Fluorine-containing dichlorine olefin, preparation method and application

Abstract

The invention provides fluorine-containing dichloro olefin, a preparation method and application. The preparation method comprises the following steps: step 1, preparing fluorine-containing alkyne R1C = CR2 through a gas-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. A gas phase dehydrochlorination catalyst used in the gas phase dehydrochlorination reaction is a fluorination catalyst Cs-Cu-Ca-F. The dehydrochlorination reaction is good in reaction effect, and the product selectivity can reach 95%; the reaction conditions of the addition reaction are mild, and the product selectivity is 95% or above. According to the fluorine-containing dichloro olefin R1CCl = CClR2 prepared by the preparation method, symmetric arrangement of chlorine atoms is optimized, so that the fluorine-containing dichloro olefin R1CCl = CClR2 is good in stability, low in dielectric constant and good in insulating property when being used as an electronic cooling liquid.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis and relates to fluorine-containing chloroolefins, and in particular to fluorine-containing dichloroolefins, a preparation method and application thereof. Background Art

[0002] Immersion liquid cooling is a typical direct contact liquid cooling method. Electronic equipment is immersed in the coolant, and heat is conducted by the circulation of the coolant. It is a safe, efficient and energy-saving cooling method. Commonly used immersion electronic coolants include fluorocarbons, hydrofluoroethers, perfluoroalkanes, perfluoroamines, perfluoropolyethers, etc. Its main technical indicators are: thermal conductivity, dielectric constant and global warming potential (GWP). 100 At present, most electronic coolants used in the market have good thermal conductivity and insulation, but their GWP 100 The value is generally high, resulting in a longer atmospheric lifetime and greater impact on the environment; or the dielectric constant of the electronic coolant is high, affecting the signal integrity and stability of the electronic components immersed therein.

[0003] 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.

[0004] Research has found that fluorinated chloroolefins are excellent electronic coolant media. Currently, there are few reports on methods for preparing fluorinated chloroolefins, especially fluorinated olefins with chlorine at the symmetrical position of the double bond.

[0005] Kemnitz et al., in analyzing the reaction pathway of fluorination of 1,1,1,2-tetrachloroethane to 1,1,1,2-tetrafluoroethane, found that 0.3-1.5% of 1,2-dichloro-1-fluoroethylene was present in the generated product.

[0006] US2009043118 discloses a method for preparing a composition containing 2,3,3,3-tetrafluoropropene, 2,3-dichloro-1,1,1-trifluoropropane, 2-chloro-1,1,1-trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane and 1,2-dichloro-3,3,3-trifluoropropene, which can be used as a heat transfer composition, by reacting 1,1,1-trifluoropropene with hydrogen fluoride and chlorine in the presence of a gas phase fluorination catalyst. The content of the produced 1,2-dichloro-3,3,3-trifluoropropene is in the range of 0 to 20.2%. CN 109071386 discloses a method for preparing 1,2-dichloro-3,3,3-trifluoropropene by reacting 1,1,2,3,3-pentachloropropene with hydrogen fluoride, with a reaction temperature of 150°C and a reaction pressure of 4.0-4.5 MPa. The total selectivity of the product 1,2-dichloro-3,3,3-trifluoropropene is 89.3%, and the yield is only 83.8%. Summary of the invention

[0007] In view of the shortcomings of the prior art, the object of the present invention is to provide a method for preparing fluorinated dichloroolefins to solve the technical problem that the selectivity of the method for preparing fluorinated dichloroolefins in the prior art needs to be further improved.

[0008] Another object of the present invention is to provide a fluorinated dichloroolefin and its application to solve the technical problem that the comprehensive performance of electronic coolants in the prior art needs to be further improved.

[0009] In order to solve the above technical problems, the present invention adopts the following technical solutions to achieve the above problems:

[0010] A method for preparing fluorine-containing dichloroolefins, the method comprising the following steps:

[0011] Step 1: preparing fluorinated alkyne R1C≡CR2 by gas phase dehydrochlorination of fluorinated monochloroolefin R1CCl=CHR2.

