

[0004] Therefore, developing new and environmentally friendly hydrofluoroether compounds has become an urgent problem to be solved. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, this application provides an oxa-hydrofluoroether compound, a synthesis method thereof, and an application thereof.

[0006] The disclosed oxa-type hydrofluoroether compound of this application only contains the halogen element fluorine and does not contain ozone-depleting substances, belonging to an environmentally friendly compound and being friendly to the environment.

[0007] In the first aspect, this application provides an oxa-hydrofluoroether compound, adopting the following technical solution: An oxa-hydrofluoroether compound, the structure of the oxa-hydrofluoroether compound is shown in formula (1): Wherein, R f is F or CF3; R is methyl or ethyl; n is an integer from 1 to 3.

[0008] Preferably, the oxa-hydrofluoroether compound is any one of the following: CF3OCF(CF3)CF2OCH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3OCF(CF3)CF2OCH2CH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCH2CH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3; CF3CF2OCF(CF3)CF2OCH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3CF2OCF(CF3)CF2OCH2CH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3.

[0009] Further preferably, the oxa-hydrofluorocarbon ether compound is any one of the following: CF3OCF(CF3)CF2OCH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3CF2OCF(CF3)CF2OCH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3OCF(CF3)CF2OCH2CH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCH2CH3; CF3CF2OCF(CF3)CF2OCH2CH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3.

[0010] More preferably, the oxa-hydrofluorocarbon ether compound is selected from the following substances: CF3OCF(CF3)CF2OCH3 or CF3CF2OCF(CF3)CF2OCH2CH3.

[0011] Second aspect, the present application provides a method for synthesizing an oxa-hydrofluorocarbon ether compound, adopting the following technical solution: A method for synthesizing an oxa-hydrofluorocarbon ether compound, the steps of the synthesis method are as follows: reacting an acyl fluoride compound, an alkylating agent and an alkali metal fluoride in a polar aprotic solvent to obtain an oxa-hydrofluorocarbon ether compound.

[0012] Preferably, the structure of the acyl fluoride compound is shown in formula (2): Wherein, R f is F or CF3; m is an integer from 1 to 3.

[0013] Preferably, the acyl fluoride compound is one or more of the following: CF3OCF(CF3)COF; CF3OCF(CF3)CF2OCF(CF3)COF; CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF; CF3CF2OCF(CF3)COF; CF3CF2OCF(CF3)CF2OCF(CF3)COF; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF.

[0014] More preferably, the acyl fluoride compound is selected from the following substances: CF3OCF(CF3)COF or CF3CF2OCF(CF3)COF.

[0015] Preferably, the alkylating agent is at least one of dialkyl sulfates, dialkyl carbonates, and halogenated hydrocarbons.

[0016] More preferably, the alkylating agent is a dialkyl sulfate.

[0017] More preferably, the dialkyl sulfate is dimethyl sulfate or diethyl sulfate.

[0018] Preferably, the alkali metal fluoride is at least one of potassium fluoride, sodium fluoride, cesium fluoride, and rubidium fluoride.

[0019] Preferably, the polar aprotic solvent is at least one of ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, acetonitrile, N,N-dimethylformamide, N,N-diethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide.

[0020] Preferably, the molar ratio of the acyl fluoride compound to the alkylating agent is 1:(1 - 1.5); More preferably, the molar ratio of the acyl fluoride compound to the alkylating agent is 1:(1 - 1.2).

[0021] Preferably, the molar ratio of the alkali metal fluoride to the acyl fluoride compound is 1:(2 - 10); More preferably, the molar ratio of the alkali metal fluoride to the acyl fluoride compound is 1:(4 - 8).

[0022] Preferably, the mass ratio of the acyl fluoride compound to the polar aprotic solvent is 1:(0.8 - 2).

[0023] More preferably, the mass ratio of the acyl fluoride compound to the polar aprotic solvent is 1:(0.8 - 1.8).

[0024] Preferably, a method for synthesizing an oxa-hydrofluorocarbon ether compound, the synthesis method comprises the following steps: (1) Under nitrogen protection, mix the alkali metal fluoride with the polar aprotic solvent; (2) After cooling, under nitrogen protection, add the acyl fluoride compound and mix; (3) Dropwise add the alkylating agent to the mixture obtained in step (2), and after the addition is complete, raise the temperature to carry out the reaction; (4) After cooling, add an alkali solution and mix, let stand, and distill to obtain an oxa-hydrofluorocarbon ether compound with a purity ≥ 99.5%.

