Mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether and preparation method and application thereof

Abstract

The present invention provides a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether and its preparation method and application, belonging to the field of fluorine chemical technology. The mixture includes perfluorononenyl 2,2,3,3-tetrafluoropropyl ether shown in formula (I), formula (II), formula (III) and formula (IV), wherein A represents 2,2,3,3-tetrafluoro n-propyloxy. The present invention also provides a preparation method of the mixture. The mixture can be used as a fluorinated liquid with good cleaning performance, and can achieve a better cleaning effect on stains on the surface of scintillation crystals.

Description

Technical Field

[0001] The invention belongs to the technical field of fluorine chemistry and relates to a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether and a preparation method and application thereof. Background Art

[0002] Electronic fluorinated liquid is an excellent heat dissipation medium. As an alternative to traditional coolants such as water, ethylene glycol, and oil, it is widely used in the heat dissipation of electronic components, especially high-power electronic components. Electronic fluorinated liquid has good thermal conductivity. It transfers heat from the high temperature area to the low temperature area by heat transfer, thereby maintaining the stability of the device's operating temperature and preventing damage to the device itself caused by overheating caused by operation.

[0003] As a heat transfer medium, a good electronic fluorinated liquid should have the following properties:

[0004] (1) High thermal conductivity: Thermal conductivity is the core indicator for evaluating the thermal conductivity of electronic fluoride liquid. The higher the thermal conductivity, the stronger the thermal conductivity of the electronic fluoride liquid and the faster the heat conduction;

[0005] (2) High heat capacity: Heat capacity is the ability of the electronic fluoride liquid to absorb heat when the temperature rises to a certain level. The higher the heat capacity, the more heat the electronic fluoride liquid absorbs when the temperature rises to the same level. That is, the higher the heat capacity, the less the temperature rises when the same amount of heat is absorbed, and the stronger the ability of the electronic fluoride liquid to continue to absorb heat.

[0006] (3) Convective heat transfer capability: Locally heated electronic fluorinated liquid can quickly transfer heat through convection. Liquids with too high a viscosity are not conducive to convection movement, and thus are not conducive to the rapid heat transfer process.

[0007] As a heat exchange fluid for electronic components, electronic fluorinated liquid should not interfere with the operation of electronic components, surrounding technicians, and the environment during use. Therefore, a good electronic fluorinated liquid should also have the following characteristics:

[0008] (1) Good insulation performance: The excellent insulation performance enables electronic fluorinated liquid to achieve immersion cooling of running devices, further improving heat exchange efficiency while not affecting the normal operation of the devices.

[0009] (2) Chemical inertness: no ignition point, no flash point, no thermal decomposition within the temperature range of heat dissipation conditions, reducing the fluctuation of thermal conductivity during the application of electronic fluorinated liquids and ensuring safe operation of devices.

[0010] (3) Good material compatibility: Common cooling objects include metals, inorganic non-metallic materials and other types of materials. Electronic fluoride liquid does not dissolve or chemically corrode the cooling objects, thus meeting the requirements of immersion cooling.

[0011] (4) Low toxicity and low irritation: safer for operators who come into contact with electronic fluoride liquid.

[0012] (5) Recyclable and renewable: It can be purified and regenerated through distillation and other methods to achieve repeated use, which reduces costs while increasing the utilization rate of electronic fluorine liquid, reduces waste liquid generation, and is beneficial to environmental protection.

[0013] The chemical inertness of electronic fluorinated fluid also determines its use as a cleaning product for precision instruments or non-aqueous cleaning.

[0014] Patent application CN113511961A discloses a hydrofluoroether and its preparation method and application, and provides a method for preparing a hydrofluoroether compound. However, the disclosure does not provide the specific structure and ratio of different species of the obtained hydrofluoroether, nor does it disclose the use of the hydrofluoroether product as a cleaning product.

[0015] Patent application CN117263779A discloses a synthesis method and application of perfluorononenyl trifluoroethyl ether. The disclosure provides key physical indicators such as the odor, density, dielectric constant, volume resistivity, thermal conductivity, viscosity, etc. of the obtained hydrofluoroether product. However, the disclosure does not provide the specific structure and proportion of the obtained hydrofluoroether, nor does it disclose the influence of the specific structure and proportion on the performance of the hydrofluoroether product.