[0012] Step 2: Fluorine-containing alkyne R1C≡CR2 is reacted with chlorine to prepare fluorine-containing dichloroolefin R1CCl=CClR2.

[0013] Where:

[0014] R1 is -H, -CF3, -CHF2, -CH2F or -CH3;

[0015] R2 is -F, -CF3, -CHF2 or -CH2F.

[0016] The present invention also has the following technical features:

[0017] In step 1, the gas phase dehydrochlorination catalyst of the gas phase dehydrochlorination reaction is a fluorination catalyst Cs-Cu-Ca-F.

[0018] In step 1, in the fluorination catalyst Cs-Cu-Ca-F, the molar ratio of Cs, Cu and Ca is (0.9-1.5):(0.1-0.5):(8-9).

[0019] In step 1, the preparation method of the fluorination catalyst Cs-Cu-Ca-F is:

[0020] Step 101, dissolving calcium oxalate and polyethylene glycol in ethylene glycol, reflux treatment under stirring, and then filtering to obtain a solid, washing the solid with deionized water until it is neutral, and then drying to obtain a calcium oxide precursor.

[0021] Step 102, dissolving the calcium oxide precursor obtained in step 101 in water to prepare a calcium oxide precursor aqueous solution, adding hydrofluoric acid dropwise to the calcium oxide precursor aqueous solution, filtering to obtain a solid, washing the solid with water to neutrality, drying, and calcining to obtain a calcium fluoride carrier.

[0022] Step 103, cesium nitrate and copper sulfate are dissolved in water to prepare a solution, and then the calcium fluoride carrier obtained in step 102 is added, impregnated, dried, and calcined to obtain the fluorination catalyst Cs-Cu-Ca-F.

[0023] In step 1, the reaction temperature of the gas phase dehydrochlorination reaction is 300-400° C., and the contact time is 10-30 seconds.

[0024] In step 2, the reaction temperature of the addition reaction is 0-50°C.

[0025] In step 2, the molar ratio of fluorine-containing alkyne R1C≡CR2 to chlorine is (1.2-2):1.

[0026] Specifically, the boiling range of the fluorobischloroolefin is 40-100°C; the dielectric constant of the fluorobischloroolefin is less than 5; the GWP of the fluorobischloroolefin is 100 The value is less than 500.

[0027] Preferably, the boiling range of the fluorobischloroolefin is 60-800°C; the dielectric constant of the fluorobischloroolefin is less than 2.5; the GWP of the fluorobischloroolefin is 100 The value is less than 150.

[0028] Specifically, the fluorinated monochloroolefin R1CCl=CHR2 is CFCl=CHCl, CH3CCl=CFCl, CF3CCl=CFCl, CH2FCCl=CHCl, CHF2CCl=CHCl, CF3CCl=CHCl, CF3CCl=CClCH3, CF3CCl=CClCHF2, CF3CCl=CClCH2F, CHF2CCl=CClCHF2, CH2FCCl=CClCH2F, CF3CH2CCl=CHCl or CF3CF2CCl=CHCl.

[0029] Specifically, the fluorobis(chloro)olefin R1CCl=CClR2 is CFCl=CHCl, CH2FCCl=CHCl, CHF2CCl=CHCl, CF3CCl=CHCl, CF3CCl=CClCH3, CF3CCl=CClCHF2, CF3CCl=CClCH2F or CF3CH2CCl=CHCl.

[0030] Preferably, the fluorobis(chloro)olefin R1CCl=CClR2 is CFCl=CHCl(E), CH2FCCl=CHCl(E), CHF2CCl=CHCl(E), CF3CCl=CHCl(E), CF3CCl=CClCH3(E), CF3CCl=CClCHF2(E), CF3CCl=CClCH2F(E) or CF3CH2CCl=CHCl(E).

[0031] The present invention also protects a fluorine-containing dichloroolefin, characterized in that the structure of the fluorine-containing dichloroolefin is R1CCl=CClR2.

