Fluorine-containing electronic cooling liquid and preparation method thereof

Abstract

The invention provides a fluorine-containing electronic cooling liquid and a preparation method thereof. The fluorine-containing electronic cooling liquid comprises fluorine-containing dichloro olefin and fluorine-containing cycloalkane, or fluorine-containing dichloro olefin and hydrofluoroether are included. The preparation method of the fluorine-containing dichloro olefin comprises the following steps: step 1, preparing fluorine-containing alkyne R1C = CR2 through a liquid phase dehydrochlorination reaction of fluorine-containing monochloro olefin R1CCl = CHR2; and 2, carrying out an addition reaction on the fluorine-containing alkyne R1C = CR2 and chlorine to prepare fluorine-containing dichloro olefin R1CCl = CClR2. According to the fluorine-containing electronic cooling liquid disclosed by the invention, symmetric arrangement of groups is optimized, so that the fluorine-containing electronic cooling liquid is good in stability, low in dielectric constant and good in insulating property; double bonds contained in molecules of the fluorine-containing electronic cooling liquid can be quickly added with OH free radicals after passing through the atmosphere, are degraded through oxidation and cannot enter the ozone layer, the ozone depletion potential (ODP) is close to 0, and the GWP100 value is further effectively reduced by adding the second component fluorine-containing cycloalkane or fluorine-containing ether with an annular structure.

Description

Technical Field

[0001] The invention belongs to the technical field of fluid heat transfer, relates to an immersion type electronic coolant, and in particular to a fluorine-containing electronic coolant and a preparation method thereof. Background Art

[0002] Commonly used immersion electronic coolants include hydrofluorocarbons, hydrofluoroethers, perfluoroalkanes, perfluoroamines, perfluoropolyethers, etc. Their main technical indicators are: thermal conductivity, breakdown voltage, volume resistivity, dielectric constant and global warming potential (GWP). 100 value), etc., and is required to have good thermal conductivity, insulation, signal fidelity and environmental friendliness.

[0003] At present, most electronic coolants used in the market have good thermal conductivity and insulation, but their GWP 100 The dielectric constant of a small amount of electronic coolant is relatively high, thus affecting the signal integrity and stability of the electronic components immersed therein.

[0004] The main component of the FC-72 two-phase immersion electronic coolant developed by 3M Company in the United States is perfluorohexane, which has a dielectric constant of 1.75 and stable thermodynamic and chemical properties, but its GWP 100 A value higher than 5000 does not meet green environmental protection standards. Summary of the invention

[0005] In view of the deficiencies in the prior art, the object of the present invention is to provide a fluorine-containing electronic coolant and a preparation method thereof, so as to solve the technical problem that the comprehensive performance of the electronic coolant in the prior art needs to be further improved.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions to achieve the above problems:

[0007] A fluorine-containing electronic coolant comprises fluorine-containing dichloroolefin and fluorine-containing cycloalkane; or comprises fluorine-containing dichloroolefin and hydrofluoroether.

[0008] The fluorine-containing dichloroolefin is R1CCl=CClR2.

[0009] The fluorinated cycloalkane is C m H n F 2m-n .

[0010] The hydrofluoroether is C x H y F 2x+2-y O.

[0011] Where:

[0012] R1 is -H, -CF3, -CHF2, -CH2F or -CH3;

[0013] R2 is -F, -CF3, -CHF2 or -CH2F;

[0014] m = 4, 5 or 6;

[0015] n = 3, 4 or 6;

[0016] x = 2, 3 or 4;

[0017] y=0, 1 or 2.

[0018] The present invention also has the following technical features:

[0019] Specifically, the invention is prepared from the following raw materials by weight: 60% to 99% of fluorine-containing dichloroolefin and 1% to 40% of fluorine-containing cycloalkane or hydrofluoroether, and the sum of the raw materials by weight is 100%.

[0020] Preferably, the invention is prepared from the following raw materials in parts by weight: 80% to 90% of fluorine-containing dichloroolefin, 10% to 20% of fluorine-containing cycloalkane or hydrofluoroether, and the sum of the parts by weight of the raw materials is 100%.