[0016] Patent application CN115572579A discloses a perfluoro compound composition for liquid cooling and its application in immersion cooling. The disclosure provides 1-(difluoromethoxy)-1,2,2-trifluoroethane, 2-fluoromethoxy-1,1,1,2-tetrafluoroethane, 2-methoxy-1,1,1,2-tetrafluoroethane, 1-methoxy-1,1,2,3-tetrafluoroethane, 1-difluoromethoxy-2,2-difluoroethane, 2-methoxy-1,1,2-trifluoroethane, 1,1-difluoro-2-methoxyethane, 1,1,1,3,3,3-hexa-2-(fluoromethoxy)propane, 1,1,2-trifluoro-1-methoxy-2(trifluoromethoxy)ethane, 1,1,1,2,3,3-hexafluoro-3-methoxypropane, 1,1,1 ,3,3,3-hexafluoro-2-methoxypropane, 1,1,2,2,3,3-hexafluoro-3-methoxypropane, 1-ethoxy-1,1,1,2-tetrafluoroethane, 2-ethoxy-1,1,2,2-tetrafluoroethane, 1,1,1-trifluoro-2-ethoxyethane, 1,1,1-trifluoro-3-methoxypropane, 1,1,1-trifluoro-2-methoxypropane, 1-ethoxy-1,2,2-trifluoroethane, 2,3-difluoro-4-(trifluoromethyl)oxetane and their azeotropic compositions in different proportions, and also provide the application of different coolants as immersion coolants for server motherboard CPU. However, the disclosure does not provide a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether with better efficacy and the effect of its application in non-aqueous cleaning.

[0017] KN Makarov et al. disclosed a method for preparing a hydrofluoroether compound in "Hexafluoropropene Trimer. Synthesis and Properties of Functional Derivatives" (Journal of Fluorine Chemistry, 10 (1977) 323-327), and the reaction mechanism is as follows:

[0018]

[0019] The disclosure uses triethylamine as an organic base and an excess of alcohol as an organic solvent. However, the disclosure does not provide a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether, nor does it provide the performance of the mixture as a non-aqueous cleaning agent.

[0020] In summary, it is difficult in the prior art to provide a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether with better heat dissipation performance so as to achieve application as an electronic fluorination liquid with better cleaning effect. Summary of the invention

[0021] In view of this, the prior art is difficult to provide a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether with better heat dissipation performance to achieve the bottleneck problem of application as an electronic fluorination liquid with better cleaning effect. The object of the present invention is to provide a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether and its preparation method and application.

[0022] To achieve the above-mentioned object of the invention, on the one hand, the present invention provides a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether, wherein the mixture comprises perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV),

[0023]

[0024] Wherein, A represents 2,2,3,3-tetrafluoro-n-propyloxy.

[0025] Preferably, the mass ratio of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV) is 0.802-0.888:0.103-0.199:1.601-1.727:97.232-97.489.

[0026] More preferably, the mass ratio of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV) is 0.815-0.834:0.128-0.167:1.639-1.695:97.338-97.378.

[0027] More preferably, the mass ratio of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV) is 0.815-0.825:0.132-0.149:1.639-1.695:97.338-97.378.

[0028] Further preferably, and as a specific embodiment of the present invention, the mass ratio of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV) is 0.819:0.149:1.687:97.344.

[0029] In another aspect, the present invention provides a method for preparing the above-mentioned mixture, comprising the following steps:

[0030] 2,2,3,3-tetrafluoropropanol is mixed with an inorganic alkali aqueous solution, hexafluoropropylene trimer is added, the mixture is reacted by heat preservation, and separated to obtain a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether.

[0031] Preferably, the inorganic base is selected from at least one of potassium hydroxide and sodium hydroxide.

[0032] More preferably, the inorganic base is potassium hydroxide.

[0033] Preferably, the concentration of the inorganic alkali aqueous solution is 10%-45%.

[0034] More preferably, the concentration of the inorganic alkali aqueous solution is 30%-45%.

[0035] More preferably, the concentration of the inorganic base aqueous solution is 40%.

[0036] Preferably, the mixing is specifically stirring evenly for a stirring time of 10-100 min.

[0037] More preferably, and as an example of the present invention, the stirring time is 30 minutes.

[0038] Preferably, the molar ratio of the 2,2,3,3-tetrafluoropropanol, the inorganic base and the hexafluoropropylene trimer is 1:1.1-1.4:1.