[0032] Where:

[0033] R1 is -H, -CF3, -CHF2, -CH2F or -CH3;

[0034] R2 is -F, -CF3, -CHF2 or -CH2F.

[0035] Furthermore, the fluorinated dichloroolefin is prepared by the preparation method of the fluorinated dichloroolefin as described above.

[0036] The present invention also protects the use of the fluorinated dichloroolefins as described above as electronic coolants.

[0037] Compared with the prior art, the present invention has the following technical effects:

[0038] (I) The dehydrochlorination reaction in the present invention has a good reaction effect, and the product selectivity can reach 95%; the addition reaction in the present invention has mild reaction conditions, and the product selectivity is above 95%.

[0039] (II) In the present invention, the catalyst Cs-Cu-Ca-F is suitable for preparing fluorine-containing alkynes by dehydrohalogenation of halogenated fluoroolefins under gas phase conditions, and is particularly suitable for preparing fluorine-containing alkynes by selective dehydrohalogenation of HCl.

[0040] (III) The fluorinated dichloroolefin R1CCl=CClR2 prepared by the present invention has good stability, low dielectric constant and good insulation performance as an electronic coolant by optimizing the symmetrical arrangement of chlorine atoms.

[0041] (IV) The fluorinated dichloroolefin R1CCl=CClR2 prepared by the present invention is used as an electronic coolant by introducing chlorine atoms into the structure of the C=C double bond, so that the boiling range of the electronic coolant is adjusted to be within an appropriate range. The double bonds contained in the molecules enter the atmosphere and react with OH free radicals, and are degraded by oxidation without entering the ozone layer. The ozone depletion potential (ODP) is close to 0, the atmospheric existence life is short, the greenhouse effect value is low, and the environmental protection performance is excellent.

[0042] The specific contents of the present invention are further explained in detail below in conjunction with embodiments. DETAILED DESCRIPTION

[0043] 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.

[0044] In the present invention, polyethylene glycol-8000 refers to polyvinyl alcohol with a number average molecular weight of 8000.

[0045] In the present invention, (Z) represents a Zusammen isomer, and (E) represents an Entgegen isomer.

[0046] In the present invention, the fluorinated dichloroolefin R1CCl=CClR2 is used as an electronic coolant and applied as a heat transfer medium in an immersion two-phase cooling system in the fields of network base stations, microprocessors, power transformers, circuit board semiconductor devices or chemical reactors.

[0047] Fluorinated dichloroolefins are used as electronic coolants to carry out relevant property tests. The specific items are as follows:

[0048] 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 dichloroolefins 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 LINL and AER ozone depletion models and calculating and simulating. GWP 100The value is obtained by relative rate test analysis. The dielectric constant is obtained by microwave network analyzer (1kHz).

[0049] In the present invention, the conversion rate and selectivity of the reactants are detected by GC-MS detection method.

[0050] 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.

[0051] Embodiment 1:

[0052] This embodiment provides a method for preparing a fluorination catalyst Cs-Cu-Ca-F, wherein the fluorination catalyst Cs-Cu-Ca-F is specifically a fluorination catalyst 0.09Cs-0.01Cu-0.90Ca-F. The method comprises the following steps:

[0053] Step 101, dissolving 0.9 mol calcium oxalate and 0.3 mol polyethylene glycol-8000 in 100 mL ethylene glycol, refluxing at 120° C. for 8 h with stirring, filtering out the solid, washing it with deionized water until it is neutral, and then drying it at 150° C. for 12 h to obtain a calcium oxide precursor.

[0054] Step 102, dissolving the calcium oxide precursor in 100 mL of distilled water to prepare a solution, slowly adding 3.6 mol of hydrofluoric acid to the calcium oxide precursor aqueous solution, filtering to obtain a solid, washing it with deionized water until it is neutral, and then drying it at 100° C. for 12 hours, and then calcining this precursor in a muffle furnace at 550° C. for 6 hours to obtain a calcium fluoride carrier.