[0025] Preferably, the temperature after cooling in step (2) is 0 - 20 °C.

[0026] Preferably, before cooling in step (2), adjust the reaction pressure to 0.01 - 1.0 MPa.

[0027] Preferably, the temperature after raising the temperature in step (3) is 30 - 120 °C, and the reaction time is 2 - 24 h.

[0028] Preferably, the temperature after cooling in step (4) is 20 - 30 °C.

[0029] Preferably, the alkali solution in step (4) is at least one of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution or potassium carbonate solution; the mass concentration of the alkali solution is 5 - 50%.

[0030] More preferably, the alkali solution is sodium hydroxide solution, and the mass concentration of the alkali solution is 10 - 20%.

[0031] In a specific feasible embodiment, the synthesis method of the oxa-hydrofluorocarbon ether compound is specifically operated as follows: S-1: Under nitrogen protection, add anhydrous alkali metal fluoride into a stainless-steel high-pressure reactor; S-2: After evacuating and replacing the reactor, continue to add a dried polar aprotic solvent; adjust the reaction pressure of the reactor to 0.01 - 1.0 MPa, while stirring to make the materials mix evenly, and while cooling the reactor; S-3: When the reactor temperature drops to 0 - 20 °C, under nitrogen protection, add the acyl fluoride compound into the mixture obtained in S-2 for mixing; S-4: Then, through a dropping funnel, add the alkylating agent dropwise into the mixture obtained in S-3 within 0.5 h; S-5: Then raise the temperature to 30 - 120 °C, continue the reaction for 2 - 24 h, and then end the reaction; S-6: When the reactor temperature drops to 20 - 30 °C, transfer the mixture obtained in S-5 to a flask, add an alkali solution, continue to stir for a period of time, and let it stand for liquid separation; S-7: Take the lower fluorine phase for distillation to obtain an oxa-hydrofluorocarbon ether compound with a purity ≥ 99.5%.

[0032] In the third aspect, the present application provides an application of an oxa-hydrofluorocarbon ether compound in the preparation of an electronic cleaning agent, an electronic fluorinated liquid or a solvent, adopting the following technical solution: The above oxa-hydrofluorocarbon ether compound or the oxa-hydrofluorocarbon ether compound prepared by the above method is applied in the preparation of an electronic cleaning agent, an electronic fluorinated liquid or a solvent.

[0033] The series of oxa-hydrofluorocarbon ether compounds provided by the present application can be applied to different fields: used as an electronic cleaning agent in fields such as semiconductor, liquid crystal, and hard disk manufacturing; used as an electronic fluorinated liquid for cooling in various links of semiconductor production and manufacturing (such as cooling of cooling machines, cooling temperature control of upper and lower electrodes in dry etching, exposure machines for chip pattern preparation, high and low temperature cooling control of chip testing systems, chip sorting equipment, etc.), cooling and heat dissipation of military radar systems, and heat dissipation systems of internal heat-generating components of wind turbines; used as a solvent in fields such as electronic coatings and screen layer diluents.

[0034] In summary, the present application includes at least one of the following beneficial technical effects: 1. For the oxa-hydrofluorocarbon ether compound disclosed in the present application, since an oxygen atom is embedded in the fluorocarbon chain structure, the fluorine-containing chain segment of the hydrofluorocarbon ether is more diversified, and the structure is no longer limited to the perfluorocarbon chain structure; 2. For the oxa-hydrofluorocarbon ether compound disclosed in the present application, the oxygen atom plays a role in reducing the surface tension, and the more oxygen atoms there are, the lower the surface tension; compared with other hydrofluorocarbon ether solvents, it has stronger permeability and better cleaning effect; 3. The oxa-hydrofluorocarbon ether compounds disclosed in the present application. On the one hand, due to the embedding of oxygen atoms in the fluorocarbon chain structure, and on the other hand, the fluorocarbon chain contains branched chains, it is easy to degrade, thus enhancing environmental friendliness. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is the GC-MS spectrum of CF3CF2OCF(CF3)CF2OCH3 prepared in Example 2. SPECIFIC EMBODIMENTS

[0036] In the following examples of the present application, the experimental methods without specific conditions are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer; the experimental materials and reagents involved in the following content are commercially available products unless otherwise specified.

[0037] Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as commonly understood by those skilled in the technical field to which the present application belongs. The terms used in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0038] The terms "comprising" and "having" and any variations thereof in the present application are intended to cover non-exclusive inclusion. For example, a process, method, device, product or equipment that includes a series of steps is not limited to the listed steps or modules, but optionally further includes steps not listed, or optionally further includes other steps inherent to these processes, methods, products or equipment.