[0039] More preferably, the molar ratio of the 2,2,3,3-tetrafluoropropanol, the inorganic base and the hexafluoropropylene trimer is 1:1.2-1.4:1.

[0040] More preferably, the molar ratio of the 2,2,3,3-tetrafluoropropanol, the inorganic base and the hexafluoropropylene trimer is 1:1.2-1.3:1.

[0041] Further preferably, and as an example of the present invention, the molar ratio of the 2,2,3,3-tetrafluoropropanol, the inorganic base and the hexafluoropropylene trimer is 1:1.3:1.

[0042] Preferably, the adding of hexafluoropropylene trimer is specifically: adding hexafluoroethylene trimer dropwise under stirring at room temperature, and controlling the dropping speed to keep the system temperature not exceeding 50°C.

[0043] Preferably, the temperature of the insulation reaction is 40-70°C.

[0044] More preferably, the temperature of the insulation reaction is 50-70°C.

[0045] More preferably, the temperature of the insulation reaction is 50-60°C.

[0046] Further preferably, and as an example of the present invention, the temperature of the insulation reaction is 60°C.

[0047] Preferably, the insulation reaction time is 3-9 hours.

[0048] More preferably, and as an example of the present invention, the insulation reaction time is 6 hours.

[0049] Preferably, the separation comprises the following steps: standing, liquid separation, washing, drying and distillation.

[0050] More preferably, the standing still is standing still for 30 minutes.

[0051] More preferably, the liquid separation is to separate the lower layer product.

[0052] More preferably, the washing is washing with a dilute hydrochloric acid aqueous solution and water.

[0053] More preferably, the washing is washing once with a 10% dilute hydrochloric acid aqueous solution and then washing twice with water.

[0054] More preferably, the washing with water is washing with water until neutrality.

[0055] More preferably, after the washing, unreacted hexafluoroethylene trimer isomers are recovered.

[0056] More preferably, the drying is performed using a desiccant.

[0057] More preferably, and as an example of the present invention, the desiccant is anhydrous sodium sulfate.

[0058] More preferably, the distillation is a reduced pressure distillation.

[0059] More preferably, during the reduced pressure distillation, the fraction collected at 176° C. is a mixture of the product perfluorononenyl 2,2,3,3-tetrafluoropropyl ether.

[0060] In another aspect, the present invention provides an electronic fluorination liquid, comprising the above mixture and the mixture obtained by the above preparation method.

[0061] In another aspect, the present invention provides the use of the above mixture and the mixture obtained by the above preparation method in electronic fluorinated liquid products.

[0062] Preferably, the electronic fluorinated liquid product is a cleaning agent.

[0063] Compared with the prior art, the present invention has the following beneficial effects:

[0064] (1) The present invention provides a new perfluorononenyl 2,2,3,3-tetrafluoropropyl ether mixture with a clear composition. The mixture can be used as an electronic fluorination liquid product and has a good washing effect on cesium iodide scintillation crystals.

[0065] (2) The present invention also provides a method for preparing the above-mentioned perfluorononenyl 2,2,3,3-tetrafluoropropyl ether mixture. The preparation method uses water as a solvent and an inorganic base as a catalyst. The steps are simple and easy to perform, the overall cost is low, and it is green and environmentally friendly.

[0066] (3) The perfluorononenyl 2,2,3,3-tetrafluoropropyl ether mixture provided by the present invention has good bioaffinity and is non-irritating to the skin and eyes. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 The product of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether mixture synthesized by the synthesis method described in Example 1 19 F-NMR spectrum.

[0068] Figure 2 The product of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether mixture synthesized by the synthesis method described in Example 1 1 H-NMR spectrum.

[0069] Figure 3 This is a liquid chromatography spectrum of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether mixture product synthesized by the synthesis method described in Example 1, wherein 1 represents the compound shown in formula (III), 2 represents the compound shown in formula (I), 3 represents the compound shown in formula (IV), and 4 represents the compound shown in formula (II).

[0070] Figure 4a It is the mass spectrum of the compound represented by formula (I) synthesized by the synthesis method described in Example 1.

[0071] Figure 4b It is the mass spectrum of the compound represented by formula (II) synthesized by the synthesis method described in Example 1.