[0055] Step 103, 0.09 mol of cesium nitrate and 0.01 mol of copper sulfate are dissolved in 100 mL of distilled water to prepare a solution, and then a calcium fluoride carrier is added. After impregnation for 10 hours, the solution is dried at 100° C. for more than 12 hours, and the precursor is calcined at 500° C. in a muffle furnace for 12 hours to obtain a fluorination catalyst 0.09Cs-0.01Cu-0.90Ca-F.

[0056] Reaction evaluation:

[0057] The fluorination catalyst 0.09Cs-0.01Cu-0.90Ca-F prepared above was used as a gas-phase dehydrochlorination catalyst. 30 mL of the gas-phase dehydrochlorination catalyst was loaded into a fixed-bed tubular reactor with a tube diameter of Φ38 mm. At a reaction temperature of 300°C, CFCl=CH2 was passed through the catalyst bed with a residence time of 30s. After reacting for 4 hours, 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 68.5%, and the CF≡CH selectivity was 84.8%.

[0058] 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:

[0059] 1 H NMR (500MHz, Chloroform-d) δ3.73 (d, J=15.0Hz, 1H).

[0060] 13 C NMR (125MHz, Chloroform-d) δ92.43 (d, J=261.9Hz), 89.50 (d, J=

[0061] 26.9Hz).

[0062] 19 F NMR(472MHz,Chloroform-d)δ-88.41--88.99(m).

[0063] The above data prove that the product is CF≡CH.

[0064] Embodiment 2:

[0065] This embodiment provides a method for preparing a fluorination catalyst Cs-Cu-Ca-F, wherein the fluorination catalyst Cs-Cu-Ca-F is specifically a fluorination catalyst 0.15Cs-0.05Cu-0.80Ca-F. The method comprises the following steps:

[0066] Step 101, dissolving 0.8 mol of calcium carbonate and 0.4 mol of polyethylene glycol-8000 in 100 mL of ethylene glycol, refluxing at 120° C. for 6 h with stirring, filtering out the solid, washing it with deionized water until it is neutral, and then drying it at 150° C. for 12 h to obtain a calcium oxide precursor.

[0067] Step 102, dissolving the calcium oxide precursor in 100 mL of distilled water to prepare a solution, slowly adding 3.2 mol of hydrofluoric acid to the aqueous solution of the calcium oxide precursor, filtering out the solid, washing it with deionized water until it is neutral, and then drying it at 100° C. for 10 hours, and then calcining the precursor in a muffle furnace at 400° C. for 12 hours to obtain a calcium fluoride carrier.

[0068] Step 103, 0.15 mol of cesium nitrate and 0.05 mol of copper sulfate are dissolved in 100 mL of distilled water to prepare a solution, and then a calcium fluoride carrier is added. After impregnation for 24 hours, the solution is dried at 100° C. for more than 12 hours, and the precursor is calcined at 600° C. in a muffle furnace for 6 hours to obtain a fluorination catalyst 0.15Cs-0.05Cu-0.80Ca-F.

[0069] Reaction evaluation:

[0070] The fluorination catalyst 0.15Cs-0.05Cu-0.80Ca-F prepared above was used as a gas-phase dehydrochlorination catalyst. 30 mL of the catalyst was loaded into a fixed-bed tubular reactor with a tube diameter of Φ38 mm. At a reaction temperature of 400°C, CF3CCl=CH2 passed through the catalyst bed with a residence time of 10 s. After reacting for 4 hours, the product was washed with water and alkali to remove HCl and then analyzed by gas chromatography. The CF3CCl=CH2 conversion rate was 76.5%, and the CF3C≡CH selectivity was 94.6%.

[0071] 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:

[0072] 1 H NMR(500MHz,Chloroform-d)δ2.45(s,1H).

[0073] 13 C NMR (125MHz, Chloroform-d) δ 114.16 (q, J = 268.1Hz), 76.12 (q, J = 5.0Hz), 71.68 (q, J = 31.0Hz).