[0021] Preferably, the fluorinated dichloroolefin is CFCl=CHCl, CF3CCl=CHCl, CF3CCl=CClCH3, CF3CCl=CClCHF2, CF3CCl=CClCH2F, CF3CH2CCl=CHCl or CF3CF2CCl=CHCl.

[0022] Preferably, the fluorinated cycloalkane is perfluorocyclobutane, heptafluorocyclobutane, perfluorocyclopentane, nonafluorocyclopentane, octafluorocyclopentane, perfluorocyclohexane or undecafluorocyclohexane.

[0023] Preferably, the hydrofluoroether is CF3CF2CF2CF2OCH3, (CF3)2CFCF2OCH3, CF3CF2CF2OCH3, (CF3)2CFCF2O CH2CH3, CF3CHFCF2OCH2CF3 or CH3CF2CF2OCF2CF3.

[0024] The present invention also protects a method for preparing the fluorine-containing electronic coolant as described above, which includes the method for preparing the fluorine-containing dichloroolefin.

[0025] The preparation method of the fluorine-containing dichloroolefin comprises the following steps:

[0026] Step 1: Fluorine-containing monochloroolefin R1CCl=CHR2 is subjected to liquid phase dehydrochlorination reaction to prepare fluorine-containing alkyne R1C≡CR2.

[0027] Step 2: Fluorine-containing alkyne R1C≡CR2 is reacted with chlorine to prepare fluorine-containing dichloroolefin R1CCl=CClR2.

[0028] Preferably, in step 1, the liquid phase dehydrochlorination catalyst of the liquid phase dehydrochlorination reaction is a phase transfer catalyst; the reaction temperature of the liquid phase dehydrochlorination reaction is 50 to 150° C.; and the liquid phase dehydrochlorination reaction is carried out in an alkaline solution.

[0029] Further preferably, in step 1, the phase transfer catalyst is triphenylphosphine, tetrabutylphosphine bromide, polyethylene glycol-8000, polyethylene glycol-10000 or polyethylene glycol-20000; and the alkaline solution is a potassium hydroxide aqueous solution with a mass concentration of 40wt.%.

[0030] Further preferably, in step 1, the amount of the phase transfer catalyst used is 1% to 5% of the mass of the fluorinated monochloroolefin R1CCl=CHR2; and the molar ratio of the alkaline solution to the fluorinated monochloroolefin R1CCl=CHR2 is (2 to 5):1.

[0031] Preferably, in step 2, the reaction temperature of the addition reaction is 0 to 50°C.

[0032] Preferably, in step 2, the molar ratio of the fluorine-containing alkyne R1C≡CR2 to chlorine is (1.2-2):1.

[0033] Compared with the prior art, the present invention has the following technical effects:

[0034] (I) The fluorine-containing electronic coolant of the present invention has good stability, low dielectric constant and good insulation performance as an electronic coolant by optimizing the symmetrical arrangement of the groups; the double bonds contained in the molecules of the fluorine-containing electronic coolant can quickly add with OH free radicals after passing through the atmosphere, degrade by oxidation, and cannot enter the ozone layer. The ozone depletion potential (ODP) is close to 0, and the GWP is further effectively reduced by adding the second component of a cyclic structure of fluorine-containing cycloalkane or fluorine-containing ether. 100 value.

[0035] (II) In the present invention, the liquid phase dehydrochlorination reaction has a good reaction effect, the raw material conversion rate can be close to 100%, and the product selectivity can reach 95%; the reaction conditions of the addition reaction are mild, and the product selectivity is above 95%.

[0036] The specific contents of the present invention are further explained in detail below in conjunction with embodiments. DETAILED DESCRIPTION

[0037] It should be noted that all raw materials and reagents in the present invention, unless otherwise specified, are all raw materials and reagents known in the prior art and can be obtained from commercial channels. All experimental methods in the present invention, unless otherwise specified, are conventional methods.