[0039] The technical solutions of the present application will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present application without creative efforts shall fall within the protection scope of the present application.

[0040] Source of raw materials: 1. Preparation of acyl fluoride compounds CF3OCF(CF3)COF, CF3OCF(CF3)CF2OCF(CF3)COF and CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF: First, 20.4 g of the catalyst tetramethylethylenediamine and 498.5 g of the aprotic polar solvent triglyme were successively sucked into a clean and dry 2 L airtight stainless-steel high-pressure reactor. Then, while stirring at a speed of 200 revolutions per minute, the reactor was cooled. When the temperature of the reactor dropped to -15 °C, carbonyl fluoride (50 g) was introduced into the reactor. After the addition, stirring was continued for 10 min. Then, hexafluoropropylene oxide (132.4 g) was introduced into the reactor at a rate of 0.1 g / min. After the addition, stirring was continued for 1 h to end the reaction. The reaction solution was transferred to a separatory funnel and allowed to stand for layering. The upper layer was the organic phase and the lower layer was the fluorine phase. Samples were taken for chromatographic analysis. The fluorine phase was a mixture containing CF3OCF(CF3)COF, CF3OCF(CF3)CF2OCF(CF3)COF, CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF, with contents of 57.3%, 36.8%, and 3.91% respectively; The fluorine phase was rectified to obtain 89.3 g of CF3OCF(CF3)COF, 57.4 g of CF3OCF(CF3)CF2OCF(CF3)COF, and 6.0 g of CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF, with a purity of ≥99%.

[0041] 2. Preparation of acyl fluoride compounds CF3CF2OCF(CF3)COF, CF3CF2OCF(CF3)CF2OCF(CF3)COF, and CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF: First, 20.4 g of the catalyst tetramethylethylenediamine and 498.5 g of the aprotic polar solvent triglyme were successively sucked into a clean and dry 2 L airtight stainless-steel high-pressure reactor. Then, while stirring at a speed of 200 revolutions per minute, the reactor was cooled. When the temperature of the reactor dropped to -15 °C, trifluoroacetyl fluoride (125.8 g) was introduced into the reactor. After the addition, stirring was continued for 10 min. Then, hexafluoropropylene oxide (132.4 g) was introduced into the reactor at a rate of 0.2 g / min. After the addition, stirring was continued for 1 h to end the reaction. The reaction solution was transferred to a separatory funnel and allowed to stand for layering. The upper layer was the organic phase and the lower layer was the fluorine phase. Samples were taken for chromatographic analysis. The fluorine phase was a mixture containing CF3CF2OCF(CF3)COF, CF3CF2OCF(CF3)CF2OCF(CF3)COF, and CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF, with contents of 30.2%, 52.6%, and 15.1% respectively; The fluorinated phase was subjected to rectification to obtain CF3CF2OCF(CF3)COF (66.3 g), CF3CF2OCF(CF3)CF2OCF(CF3)COF (115.4 g), and CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF (33.1 g) respectively, with a purity of ≥99%.

[0042] Example 1: Preparation of CF3OCF(CF3)CF2OCH3: In a 2 L jacketed stainless steel high-pressure reactor equipped with a stirrer, a pressure gauge, and a feeding funnel, under nitrogen protection, potassium fluoride (25.00 g, 0.43 mol) was added, and then the reactor was sealed. Subsequently, the reactor was evacuated and replaced three times. Under nitrogen protection, dried diethylene glycol dimethyl ether (800 g) was added, and the pressure of the reactor was released to 0.01 MPa. While stirring at a speed of 300 revolutions per minute, the temperature was lowered to 0 °C. Under nitrogen protection, CF3OCF(CF3)COF (500 g, 2.16 mol) was continuously added to the above mixture. Then, dimethyl sulfate (325.42 g, 2.58 mol) was started to be added dropwise and completed within 0.5 h. The temperature of the reactor was raised to 60 °C, and the mixture was continuously stirred for 8 h to end the reaction. After the temperature of the reactor was lowered to room temperature (25 °C), the reaction solution was transferred to a flask, a 10% sodium hydroxide aqueous solution by mass (340 g) was added and stirred for 10 minutes, the stirring was turned off and left standing for 0.5 h, and the lower fluorinated phase was released for distillation to obtain the target product CF3OCF(CF3)CF2OCH3.