[0074] 19 F NMR (472MHz, Chloroform-d) δ-50.64 (d, J=39.7Hz).

[0075] The above data prove that the product obtained is CF3C≡CH.

[0076] Embodiment 3:

[0077] This embodiment provides a method for preparing a fluorination catalyst Cs-Cu-Ca-F, wherein the fluorination catalyst Cs-Cu-Ca-F is specifically a fluorination catalyst 0.12Cs-0.03Cu-0.85Ca-F. The method comprises the following steps:

[0078] Step 101, dissolving 0.85 mol of calcium carbonate and 0.5 mol of polyethylene glycol-8000 in 100 mL of ethylene glycol, refluxing at 120° C. for 6 h with stirring, filtering out the solid, washing it with deionized water until it is neutral, and then drying it at 150° C. for 12 h to obtain a calcium oxide precursor.

[0079] Step 102, dissolving the calcium oxide precursor in 100 mL of distilled water to prepare a solution, slowly adding 3.4 mol of ammonium fluoride solution into the calcium oxide precursor aqueous solution, filtering to obtain a solid, washing it with deionized water until it is neutral, and then drying it at 100° C. for 10 hours, and then calcining this precursor in a muffle furnace at 500° C. for 8 hours to obtain a calcium fluoride carrier.

[0080] Step 103, 0.12 mol of cesium nitrate and 0.03 mol of copper sulfate are dissolved in 100 mL of distilled water to prepare a solution, and then a calcium fluoride carrier is added. After impregnation for 20 hours, the solution is dried at 100° C. for more than 12 hours, and the precursor is calcined at 550° C. in a muffle furnace for 8 hours to obtain a 0.12Cs-0.03Cu-0.85Ca-F catalyst.

[0081] Reaction evaluation:

[0082] The fluorination catalyst 0.12Cs-0.03Cu-0.85Ca-F prepared above was used as a gas-phase dehydrochlorination catalyst. 30 mL of the catalyst was loaded into a fixed-bed tubular reactor with a tube diameter of Φ38 mm. At a reaction temperature of 350°C, CF3CH2CCl=CH2 was passed through the catalyst bed with a residence time of 20 s. After reacting for 4 hours, the product was washed with water and alkali to remove HCl and then analyzed by gas chromatography. The CF3CH2CCl=CH2 conversion rate was 78.1%, and the CF3CH2C≡CH selectivity was 96.3%.

[0083] 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:

[0084] 1 H NMR (500MHz, Chloroform-d) δ3.37 (qd, J=9.0, 3.0Hz, 2H), 2.65 (t, J=3.0Hz, 1H).

[0085] 13 C NMR (125MHz, Chloroform-d) δ120.89 (qdd, J=268.1, 6.9, 1.1Hz), 78.20 (d, J=8.0Hz), 72.18 (pd, J=3.8, 1.2Hz), 24.17-22.37 (m).

[0086] 19 F NMR(472MHz,Chloroform-d)δ-70.41.

[0087] The above data prove that the product obtained is CF3CH2C≡CH.

[0088] Embodiments 4 to 13:

[0089] This embodiment provides a method for preparing fluorinated alkynes. The method uses the fluorination catalyst 0.12Cs-0.03Cu-0.85Ca-F prepared in Example 3 to prepare fluorinated alkynes through a gas phase dehydrochlorination reaction. The methods for preparing fluorinated alkynes in Examples 4 to 13 are basically the same as the method for preparing fluorinated alkynes in Example 3, and the only difference is that the raw materials used in Examples 4 to 13 are different, namely, fluorinated monochloroolefins.

[0090] The reaction results of Examples 4 to 13 are shown in Table 1.

[0091] Table 1 Reaction results of Examples 4 to 13

[0092]

[0093]

[0094] Embodiment 14:

[0095] This example provides a method for preparing fluorinated dichloroolefins. In this method, 0.2 mol of CF≡CH prepared in Example 1 is added to a 150 ml stainless steel belt stirring autoclave. The reaction temperature is 50° C. After stirring, 0.1 mol of Cl2 is introduced. The reaction pressure is maintained at 0.5 MPa. The reaction is carried out for 6 hours. The temperature is lowered to stop the reaction. The product is analyzed by gas chromatography. The conversion rate of CF≡CH is 49.8%, and the selectivity of CFCl=CHCl is 98.5%.