[0072] Figure 4c It is the mass spectrum of the compound represented by formula (III) synthesized by the synthesis method described in Example 1.

[0073] Figure 4d It is the mass spectrum of the compound represented by formula (IV) synthesized by the synthesis method described in Example 1. DETAILED DESCRIPTION

[0074] The following non-limiting examples can enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way. The following content is only an exemplary description of the scope of the present invention, and those skilled in the art can make various changes and modifications to the invention of the present invention based on the disclosed content, and they should also fall within the scope of the present invention.

[0075] The present invention is further described below by way of specific examples. The various chemical reagents used in the examples of the present invention are obtained through conventional commercial channels unless otherwise specified. Unless otherwise specified, the contents described below are all weight contents. Unless otherwise specified, it is understood that the process is carried out at room temperature.

[0076] In the following examples and comparative examples, the main raw materials are from the following sources:

[0077]

[0078] In the following examples, the characterization conditions of the products are as follows:

[0079]

[0080]

[0081] Example 1

[0082] A method for synthesizing a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ethers.

[0083] 2,2,3,3-tetrafluoropropanol (132g, 1mol) and 40% potassium hydroxide aqueous solution (168g of 40% KOH aqueous solution, KOH content 67.2g, 1.2mol) were mixed and stirred for 30min, and hexafluoropropylene trimer (450g, 1mol) was added dropwise at room temperature, and the dropping speed was controlled to keep the system temperature not exceeding 50℃. After about 1h of dropwise addition, the oil bath was heated to 60℃ and kept warm for 6h, and the reaction was completed. The lower layer product was separated. It was washed with dilute hydrochloric acid aqueous solution (10%) (30mL×1) and water (50mL×2) in turn until neutral. After recovering the unreacted hexafluoropropylene trimer, it was dried over anhydrous sodium sulfate and then distilled under reduced pressure. The 176℃ fraction was collected to obtain a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ethers with a yield of 65.2%.

[0084] Among them, the calculation method of the yield of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether is:

[0085] Perfluorononenyl 2,2,3,3-tetrafluoropropyl ether yield =

[0086] n 全氟壬烯基2,2,3,3-四氟丙基醚 ÷n 2，2，3，3-四氟丙醇 ×100%=m 产物 ÷M 全氟壬烯基2,2,3,3-四氟丙基醚 ÷1mol×100%

[0087] Among them, n represents the amount of substance (mol), m represents the mass (g), and M represents the relative molecular mass (g / mol).

[0088] The product perfluorononenyl 2,2,3,3-tetrafluoropropyl ether was characterized as follows:

[0089] (1) Elemental analysis (combustion method) detection:

[0090] C: 25.43% (calculated value: 25.64%); H: 0.69% (calculated value: 0.54%); F: 70.83% (calculated value: 70.98%). The molecular formula of the product is C 12 H3OF 21 .

[0091] (2) Nuclear Magnetic Resonance Detection:

[0092] The product synthesized in Example 1 was tested by hydrogen nuclear magnetic resonance spectrum and fluorine nuclear magnetic resonance spectrum. 19 F-NMR nuclear magnetic resonance spectrum Figure 1 shown. 1 H-NMR nuclear magnetic resonance spectrum Figure 2 shown.

[0093] 19 F-NMR (ppm): -57.95~-58.56(d,CF3); -59.99~-60.66(m,CF3); -67-07~-70.96(m,CF3)-73.10~-74.77( m, CF3); -127.45 (m, CF2); -140.13~-140.75 (m, CF2); -156.08~-156.46 (=CF); -160.06~-160.48 (=CF).

[0094] 1 H-NMR (ppm): 6.06 and 6.02 (t, 1H, 2 isomers of CF2H); 4.22 and 4.20 (q, 2H, 2 isomers of CF2-CH2-O).

[0095] (3) Infrared spectrum detection:

[0096] IR(cm -1 ): 2984.2(CH); 1611.7(C=C); 1310.1, 1230, 1135.1, 1115.7,

[0097] 1016.2, 755.6(CF).

[0098] (4) Chromatography-mass spectrometry detection:

[0099] The chromatographic conditions were as follows:

[0100] Chromatographic column: DB-5ms 30M*0.25mm*0.5um;

[0101] Inlet: constant flow at 250°C, flow rate 1ml / min, split mode: 50:14;

[0102] Column temperature: He as carrier gas;

[0103] Column temperature (℃) Maintenance time (min) Heating rate (℃ / min) 50 2 6 300 8 10

[0104] Detector: Gas-gas detector scanning range 30-500 mm / z;

[0105] Injection volume: 0.1 μL for empty needle.