[0038] In the present invention, polyethylene glycol-8000 refers to polyvinyl alcohol with a number average molecular weight of 8000; polyethylene glycol-10000 refers to polyvinyl alcohol with a number average molecular weight of 10000; polyethylene glycol-20000 refers to polyvinyl alcohol with a number average molecular weight of 20000.

[0039] In the present invention, (Z) represents a Zusammen isomer, and (E) represents an Entgegen isomer.

[0040] In the present invention, the preparation method of the fluorine-containing electronic coolant is to stir and mix the fluorine-containing dichloroolefin and one of the fluorine-containing cycloalkane or hydrofluoroether at a set ratio at room temperature to obtain the fluorine-containing electronic coolant, wherein the stirring speed is 500-800 r / min and the time is 10-60 min.

[0041] The present invention optimizes the arrangement of the fluorinated olefin groups of the first component to effectively reduce the dielectric constant and improve the insulation performance. By constructing a C=C double bond, adding a second component of a cyclic structure of fluorinated cycloalkanes, or supplementing fluorinated ethers, the GWP is effectively reduced. 100 value.

[0042] In the thermal stability test of the present invention, a certain amount of electronic coolant is added to a pressure-resistant glass bottle with a bottle stopper, and stirred continuously for 1000 hours at a temperature of 80°C. Fluorinated chloroolefins can be inhibited from further deterioration due to the presence of hydrogen atoms, thereby improving their thermal stability. The ODP value is obtained by establishing ozone depletion models such as LINL and AER, and calculating and simulating. GWP 100 The value is obtained by relative rate test analysis. The dielectric constant is obtained by microwave network analyzer (1kHz).

[0043] In the present invention, the conversion rate and selectivity of the reactants are detected by GC-MS detection method.

[0044] Specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solution of this application fall within the protection scope of the present invention.

[0045] Embodiment 1:

[0046] This embodiment provides a method for preparing fluorine-containing alkynes, which comprises the following steps:

[0047] Into a reactor with a stirrer, 28 g of KOH (40 wt%) aqueous solution, 8.05 g of CFCl=CH2 and 0.16 g of polyethylene glycol-10000 (2 wt%) were added in sequence, stirring was started, the reaction temperature was controlled at 80°C, and after reacting for 4 hours, the reaction materials were cooled to room temperature, and organic matter was collected by air bag for gas chromatography analysis. The product was washed with water and alkali to remove HCl and HF, and then analyzed by gas chromatography. The CFCl=CH2 conversion rate was 98.5%, and the CF≡CH selectivity was 93.1%.

[0048] The above product was separated and purified to obtain a sample with a purity of 99.5%, and the results of nuclear magnetic resonance detection were as follows:

[0049] 1 H NMR (500MHz, Chloroform-d) δ3.73 (d, J=15.0Hz, 1H).

[0050] 13 C NMR (125MHz, Chloroform-d) δ92.43 (d, J = 261.9Hz), 89.50 (d, J = 26.9Hz).

[0051] 19 F NMR(472MHz,Chloroform-d)δ-88.41--88.99(m).

[0052] The above data prove that the product is CF≡CH.

[0053] Embodiment 2:

[0054] This embodiment provides a method for preparing fluorine-containing alkynes, which comprises the following steps:

[0055] Into a reactor with a stirrer, 42 g of KOH (40 wt%) aqueous solution, 13.05 g of CF3CH=CHCl and 0.26 g of triphenylphosphine (2 wt%) were added in sequence, stirring was turned on, and the reaction temperature was controlled at 80°C. After reacting for 4 hours, the reaction materials were cooled to room temperature, and the organic matter was collected by gas bag for gas chromatography analysis. The results showed that the conversion rate of CF3CH=CHCl was ~100%, and the selectivity of CF3C≡CH was 97.5%.

[0056] The above product was separated and purified to obtain a sample with a purity of 99.5%, and the results of nuclear magnetic resonance detection were as follows:

[0057] 1 H NMR(500MHz,Chloroform-d)δ2.45(s,1H).

[0058] 13C NMR (125MHz, Chloroform-d) δ 114.16 (q, J = 268.1Hz), 76.12 (q, J = 5.0Hz), 71.68 (q, J = 31.0Hz).