[0096] 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:

[0097] 1 H NMR (500MHz, Chloroform-d) δ5.91 (d, J = 52.4Hz, 1H).

[0098] 13 C NMR (125MHz, Chloroform-d) δ144.79 (d, J = 252.1Hz), 100.71 (d, J = 20.0Hz).

[0099] 19 F NMR(472MHz,Chloroform-d)δ-79.39.

[0100] The above data prove that the product obtained is CFCl=CHCl.

[0101] Embodiment 15:

[0102] This example provides a method for preparing fluorinated dichloroolefins. The method comprises adding 0.12 mol of CF3C≡CH4 prepared in Example 2 into a 150 ml stainless steel stirring autoclave. The reaction temperature is 0°C. After stirring is started, 0.1 mol of Cl2 is introduced. The reaction pressure is maintained at 0.5 MPa. The reaction is carried out for 12 h. The temperature is then lowered to stop the reaction. The product is analyzed by gas chromatography. The conversion rate of CF3C≡CH4 is 83.1%, and the selectivity of CF3CCl=CHCl is 97.5%.

[0103] 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:

[0104] 1 H NMR (500MHz, CDCl3) δ7.16 (d, J=1.2Hz, 1H).

[0105] 13 C NMR (126MHz, CDCl3) δ 125.65 (q, J = 5.6Hz), 124.68 (q, J = 38.0Hz), 119.87 (q, J = 272.5Hz).

[0106] 19 F NMR (471MHz,CDCl3)δ-68.31.

[0107] The above data prove that the product obtained is CF3CCl=CHCl.

[0108] Embodiment 16:

[0109] This example provides a method for preparing fluorinated dichloroolefins. The method comprises adding 0.15 mol of CF3CH2C≡CH prepared in Example 3 into a 150 ml stainless steel belt stirring autoclave, the reaction temperature is 30°C, stirring is started, 0.1 mol of Cl2 is introduced, the reaction pressure is maintained at 0.5 MPa, the reaction is carried out for 9 hours, the temperature is lowered to stop the reaction, and the product is analyzed by gas chromatography. The conversion rate of CF3CH2C≡CH is 66.5%, and the selectivity of CF3CH2CCl=CHCl is 98.1%.

[0110] 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:

[0111] 1 H NMR (500MHz, Chloroform-d) δ6.15 (t, J=1.0Hz, 1H), 3.29 (qd, J=9.0, 1.0Hz, 2H).

[0112] 13C 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).

[0113] 19 F NMR(472MHz,Chloroform-d)δ-63.70.

[0114] The above data prove that the product obtained is CF3CH2CCl=CHCl.

[0115] Embodiments 17 to 26:

[0116] This example provides a method for preparing fluorinated dichloroolefins. This method is basically the same as the method for preparing fluorinated dichloroolefins in Example 16. The only difference is that different fluorinated alkynes are used as reaction raw materials in Examples 17 to 26. The reaction results of Examples 17 to 26 are shown in Table 2.

[0117] Table 2 Reaction results of Examples 17 to 25

[0118]

[0119]

[0120] The fluorinated dichloroolefins obtained according to Examples 14 to 26 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.