[0106] The results are as follows Figure 3 , Figure 4a , Figure 4b , Figure 4c and Figure 4d shown.

[0107] according to Figure 4a , Figure 4b , Figure 4c and Figure 4d From the mass spectrometry results given, it can be inferred that the mixture product of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether prepared in Example 1 is composed of compounds represented by formula (I), formula (II), formula (III) and formula (IV):

[0108]

[0109] Wherein, A is 2,2,3,3-tetrafluoro-n-propyloxy.

[0110] It can be seen that the compounds represented by formula (I), formula (II), formula (III) and formula (IV) are isomers of each other. The chromatographic purity of the four compounds represented by formula (I), formula (II), formula (III) and formula (IV) is shown in the following table:

[0111] Compound content Formula (I) Formula (II) Formula (III) Formula (IV) Example 1 0.819％ 0.149％ 1.687％ 97.344％

[0112] Example 2

[0113] The difference compared with Example 1 is that the 40% potassium hydroxide aqueous solution (168 g of 40% KOH aqueous solution, wherein the KOH content is 67.2 g, 1.2 mol) is replaced by a 40% sodium hydroxide aqueous solution (120 g of 40% NaOH aqueous solution, wherein the NaOH content is 48 g, 1.2 mol), and the rest are the same.

[0114] Example 3

[0115] The difference compared with Example 1 is that 40% potassium hydroxide aqueous solution (168g of 40% KOH aqueous solution, wherein the KOH content is 67.2g, 1.2mol) is replaced by 10% potassium hydroxide aqueous solution (672g of 10% KOH aqueous solution, wherein the KOH content is 67.2g, 1.2mol), and the rest are the same.

[0116] Example 4

[0117] The difference compared with Example 1 is that 40% potassium hydroxide aqueous solution (168 g of 40% KOH aqueous solution, wherein the KOH content is 67.2 g, 1.2 mol) is replaced by 20% potassium hydroxide aqueous solution (336 g of 20% KOH aqueous solution, wherein the KOH content is 67.2 g, 1.2 mol), and the rest are the same.

[0118] Example 5

[0119] The difference compared with Example 1 is that 40% potassium hydroxide aqueous solution (168g of 40% KOH aqueous solution, wherein the KOH content is 67.2g, 1.2mol) is replaced by 20% potassium hydroxide aqueous solution (224g of 30% KOH aqueous solution, wherein the KOH content is 67.2g, 1.2mol), and the rest are the same.

[0120] Example 6

[0121] The difference compared with Example 1 is that 40% potassium hydroxide aqueous solution (168g of 40% KOH aqueous solution, wherein the KOH content is 67.2g, 1.2mol) is replaced by 20% potassium hydroxide aqueous solution (149g of 45% KOH aqueous solution, wherein the KOH content is 67.2g, 1.2mol), and the rest are the same.

[0122] Example 7

[0123] The difference compared with Example 1 is that 40% potassium hydroxide aqueous solution (168g of 40% KOH aqueous solution, wherein the KOH content is 67.2g, 1.2mol) is replaced by 40% potassium hydroxide aqueous solution (154g of 40% KOH aqueous solution, wherein the KOH content is 61.6g, 1.1mol), and the rest are the same.

[0124] Example 8

[0125] The difference compared with Example 1 is that 40% potassium hydroxide aqueous solution (168g of 40% KOH aqueous solution, wherein the KOH content is 67.2g, 1.2mol) is replaced by 40% potassium hydroxide aqueous solution (182g of 40% KOH aqueous solution, wherein the KOH content is 72.8g, 1.3mol), and the rest are the same.

[0126] Example 9

[0127] The difference compared with Example 1 is that 40% potassium hydroxide aqueous solution (168g of 40% KOH aqueous solution, wherein the KOH content is 67.2g, 1.2mol) is replaced by 40% potassium hydroxide aqueous solution (196g of 40% KOH aqueous solution, wherein the KOH content is 78.4g, 1.4mol), and the rest are the same.

[0128] Example 10

[0129] The difference from Example 1 is that the reaction temperature is controlled to 40° C. in an oil bath, and the rest is the same.