[0043] Example 2: Preparation of CF3CF2OCF(CF3)CF2OCH3: In a 2L jacketed stainless steel high-pressure reactor equipped with a stirrer, a pressure gauge, and a feeding funnel, under nitrogen protection, potassium fluoride (29.05 g, 0.50 mol) was added, and then the reactor was sealed. Subsequently, the reactor was evacuated and replaced three times. Under nitrogen protection, dried tetraethylene glycol dimethyl ether (900 g) was added, and the pressure of the reactor was released to 0.01 MPa. While stirring at a speed of 300 revolutions per minute, the temperature was lowered to 10 °C. Under nitrogen protection, CF3CF2OCF(CF3)COF (557.84 g, 2.12 mol) was continuously added to the above mixture. Then, dimethyl sulfate (315.33 g, 2.5 mol) was started to be dropped, and the dropping was completed within 0.5 h. The temperature of the reactor was raised to 90 °C, and the mixture was continuously stirred for 8 h to end the reaction. After the temperature of the reactor was lowered to room temperature of 25 °C, the reaction solution was transferred to a flask, 10% sodium hydroxide aqueous solution by mass (320 g) was added and stirred for 10 minutes, the stirring was stopped and left standing for 0.5 h, and the lower fluorine phase was released for distillation to obtain the target product CF3CF2OCF(CF3)CF2OCH3. The product structure was confirmed by GC-MS, as shown in Figure 1 .

[0044] Example 3: Preparation of CF3OCF(CF3)CF2OCF(CF3)CF2OCH3: In a 2L jacketed stainless steel high-pressure reactor equipped with a stirrer, a pressure gauge, and a feeding funnel, under nitrogen protection, cesium fluoride (65.32 g, 0.43 mol) was added, and then the reactor was sealed. Subsequently, the reactor was evacuated and replaced three times. Under nitrogen protection, dried diethylene glycol dimethyl ether (800 g) was added, and the pressure of the reactor was released to 0.01 MPa. While stirring at a speed of 300 revolutions per minute, the temperature was lowered to 20 °C. Under nitrogen protection, CF3OCF(CF3)CF2OCF(CF3)COF (655.7 g, 2.15 mol) was continuously added to the above mixture. Then, dimethyl sulfate (325.42 g, 2.58 mol) was started to be dropped, and the dropping was completed within 0.5 h. The temperature of the reactor was raised to 90 °C, and the mixture was continuously stirred for 8 h to end the reaction. After the temperature of the reactor was lowered to room temperature of 25 °C, the reaction solution was transferred to a flask, 10% sodium hydroxide aqueous solution by mass (350 g) was added and stirred for 10 minutes, the stirring was stopped and left standing for 0.5 h, and the lower fluorine phase was released for distillation to obtain the target product CF3OCF(CF3)CF2OCF(CF3)CF2OCH3.

[0045] Example 4: Preparation of CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH3: In a 2L jacketed stainless steel high-pressure reactor equipped with a stirrer, a pressure gauge, and a feeding funnel, under nitrogen protection, cesium fluoride (65.32 g, 0.43 mol) was added, and then the reactor was sealed. Subsequently, the reactor was evacuated and replaced three times. Under nitrogen protection, dried diethylene glycol dimethyl ether (800 g) was added, and the pressure of the reactor was reduced to 0.01 MPa. While stirring at a speed of 300 revolutions per minute, the temperature was lowered to 20 °C. Under nitrogen protection, CF3CF2OCF(CF3)CF2OCF(CF3)COF (963.2 g, 2.15 mol) was continuously added to the above mixture. Then, dimethyl sulfate (325.42 g, 2.58 mol) was started to be dropped, and the dropping was completed within 0.5 h. The temperature of the reactor was raised to 90 °C, and the mixture was continuously stirred for 8 h to end the reaction. After the temperature of the reactor was lowered to room temperature of 25 °C, the reaction solution was transferred to a flask, 10% sodium hydroxide aqueous solution by mass (350 g) was added and stirred for 10 minutes, the stirring was stopped and left standing for 0.5 h, and the lower fluorine phase was released for distillation to obtain the target product CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH3.