[0059] 19 F NMR (472MHz, Chloroform-d) δ-50.64 (d, J=39.7Hz).

[0060] The above data prove that the product obtained is CF3C≡CH.

[0061] Embodiment 3~7:

[0062] This example provides a method for preparing fluorine-containing alkynes. The method is basically the same as the method in Example 2, except that the phase transfer catalyst and reaction conditions are different. The reaction results are shown in Table 1.

[0063] Table 1 Reaction results of Examples 3 to 7

[0064]

[0065] Embodiments 8 to 18:

[0066] This example provides a method for preparing fluorine-containing alkynes, which is basically the same as the preparation method in Example 2, except that the reaction raw materials are different. The reaction results are shown in Table 2.

[0067] Table 2 Reaction results of Examples 8 to 18

[0068] Example raw material Reaction conversion rate / % Product selectivity / % 8 <![CDATA[CF3CCl=CHF]]> 97.4 95.3 9 <![CDATA[CH3CH=CFCl]]> 95.2 95.8 10 <![CDATA[CH2FCH=CHCl]]> 97.5 96.3 11 <![CDATA[CHF2CH=CHCl]]> 98.5 97.3 12 <![CDATA[CF3CCl=CHCH3]]> 98.5 97.3 13 <![CDATA[CF3CCl=CHCHF2]]> 99.7 96.6 14 <![CDATA[CF3CCl=CHCFH2]]> 99.8 97.3 15 <![CDATA[CHF2CCl=CHCHF2]]> 96.5 94.2 16 <![CDATA[CH2FCCl=CHCH2F]]> 97.8 95.6 17 <![CDATA[CF3CH2CCl=CH2]]> 97.9 95.2 18 <![CDATA[CF3CF2CCl=CH2]]> 98.2 96.1

[0069] Embodiment 19:

[0070] This embodiment provides a method for preparing fluorinated dichloroolefins, which comprises the following steps:

[0071] To a 150 ml stainless steel belt stirring autoclave was added 0.2 mol of CF≡CH prepared in Example 1. The reaction temperature was 50° C. After stirring was started, 0.1 mol of Cl2 was introduced. The reaction pressure was maintained at 0.5 MPa. The reaction was continued for 6 h. The temperature was lowered to stop the reaction. The product was analyzed by gas chromatography. The conversion rate of CF≡CH was 49.8%, and the selectivity of CFCl=CHCl was 98.5%.

[0072] The above product was separated and purified to obtain a sample with a purity of 99.9%, and the results of nuclear magnetic resonance detection were as follows:

[0073] 1H NMR (500MHz, Chloroform-d) δ5.91 (d, J = 52.4Hz, 1H).

[0074] 13 C NMR (125MHz, Chloroform-d) δ144.79 (d, J = 252.1Hz), 100.71 (d, J = 20.0Hz).

[0075] 19 F NMR(472MHz,Chloroform-d)δ-79.39.

[0076] The above data prove that the product obtained is CFCl=CHCl.

[0077] Embodiment 20:

[0078] This embodiment provides a method for preparing fluorinated dichloroolefins, which comprises the following steps:

[0079] To a 150 ml stainless steel stirred autoclave was added 0.12 mol of CF3C≡CH2 obtained in Example 2. The reaction temperature was 0°C. After stirring was started, 0.1 mol of Cl2 was introduced. The reaction pressure was maintained at 0.5 MPa. The reaction was continued for 12 h. The temperature was lowered to stop the reaction. The product was analyzed by gas chromatography. The conversion rate of CF3C≡CH2 was 83.1%, and the selectivity of CF3CCl=CHCl was 97.5%.

[0080] The above product was separated and purified to obtain a sample with a purity of 99.9%, and the results of nuclear magnetic resonance detection were as follows:

[0081] 1 H NMR (500MHz, CDCl3) δ7.16 (d, J=1.2Hz, 1H).