[0130] Embodiment 11

[0131] The difference from Example 1 is that the reaction temperature is controlled to 50° C. in an oil bath, and the rest is the same.

[0132] Example 12

[0133] The difference from Example 1 is that the reaction temperature is controlled to 70° C. in an oil bath, and the rest is the same.

[0134] Comparative Example 1

[0135] Perfluorononenyl trifluoroethyl ether synthesized by the perfluorononenyl trifluoroethyl ether synthesis method provided in Example 1 of patent application CN117263779A.

[0136] Comparative Example 2

[0137] Referring to the synthesis method provided in Example 1 of patent application CN113511961A, perfluorononenyl 2,2,3,3-tetrafluoropropyl ether was synthesized. The details are as follows:

[0138] 450g of hexafluoropropylene trimer, 132g of 2,2,3,3-tetrafluoropropanol and 1.5L of diethylene glycol dimethyl ether solvent were added to a 5L reactor, the reaction temperature was controlled at -10°C, 101g of triethylamine was weighed and continuously added to the reaction system and the reaction temperature was maintained at -10°C, and the reaction time was 2h. After the reaction was completed, the liquid was separated and rectified to obtain a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether.

[0139] Comparative Example 3

[0140] Referring to the synthesis method provided in Example 1 of patent application CN117263779A, perfluorononenyl 2,2,3,3-tetrafluoropropyl ether was synthesized. The details are as follows:

[0141] Preparation:

[0142] 2,2,3,3-Tetrafluoropropanol: 66 g; DMF (N,N-dimethylformamide): 2 g; triethylamine 20 g; hexafluoropropylene trimer 120 g.

[0143] 2,2,3,3-tetrafluoropropanol, polar solvent DMF and triethylamine are added to a 1000ml three-necked flask or four-necked flask filled with reflux in sequence, stirred and dissolved evenly, 120g of hexafluoropropylene trimer is added dropwise, stirring continuously, and the dropping time is 30 minutes. During the period, there is an exothermic reaction, and the temperature is reduced and kept at 30-40°C. The reaction is continued for 180 minutes, and then 300g of deionized water is added, stirred for 20 minutes, and separated in a separatory funnel. The lower layer of liquid containing the target product is added to a container, 200g of deionized water is added, and neutralized to neutrality with 10% hydrochloric acid solution under continuous stirring, and separated in a separatory funnel. The lower layer of liquid is taken and washed with deionized water for three times by repeated oscillation, and the lower layer of liquid containing the target product is taken for rectification and purification, and the rectification fraction in the temperature zone of 173-178°C is taken.

[0144] The yield calculation method provided in Example 1 was used to calculate the yield of the mixture prepared in the above Examples 1-12, and the results are summarized in the following table:

[0145]

[0146] The method for detecting the content of the four perfluorononenyl 2,2,3,3-tetrafluoropropyl ether isomers of formula (I), formula (II), formula (III) and formula (IV) in the mixture provided in Example 1 was used to calculate the proportions of the components in the mixtures prepared in the above Examples 1-12 and Comparative Examples 2-3. The results are shown in the following table (unit: parts by mass, "-" means not detected):

[0147]

[0148]

[0149] From the data in the above table, it can be seen that in Comparative Example 2, the compound represented by formula (II) was not detected, and in Comparative Example 3, the compounds represented by formula (I) and formula (II) were not detected. This is because organic solvents and triethylamine were added during the synthesis process, resulting in the separation of the compounds represented by formula (I) and formula (II) or their corresponding hexafluoropropylene trimer precursors during the synthesis and purification of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether product.

[0150] Effect evaluation

[0151] 1. Physical and chemical properties of mixtures of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether

[0152] The key physical and chemical properties of the mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether prepared in Example 1 are shown in the following table:

[0153]

[0154] It can be seen from the test data in the above table that the mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether provided by the present invention has a relatively high boiling point and is suitable as a full immersion single-phase liquid coolant.

[0155] 2. Evaluation of the effect of mixtures of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether as nonaqueous detergents

[0156] Cesium iodide (CsI) crystal is a scintillation crystal with excellent performance, which is widely used in low-energy area security equipment, high-energy physics, radiation detectors, space physics, medical SPECT and other fields. However, since cesium iodide crystal is very soluble in water, general aqueous detergents cannot clean cesium iodide crystals. The perfluorononenyl 2,2,3,3-tetrafluoropropyl ether mixture provided by the present invention can be used as an excellent non-aqueous detergent to effectively reduce the dissolution effect on the surface of cesium iodide crystals while cleaning the dirt on the surface of cesium iodide.