[0121] Embodiment 27:

[0122] This example shows the application of fluorinated dichloroolefin CFCl=CHCl(E) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0123] Embodiment 28:

[0124] This example shows the application of fluorinated dichloroolefin CH3ClC=CFCl(Z) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0125] Embodiment 29:

[0126] This example shows the application of fluorinated dichloroolefin CF3CCl=CFCl(E) as electronic coolant, and develops boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0127] Embodiment 30:

[0128] This example shows the application of fluorinated dichloroolefin CH2FCCl=CHCl(E) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0129] Embodiment 31:

[0130] This example shows the application of fluorinated dichloroolefin CH2FCCl=CHCl(Z) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0131] Embodiment 32:

[0132] This example shows the application of fluorinated dichloroolefin CHF2CCl=CHCl(Z) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0133] Embodiment 33:

[0134] This example shows the application of fluorinated dichloroolefin CHF2CCl=CHCl(E) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0135] Embodiment 34:

[0136] This example shows the application of fluorinated dichloroolefin CF3CCl=CHCl(Z) as electronic coolant, and the boiling point, stability, ODP value, GWP 100The test results and performance are detailed in Table 3 and Table 4.

[0137] Embodiment 35:

[0138] This example shows the application of fluorinated dichloroolefin CF3CCl=CHCl(E) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0139] Embodiment 36:

[0140] This example shows the application of fluorinated dichloroolefin CF3CCl=CClCH3(Z) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0141] Embodiment 37:

[0142] This example shows the application of fluorinated dichloroolefin CF3CCl=CClCH3(E) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0143] Embodiment 38:

[0144] This example shows the application of fluorinated dichloroolefin CF3CCl=CClCHF2(Z) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0145] Embodiment 39:

[0146] This example shows the application of fluorinated dichloroolefin CF3CCl=CClCHF2(E) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0147] Embodiment 40:

[0148] This example shows the application of fluorinated dichloroolefin CF3CCl=CClCH2F(Z) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0149] Embodiment 41:

[0150] This example shows the application of fluorinated dichloroolefin CF3CCl=CClCH2F(E) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0151] Embodiment 42:

[0152] This example shows the application of fluorinated dichloroolefin CF3CH2CCl=CHCl(E) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0153] Embodiment 43:

[0154] This example shows the application of fluorinated dichloroolefin CF3CF2CCl=CHCl(E) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0155] Embodiment 44:

[0156] This example shows the application of fluorinated dichloroolefin CF3CF2CCl=CHCl(Z) as electronic coolant, and the boiling point, stability, ODP value, GWP 100 The test results and performance are detailed in Table 3 and Table 4.

[0157] Performance Test:

[0158] The fluorinated dichloroolefin electronic coolant in Examples 27 to 44 was added into pressure-resistant glass bottles with stoppers, respectively, and stirred continuously for 1000 hours at a temperature of 80° C. Then, the purity before and after the test was tested by GC, as shown in Table 3, and it was found that the change was small. Therefore, the fluorinated dichloroolefin electronic coolant of the present invention has excellent thermal stability.

[0159] Table 3 Boiling point and stability before and after the test in Examples 27 to 44

[0160]

[0161]

[0162] ODP values ​​and GWP values ​​of the fluorinated dichloroolefin electronic coolants in Examples 27 to 44 100 The values ​​and dielectric constants are shown in Table 4.

[0163] Table 4 ODP values ​​and GWP in Examples 27 to 44 100 Value and dielectric constant

[0164]

[0165]

[0166] As can be seen from Table 4, the fluorinated dichloroolefin electronic coolant in Examples 27 to 44 introduces chlorine atoms into the C=C double bond structure to adjust the boiling point of the electronic coolant, and the -CCl=CCl- double bond is easily broken and decomposed in the atmosphere, and the ODP value is low, while the GWP of the fluorinated electronic coolant is reduced. 100 The value significantly improves the environmental performance of fluorine-containing electronic coolant. In addition, the dielectric constant of fluorine-containing electronic coolant is less than 3, which meets the use requirements.

[0167] Comprehensive consideration of the GWP of fluorinated dichloroolefins 100 According to the dielectric constants and dielectric constants, it is found that the fluorinated dichloroolefins of Zusammen isomer (trans isomer) are more advantageous, and CFCl=CHCl(E), CH2FCCl=CHCl(E), CHF2CCl=CHCl(E), CF3CCl=CHCl(E), CF3CCl=CClCH3(E), CF3CCl=CClCHF2(E), CF3CCl=CClCH2F(E) and CF3CH2CCl=CHCl(E) are preferred.