[0082] 13 C NMR (126MHz, CDCl3) δ 125.65 (q, J = 5.6Hz), 124.68 (q, J = 38.0Hz), 119.87 (q, J = 272.5Hz).

[0083] 19 F NMR (471MHz,CDCl3)δ-68.31.

[0084] The above data prove that the product obtained is CF3CCl=CHCl.

[0085] Embodiment 21:

[0086] This embodiment provides a method for preparing fluorinated dichloroolefins, which comprises the following steps:

[0087] To a 150 ml stainless steel stirred autoclave was added 0.15 mol CF3CH2C≡CH, the reaction temperature was 30°C, stirring was started, 0.1 mol Cl2 was introduced, the reaction pressure was maintained at 0.5 MPa, the reaction was carried out for 9 h, the temperature was lowered to stop the reaction, and the product was analyzed by gas chromatography. The conversion rate of CF3CH2C≡CH was 66.5%, and the selectivity of CF3CH2CCl=CHCl was 98.1%.

[0088] The above product was separated and purified to obtain a sample with a purity of 99.9%, and the results of nuclear magnetic resonance detection were as follows:

[0089] 1 H NMR (500MHz, Chloroform-d) δ6.15 (t, J=1.0Hz, 1H), 3.29 (qd, J=9.0, 1.0Hz, 2H).

[0090] 13 C NMR (125MHz, Chloroform-d) δ 124.62 (qd, J = 803.9, 6.1Hz), 123.54 (dd, J = 6.6, 4.7Hz), 122.02-121.69 (m), 39.55 (qq, J = 26.9, 5.7Hz).

[0091] 19 F NMR(472MHz,Chloroform-d)δ-63.70.

[0092] The above data prove that the product obtained is CF3CH2CCl=CHCl.

[0093] Embodiments 22 to 31:

[0094] This example provides a method for preparing fluorinated dichloroolefins. This method is basically the same as the preparation method in Example 21, the only difference being that the reaction raw materials are different. The reaction results are shown in Table 3.

[0095] Table 3 Reaction results of Examples 22 to 31

[0096] Example raw material Reaction conversion rate / % Product selectivity / % 22 <![CDATA[CH3C≡CF]]> 66.3 96.6 23 <![CDATA[CF3CC≡CF]]> 66.4 98.6 24 <![CDATA[CH2FC≡CH]]> 66.1 97.6 25 <![CDATA[CHF2C≡CH]]> 66.5 97.5 26 <![CDATA[CF3C≡CCH3]]> 66.2 96.2 27 <![CDATA[CF3C≡CCHF2]]> 66.4 98.6 28 <![CDATA[CF3C≡CCH2F]]> 66.5 97.5 29 <![CDATA[CHF2C≡CCHF2]]> 66.6 95.6 30 <![CDATA[CH2FC≡CCH2F]]> 66.2 96.5 31 <![CDATA[CF3CF2C≡CH]]> 66.3 96.2

[0097] The fluorinated dichloroolefins obtained according to Examples 19 to 31 are: CFCl=CHCl, CH3CCl=CFCl, CF3CCl=CFCl, CH2FCCl=CHCl, CHF2CCl=CHCl, CF3CCl=CHCl, CF3CCl=CClCH3, CF3CCl=CClCHF2, CF3CCl=CClCH2F, CHF2CCl=CClCHF2, CH2FCCl=CClCH2F, CF3CH2CCl=CHCl and CF3CF2CCl=CHCl, and the samples with a purity of more than 99.9% are obtained by distillation separation.

[0098] Embodiment 32:

[0099] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 90% of fluorine-containing dichloroolefin CFCl=CHCl(E) and 10% of perfluorocyclohexane.

[0100] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0101] Embodiment 33:

[0102] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 70% of fluorine-containing dichloroolefin CH3CCl=CFCl(Z) and 30% of undecafluorocyclohexane.

[0103] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0104] Embodiment 34:

[0105] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 60% of fluorine-containing dichloroolefin CF3CCl=CFCl(E) and 40% of octafluorocyclopentane.

[0106] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0107] Embodiment 35:

[0108] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 80% of fluorine-containing dichloroolefin CH2FCCl=CHCl(E) and 20% of nonafluorocyclopentane.