[0157] The specific test verification process is as follows:

[0158] Cesium iodide crystal blocks (3 cm×3 cm×1 cm) were purchased from Jinhong Crystal Materials (Shanghai) Co., Ltd.

[0159] The entire process of the cesium iodide cleaning experiment was carried out in a glove box filled with argon.

[0160] Step 1: Use an electronic balance to accurately weigh the mass of each piece of cesium iodide crystal to be tested.

[0161] Step 2: Construct a surface contamination model of the cesium iodide crystal block.

[0162] The 3cm×3cm surface of cesium iodide was contaminated with pollutants (a black marker (Morning Light M01) was used to cover the 3cm×3cm surface, a blue marker (Trader SCA-400) was used to cover the 3cm×3cm surface, and a drop of pluronic-123 (Sigma, 1 drop weighs about 0.07g) was dropped on the 3cm×3cm surface as pollutants) to obtain a surface contamination model.

[0163] Step 3: Cleaning: Use the products of equal mass provided in the embodiments and comparative examples for cleaning, and then use a clean ear cleaning bulb to blow dry the surface.

[0164] Step 4: Use an electronic balance to accurately weigh the mass of each cesium iodide crystal block after washing and calculate the mass change rate; at the same time, observe the washing effect and score it.

[0165] The test results are as follows:

[0166] (1) Mass change rate of cesium iodide crystal block.

[0167] Mass change rate = (mass of cesium iodide after cleaning - mass of cesium iodide before cleaning) ÷ mass of cesium iodide after cleaning × 100%.

[0168] The experimental results are summarized in the following table:

[0169]

[0170] (2) Sensory evaluation of washing effect.

[0171] The sensory weighted scoring criteria are shown in the following table:

[0172]

[0173] Sensory weighted score = washing cleanliness and washing difficulty score × 35% + crystal surface smoothness score after cleaning × 65%

[0174] The test results are summarized in the following table:

[0175]

[0176] It can be seen that each embodiment, especially embodiment 1, embodiments 6-9 and embodiment 12, has a better cleaning effect on marker dirt and polymers (such as pluronic-123) on the surface of the scintillation crystal cesium iodide crystal, and the cleaning is more thorough and easier. The products provided in comparative examples 1-3 have a slight erosion effect on the surface of the scintillation crystal cesium iodide.

[0177] 3. Biosafety Assessment of Mixtures of Perfluorononenyl 2,2,3,3-Tetrafluoropropyl Ether

[0178] 3.1 Acute skin irritation:

[0179] Basis: OECD TG 404.

[0180] Test method: The experimental animals were kept in single cages and had been adapted to the experimental animal room environment for at least 5 days before the test. The hair on both sides of the animal spine was removed 24 hours before the test, and healthy and intact skin areas were selected for the test.

[0181] Take 0.5mL of the test sample and drop it on a 2.5cm×2.5cm gauze, then apply it to the hairless skin of the unit and fix it with a non-irritating adhesive tape. First, use one animal for a preliminary test. The first test patch was removed after 3 minutes of application on the skin, and no severe skin reaction was observed. The second test patch was used and removed after 1 hour. At this time, the observation results showed that the animal skin was exposed to the test sample for a period of time that could be extended to 4 hours. The third test patch was used and removed after 4 hours, and no severe skin reaction was observed. Therefore, two additional rabbit animals were used for confirmation tests. Observe the skin reaction 1h, 24h, 48h and 72h after the removal of the test sample, and perform skin reaction scoring.

[0182] 3.2 Acute eye irritation:

[0183] Basis: OECD TG 405 test method.

[0184] Test method: The experimental animals were housed in single cages and had been adapted to the experimental animal room environment for at least 5 days before the test. 24 hours before the test, 1 drop of 2% sodium fluorescein saline solution was dripped into the conjunctival sac of the experimental animal's eyes. After 15 seconds, the eyes were gently rinsed with warm saline and then examined with a slit lamp to ensure that the animal's eyes were suitable for the test.