[0046] Example 5: Preparation of CF3OCF(CF3)CF2OCH2CH3: In a 2L jacketed stainless steel high-pressure reactor equipped with a stirrer, a pressure gauge, and a feeding funnel, under nitrogen protection, potassium fluoride (25 g, 0.43 mol) was added, and then the reactor was sealed. Subsequently, the reactor was evacuated and replaced three times. Under nitrogen protection, dried N,N-dimethylformamide (900 g) was added, and the pressure of the reactor was reduced to 0.01 MPa. While stirring at a speed of 300 revolutions per minute, the temperature was lowered to 0 °C. Under nitrogen protection, CF3OCF(CF3)COF (500 g, 2.16 mol) was continuously added to the above mixture. Then, diethyl sulfate (397.81 g, 2.58 mol) was started to be dropped, and the dropping was completed within 0.5 h. The temperature of the reactor was raised to 60 °C, and the mixture was continuously stirred for 8 h to end the reaction. After the temperature of the reactor was lowered to room temperature of 25 °C, the reaction solution was transferred to a flask, 15% sodium hydroxide aqueous solution by mass (230 g) was added and stirred for 10 minutes, the stirring was stopped and left standing for 0.5 h, and the lower fluorine phase was released for distillation to obtain the target product CF3OCF(CF3)CF2OCH2CH3.

[0047] Example 6: Preparation of CF3OCF(CF3)CF2OCF(CF3)CF2OCH2CH3: In a 2L jacketed stainless steel high-pressure reactor equipped with a stirrer, a pressure gauge, and a charging funnel, under nitrogen protection, potassium fluoride (17.43 g, 0.3 mol) was added, and then the reactor was sealed. Subsequently, the reactor was evacuated and replaced three times. Under nitrogen protection, dried N,N-dimethylformamide (1000 g) was added, and the pressure of the reactor was released to 0.01 MPa. While stirring at a speed of 300 revolutions per minute, the temperature was lowered to 0 °C. Under nitrogen protection, CF3OCF(CF3)CF2OCF(CF3)COF (796 g, 2 mol) was continuously added to the above mixture. Then, diethyl sulfate (320.72 g, 2.08 mol) was started to be added dropwise and completed within 0.5 h. The temperature of the reactor was raised to 90 °C, and the mixture was continuously stirred for 10 h to end the reaction. After the temperature of the reactor dropped to room temperature (25 °C), the reaction solution was transferred to a flask, a 10% sodium hydroxide aqueous solution by mass (70 g) was added and stirred for 10 minutes, the stirring was stopped and left standing for 0.5 h, and the lower fluorine phase was released for distillation to obtain the target product CF3OCF(CF3)CF2OCF(CF3)CF2OCH2CH3.

[0048] Example 7: Preparation of CF3CF2OCF(CF3)CF2OCH2CH3: In a 2L jacketed stainless steel high-pressure reactor equipped with a stirrer, a pressure gauge, and a charging funnel, under nitrogen protection, potassium fluoride (25 g, 0.43 mol) was added, and then the reactor was sealed. Subsequently, the reactor was evacuated and replaced three times. Under nitrogen protection, dried N,N-dimethylformamide (900 g) was added, and the pressure of the reactor was released to 0.01 MPa. While stirring at a speed of 300 revolutions per minute, the temperature was lowered to 0 °C. Under nitrogen protection, CF3CF2OCF(CF3)COF (564 g, 2 mol) was continuously added to the above mixture. Then, diethyl sulfate (331.51 g, 2.15 mol) was started to be added dropwise and completed within 0.5 h. The temperature of the reactor was raised to 80 °C, and the mixture was continuously stirred for 6 h to end the reaction. After the temperature of the reactor dropped to room temperature (25 °C), the reaction solution was transferred to a flask, a 10% sodium hydroxide aqueous solution by mass (120 g) was added and stirred for 10 minutes, the stirring was stopped and left standing for 0.5 h, and the lower fluorine phase was released for distillation to obtain the target product CF3CF2OCF(CF3)CF2OCH2CH3.

[0049] Example 8: Preparation of CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3: In a 2L jacketed stainless steel high-pressure reactor equipped with a stirrer, a pressure gauge, and a charging funnel, under nitrogen protection, cesium fluoride (65.32 g, 0.43 mol) was added, and then the reactor was sealed. Subsequently, the reactor was evacuated and replaced three times. Under nitrogen protection, dried diethylene glycol dimethyl ether (800 g) was added, and the pressure of the reactor was released to 0.01 MPa. While stirring at a speed of 300 revolutions per minute, the temperature was lowered to 20 °C. Under nitrogen protection, CF3CF2OCF(CF3)CF2OCF(CF3)COF (896 g, 2 mol) was continuously added to the above mixture. Then, diethyl sulfate (333.03 g, 2.16 mol) was started to be dropped, and the dropping was completed within 0.5 h. The temperature of the reactor was raised to 90 °C, and the mixture was stirred for 10 h to end the reaction. After the temperature of the reactor was lowered to room temperature (25 °C), the reaction solution was transferred to a flask, 15% sodium hydroxide aqueous solution by mass (90 g) was added and stirred for 10 minutes, the stirring was stopped and left standing for 0.5 h, and the lower fluorine phase was released for distillation to obtain the target product CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3.