Claims

1. A method for preparing fluorinated dichloroolefins, characterized in that: The method comprises the following steps: Step 1, preparing fluorinated alkyne R1C≡CR2 by gas phase dehydrochlorination of fluorinated monochloroolefin R1CCl=CHR2; Step 2, fluorine-containing alkyne R1C≡CR2 and chlorine are reacted to prepare fluorine-containing dichloroolefin R1CCl=CClR2; Where: R1 is -H, -CF3, -CHF2, -CH2F or -CH3; R2 is -F, -CF3, -CHF2 or -CH2F.

2. The method for preparing fluorinated dichloroolefins according to claim 1, characterized in that: In step 1, the gas-phase dehydrochlorination catalyst for the gas-phase dehydrochlorination reaction is a fluorination catalyst Cs-Cu-Ca-F; in the fluorination catalyst Cs-Cu-Ca-F, the molar ratio of Cs, Cu and Ca is (0.9-1.5):(0.1-0.5):(8-9).

3. The method for preparing fluorinated dichloroolefins according to claim 2, characterized in that: In step 1, the preparation method of the fluorination catalyst Cs-Cu-Ca-F is: Step 101, dissolving calcium oxalate and polyethylene glycol in ethylene glycol, reflux treatment under stirring, and then filtering to obtain a solid, washing the solid with deionized water until it is neutral, and then drying to obtain a calcium oxide precursor; Step 102, dissolving the calcium oxide precursor obtained in step 101 in water to prepare a calcium oxide precursor aqueous solution, adding hydrofluoric acid dropwise to the calcium oxide precursor aqueous solution, filtering to obtain a solid, washing the solid with water to neutrality, drying, and calcining to obtain a calcium fluoride carrier; Step 103, cesium nitrate and copper sulfate are dissolved in water to prepare a solution, and then the calcium fluoride carrier obtained in step 102 is added, impregnated, dried, and calcined to obtain the fluorination catalyst Cs-Cu-Ca-F.

4. The method for preparing fluorinated dichloroolefins according to claim 1, characterized in that: In step 1, the reaction temperature of the gas phase dehydrochlorination reaction is 300-400° C., and the contact time is 10-30 seconds; In step 2, the reaction temperature of the addition reaction is 0-50° C.; the molar ratio of the fluorine-containing alkyne R1C≡CR2 to chlorine is (1.2-2):

1.

5. The method for preparing fluorinated dichloroolefins according to claim 1, characterized in that: The boiling range of the fluorobischloroolefin is 40-100°C; the dielectric constant of the fluorobischloroolefin is less than 5; the GWP of the fluorobischloroolefin is 100 The value is less than 500.

6. The method for preparing fluorinated dichloroolefins according to claim 5, characterized in that: The boiling range of the fluorobischloroolefin is 60-800°C; the dielectric constant of the fluorobischloroolefin is less than 2.5; the GWP of the fluorobischloroolefin is 100 The value is less than 150.

7. The method for preparing fluorinated dichloroolefins according to claim 1, characterized in that: The fluorobis(chloro)olefin R1CCl=CClR2 is CFCl=CHCl(E), CH2FCCl=CHCl(E), CHF2CCl=CHCl(E), CF3CCl=CHCl(E), CF3CCl=CClCH3(E), CF3CCl=CClCHF2(E), CF3CCl=CClCH2F(E) or CF3CH2CCl=CHCl(E).

8. A fluorinated dichloroolefin, characterized in that: The structure of fluorinated dichloroolefins is R1CCl=CClR2; Where: R1 is -H, -CF3, -CHF2, -CH2F or -CH3; R2 is -F, -CF3, -CHF2 or -CH2F.

9. The fluorinated dichloroolefin according to claim 8, characterized in that The fluorinated dichloroolefin is prepared by the preparation method of the fluorinated dichloroolefin as claimed in any one of claims 1 to 7.

10. Use of the fluorinated dichloroolefin as claimed in claim 8 as electronic coolant.

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