[0185] 0.1 mL of the test sample was dripped into the conjunctival sac of one eye, and the other eye was left untreated as a normal control. The eye was not rinsed within 24 hours after the test sample was dripped. One animal was used in the initial test, and no corrosion or severe irritation was observed, so 2 more animals were added for confirmation testing.

[0186] Eye examination and scoring were performed at 1h, 24h, 48h and 72h after exposure. If the animals showed no eye damage at 72h, the test could be terminated; if the animals showed no particularly severe damage, the damage should be observed to be fully recovered or on the 21st day, and the observation results on the 7th, 14th and 21st days should be recorded.

[0187] 3.3 Acute oral toxicity:

[0188] Basis: OECD TG 401 test method.

[0189] Test method: Animals were acclimated in the barrier environment animal room for 6 days before the test, and fasted overnight before exposure. The maximum limit method was used after the test, and the oral dose was 2000.08 mg / kg. After exposure, fasting continued for 3 hours, and poisoning symptoms or behavioral changes were observed every day. Animals were weighed once a week, and gross anatomical observations were performed on animals that died of poisoning or survived 14 days after exposure.

[0190] 3.4 Acute inhalation toxicity:

[0191] Basis: OECD TG 403 test method.

[0192] Test method: Before the test, the animals were acclimated in the barrier environment animal room for 6 days. During the test, the animals were weighed and marked. The experimental animals were placed in the re-exposure fixing tank and connected to the exposure chamber, and the samples were placed in the injection device. The single concentration oral and nasal exposure system was used for exposure. Parameter settings before exposure (assuming the exposure concentration was 20000mg / m 3 ; Exposure time 4 hours; average aerosol flow 4.974 / min; average dilution flow 0.388 / min; average exhaust flow 8.558 / min), after the exposure, the operation results were obtained (concentration 20690.9mg / m 3 The poisoning process and the poisoning and death of animals during the observation period were observed and recorded. The observation period was generally 14 days. After the observation period, the surviving animals were killed for gross autopsy.

[0193] The results of measuring the mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether provided in Example 1 by the above method are shown in the following table:

[0194] Acute skin irritation Acute eye irritation Acute oral toxicity Acute inhalation toxicity none none <![CDATA[LD 50 >2000.08mg / kg]]> <![CDATA[LC 50 >20690.9mg / m 3 ]]>

[0195] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether, characterized in that: The mixture includes perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV), Wherein, A represents 2,2,3,3-tetrafluoro-n-propyloxy; The mass ratio of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV) is 0.802-0.888:0.103-0.199:1.601-1.727:97.232-97.

489.

2. The mixture according to claim 1, characterized in that The mass ratio of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV) is 0.815-0.834: 0.128-0.167: 1.639-1.695: 97.338-97.

378.

3. The mixture according to claim 2, characterized in that The mass ratio of the perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV) is 0.815-0.825:0.132-0.149:1.639-1.695:97.338-97.

378.

4. The mixture according to claim 3, characterized in that The mass ratio of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether represented by formula (I), formula (II), formula (III) and formula (IV) is 0.819:0.149:1.687:97.

344.

5. The method for preparing the mixture according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: mixing 2,2,3,3-tetrafluoropropanol with an inorganic alkali aqueous solution, adding hexafluoropropylene trimer, reacting at a temperature of 40 °C, and separating to obtain a mixture of perfluorononenyl 2,2,3,3-tetrafluoropropyl ether; Wherein, the inorganic base is selected from at least one of potassium hydroxide and sodium hydroxide; the concentration of the inorganic base aqueous solution is 10%-45%; the molar ratio of the 2,2,3,3-tetrafluoropropanol, the inorganic base and the hexafluoropropylene trimer is 1:1.1-1.4:1; The temperature of the heat preservation reaction is 40-70°C.

6. The preparation method according to claim 5, characterized in that: The time of the heat preservation reaction is 3-9 hours; the separation comprises the following steps: standing, liquid separation, washing, drying and distillation.

7. An electronic fluorination liquid, characterized in that: The invention comprises the mixture described in any one of claims 1 to 4 or the mixture prepared by the preparation method described in any one of claims 5 to 6.

8. Use of the mixture according to any one of claims 1 to 4, or the mixture prepared by the preparation method according to any one of claims 5 to 6, or the electronic fluorinated liquid according to claim 7 in the production of electronic fluorinated liquid products.

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