[0050] The reaction results of Examples 1-8 are shown in Table 1.

[0051] Table 1 Reaction Results of Examples 1-8 As can be seen from Table 1, by reacting an acyl fluoride compound with a dialkyl sulfate, the corresponding oxa-type hydrofluoroether compound can be synthesized, and the yield of the target product > 80%, the product purity > 99.5%, having the prospect of large-scale production.

[0052] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0053] The above-described embodiments only represent several implementation manners of the present application. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the patent of the present application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several improvements and optimizations can be made, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. An oxa-hydrofluoroether compound, characterized in that: The structure of the oxahydrofluoroether compound is shown in formula (1): Among them, R f is F or CF3; R is methyl or ethyl; n is an integer of 1-3.

2. An oxyhydrofluoroether compound according to claim 1, characterized in that: The oxa-hydrofluoroether compound is any one of the following: CF3OCF(CF3)CF2OCH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3OCF(CF3)CF2OCH2CH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCH2CH3; CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3; CF3CF2OCF(CF3)CF2OCH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3; CF3CF2OCF(CF3)CF2OCH2CH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3.

3. A method for synthesizing an oxa-hydrofluoroether compound, characterized in that: The synthesis method comprises the following steps: reacting an acyl fluoride compound, an alkylating agent and an alkali metal fluoride in a polar aprotic solvent to obtain an oxahydrofluoroether compound.

4. The method for synthesizing an oxa-hydrofluoroether compound according to claim 3, characterized in that: The structure of the acyl fluoride compound is shown in formula (2): Formula 2 Among them, R f is F or CF3; m is an integer of 1-3.

5. The method for synthesizing an oxa-hydrofluoroether compound according to claim 4, characterized in that: The acyl fluoride compound is one or more of the following: CF3OCF(CF3)COF; CF3OCF(CF3)CF2OCF(CF3)COF; CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF; CF3CF2OCF(CF3)COF; CF3CF2OCF(CF3)CF2OCF(CF3)COF; CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF.

6. The method for synthesizing an oxa-hydrofluoroether compound according to claim 3, characterized in that: The alkylating agent is at least one of dialkyl sulfate, dialkyl carbonate, and halogenated hydrocarbon; The alkali metal fluoride is at least one of potassium fluoride, sodium fluoride, cesium fluoride and rubidium fluoride; The polar aprotic solvent is at least one of ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, acetonitrile, N,N-dimethylformamide, N,N-diethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide.

7. The method for synthesizing an oxa-hydrofluoroether compound according to claim 3, characterized in that: The molar ratio of the acyl fluoride compound to the alkylating agent is 1:(1-1.5); The molar ratio of the alkali metal fluoride to the acyl fluoride compound is 1:(2-10); The mass ratio of the acyl fluoride compound to the polar aprotic solvent is 1:(0.8-2).

8. The method for synthesizing an oxa-hydrofluoroether compound according to any one of claims 3 to 7, characterized in that: The synthesis method steps are as follows: (1) Under nitrogen protection, mixing an alkali metal fluoride and a polar aprotic solvent; (2) After cooling, under nitrogen protection, add acyl fluoride compounds and mix; (3) adding an alkylating agent dropwise to the mixture obtained in step (2), and after the addition is complete, heating the mixture to react; (4) After cooling, adding alkali solution to mix, standing, and distilling to obtain an oxyhydrofluoroether compound with a purity of ≥99.5%.

9. The method for synthesizing an oxa-hydrofluoroether compound according to claim 8, characterized in that: The temperature after cooling in step (2) is 0-20°C; In the step (2), before cooling, the reaction pressure is adjusted to 0.01-1.0 MPa; The temperature after heating in step (3) is 30-120° C., and the reaction time is 2-24 h; The temperature after cooling in step (4) is 20-30°C; In the step (4), the alkali solution is at least one of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution or potassium carbonate solution; and the mass concentration of the alkali solution is 5-50%.

10. Use of the oxyhydrofluoroether compound according to claim 1 or 2, or the oxyhydrofluoroether compound prepared by the method according to any one of claims 3 to 9, in the preparation of electronic cleaning agents, electronic fluorination liquids or solvents.

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