[0109] The ODP value and GWP of the fluorinated electronic coolant in this example100 The performance test results are shown in Table 4.

[0110] Embodiment 36:

[0111] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 90% of fluorine-containing dichloroolefin CH2FCCl=CHCl(Z) and 10% of perfluorocyclopentane.

[0112] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0113] Embodiment 37:

[0114] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 95% of fluorine-containing dichloroolefin CHF2CCl=CHCl(Z) and 5% of heptafluorocyclobutane.

[0115] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0116] Embodiment 38:

[0117] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 99% of fluorine-containing dichloroolefin CHF2CCl=CHCl(E) and 1% of perfluorocyclobutane.

[0118] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0119] Embodiment 39:

[0120] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 96% of fluorine-containing dichloroolefin CF3CCl=CHCl(Z) and 4% of CF3CF2CF2CF2OCH3.

[0121] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0122] Embodiment 40:

[0123] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials in parts by weight: 96% of fluorine-containing dichloroolefin CF3CCl=CHCl(E) and 4% of (CF3)2CFCF2OCH3.

[0124] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0125] Embodiment 41:

[0126] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials in parts by weight: 94% of fluorine-containing dichloroolefin CF3CCl=CClCH3(Z) and 6% of CF3CHFCF2OCH2CF3.

[0127] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0128] Embodiment 42:

[0129] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials in parts by weight: 95% of fluorine-containing dichloroolefin CF3CCl=CClCH3(E) and 5% of CH3CF2CF2OCF2CF3.

[0130] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0131] Embodiment 43:

[0132] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 95% of fluorine-containing dichloroolefin CF3CCl=CClCHF2(Z) and 5% of undecafluorocyclohexane.

[0133] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0134] Embodiment 44:

[0135] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 90% of fluorine-containing dichloroolefin CF3CCl=CClCHF2(E) and 10% of octafluorocyclopentane.

[0136] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0137] Embodiment 45:

[0138] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 90% of fluorine-containing dichloroolefin CF3CCl=CClCH2F(Z) and 10% of heptafluorocyclobutane.

[0139] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0140] Embodiment 46:

[0141] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials, measured by weight: 88% of fluorine-containing dichloroolefin CF3CCl=CClCH2F(E) and 12% of nonafluorocyclopentane.

[0142] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0143] Embodiment 47:

[0144] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials in parts by weight: 92% of fluorine-containing dichloroolefin CF3CH2CCl=CHCl(E) and 8% of (CF3)2CFCF2OCH3.

[0145] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0146] Embodiment 48:

[0147] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials in parts by weight: 99% of fluorine-containing dichloroolefin CF3CF2CCl=CHCl(E) and 1% of CH3CF2CF2OCF2CF3.

[0148] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0149] Embodiment 49:

[0150] This embodiment provides a fluorine-containing electronic coolant, which is made of the following raw materials in parts by weight: 95% of fluorine-containing dichloroolefin CF3CF2CCl=CHCl(Z) and 5% of (CF3)2CFCF2OCH3.

[0151] The ODP value and GWP of the fluorinated electronic coolant in this example 100 The performance test results are shown in Table 4.

[0152] Table 4 ODP values ​​and GWP of Examples 32 to 49 100 value

[0153] Example ODP value <![CDATA[GWP 100 Value]]> 32 0.0013 15.9 33 0.0011 8.7 34 0.0013 16.5 35 0.001 4.9 36 0.001 5.5 37 0.0009 4.8 38 0.0008 4.8 39 0.0008 4.4 40 0.0008 4.4 41 0.0007 3.8 42 0.0007 3.8 43 0.0006 3.7 44 0.0008 4.5 45 0.0008 4.5 46 0.0008 4.2 47 0.0008 4.2 48 0.0008 5.1 49 0.0008 5.1

Claims

1. A fluorine-containing electronic coolant, characterized in that: Containing fluorinated dichloroolefins and fluorinated cycloalkanes; or containing fluorinated dichloroolefins and hydrofluoroethers; The fluorinated dichloroolefin is R1CCl=CClR2; The fluorinated cycloalkane is C m H n F 2m-n ; The hydrofluoroether is C x H y F 2x+2-y O; Where: R1 is -H, -CF3, -CHF2, -CH2F or -CH3; R2 is -F, -CF3, -CHF2 or -CH2F; m = 4, 5 or 6; n = 3, 4 or 6; x = 2, 3 or 4; y=0, 1 or 2.

2. The fluorine-containing electronic coolant according to claim 1, characterized in that: The invention is prepared from the following raw materials by weight: 60% to 99% of fluorine-containing dichloroolefin and 1% to 40% of fluorine-containing cycloalkane or hydrofluoroether, and the sum of the raw materials by weight is 100%.

3. The fluorine-containing electronic coolant according to claim 2, characterized in that: The invention is prepared from the following raw materials by weight: 80% to 90% of fluorine-containing dichloroolefin and 10% to 20% of fluorine-containing cycloalkane or hydrofluoroether, and the sum of the raw materials by weight is 100%.

4. The fluorine-containing electronic coolant according to claim 1, characterized in that: The fluorinated dichloroolefin is CFCl=CHCl, CF3CCl=CHCl, CF3CCl=CClCH3, CF3CCl=CClCHF2, CF3CCl=CClCH2F, CF3CH2CCl=CHCl or CF3CF2CCl=CHCl; The fluorinated cycloalkane is perfluorocyclobutane, heptafluorocyclobutane, perfluorocyclopentane, nonafluorocyclopentane, octafluorocyclopentane, perfluorocyclohexane or undecafluorocyclohexane; The hydrofluoroether is CF3CF2CF2CF2OCH3, (CF3)2CFCF2OCH3, CF3CF2CF2OCH3, (CF3)2CFCF2OCH2CH3, CF3CHFCF2OCH2CF3 or CH3CF2CF2OCF2CF3.

5. A method for preparing a fluorine-containing electronic coolant as claimed in any one of claims 1 to 4, comprising the method for preparing a fluorine-containing dichloroolefin; characterized in that: The preparation method of the fluorine-containing dichloroolefin comprises the following steps: Step 1: Fluorine-containing monochloroolefin R1CCl=CHR2 is subjected to liquid phase dehydrochlorination reaction to prepare fluorine-containing alkyne R1C≡CR2; Step 2: Fluorine-containing alkyne R1C≡CR2 is reacted with chlorine to prepare fluorine-containing dichloroolefin R1CCl=CClR2.

6. The method for preparing the fluorine-containing electronic coolant according to claim 5, characterized in that: In step 1, the liquid phase dehydrochlorination catalyst of the liquid phase dehydrochlorination reaction is a phase transfer catalyst; The reaction temperature of the liquid phase dehydrochlorination reaction is 50-150° C.; the liquid phase dehydrochlorination reaction is carried out in an alkaline solution.

7. The method for preparing the fluorine-containing electronic coolant according to claim 6, characterized in that: In step 1, the phase transfer catalyst is triphenylphosphine, tetrabutylphosphine bromide, polyethylene glycol-8000, polyethylene glycol-10000 or polyethylene glycol-20000; the alkaline solution is a potassium hydroxide aqueous solution with a mass concentration of 40wt.%.

8. The method for preparing the fluorine-containing electronic coolant according to claim 6, characterized in that: In step 1, the amount of the phase transfer catalyst used is 1% to 5% of the mass of the fluorinated monochloroolefin R1CCl=CHR2; the molar ratio of the alkaline solution to the fluorinated monochloroolefin R1CCl=CHR2 is (2 to 5):

1.

9. The method for preparing the fluorine-containing electronic coolant according to claim 5, characterized in that: In step 2, the reaction temperature of the addition reaction is 0-50°C.

10. The method for preparing the fluorine-containing electronic coolant according to claim 5, characterized in that: In step 2, the molar ratio of fluorine-containing alkyne R1C≡CR2 to chlorine is (1.2-2):1.

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