Fluorine-containing dichloroalkenes, methods of making and use

Abstract

The application provides a fluorine-containing dichloroalkene, a preparation method and application, and comprises the following steps: in step one, fluorine-containing monochloroalkene R1CCl=CHR2 is subjected to a gas-phase dehydrochlorination reaction to prepare fluorine-containing alkyne R1C=CR2; in step two, the fluorine-containing alkyne R1C=CR2 is subjected to an addition reaction with chlorine to prepare fluorine-containing dichloroalkene R1CCl=CClR2. The gas-phase dehydrochlorination catalyst for the gas-phase dehydrochlorination reaction is fluorinated catalyst Cs-Cu-Ca-F. The dehydrochlorination reaction has good reaction effect, and the product selectivity can reach 95%; the addition reaction has mild reaction conditions, and the product selectivity is above 95%. The fluorine-containing dichloroalkene R1CCl=CClR2 prepared by the application has good stability, low dielectric constant and good insulation performance as an electronic cooling liquid by optimizing the symmetrical arrangement of chlorine atoms.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, and relates to fluorochloroolefins, specifically to a fluorodichloroolefin, its preparation method, and its application. Background Technology

[0002] Immersion liquid cooling is a typical direct-contact liquid cooling method. Electronic equipment is immersed in coolant, and heat is conducted through 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, and perfluoropolyethers. Their main technical indicators include thermal conductivity, dielectric constant, and global warming potential (GWP). 100 Electronic coolants, in particular, require good thermal conductivity, insulation, and environmental friendliness (GWP). Currently, most electronic coolants on the market possess good thermal conductivity and insulation, but their GWP... 100 The dielectric constant of the electronic coolant is generally high, resulting in a longer atmospheric lifespan and a greater impact on the environment; or the dielectric constant of the electronic coolant is high, affecting the integrity and stability of the signals of the electronic components immersed in it.

[0003] The main component of FC-72 dual-phase immersion electronic coolant developed by 3M is perfluorohexane, which has a dielectric constant of 1.75 and is thermodynamically and chemically stable, but its GWP (Gross Potentially High Power Content) is low. 100 A value higher than 5000 does not meet the standards for green environmental protection.

[0004] Studies have found that fluorochloroolefins are a high-performance electronic coolant medium. Currently, there are few reported methods for preparing fluorochloroolefins, especially those with chlorine at symmetrical double bond positions.

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

[0006] US2009043118 discloses a method for producing a composition comprising 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 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 1,2-dichloro-3,3,3-trifluoropropene produced is in the range of 0-20.2%. 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, the reaction temperature is 150℃, the reaction pressure is 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

[0007] In view of the deficiencies in the prior art, the purpose of the present application is to provide a preparation method of fluorine-containing dichloroalkene, solving the technical problem that the selectivity of the preparation method of fluorine-containing dichloroalkene in the prior art needs to be further improved.

[0008] Another purpose of the present application is to provide a fluorine-containing dichloroalkene and application, solving the technical problem that the comprehensive performance of the electronic coolant in the prior art needs to be further improved.

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

[0010] A preparation method of fluorine-containing dichloroalkene, comprising the following steps:

[0011] Step one, preparing fluorine-containing acetylene R1C≡CR2 by gas phase dehydrochlorination reaction of fluorine-containing monochloroalkene R1CCl=CHR2.

[0012] Step two, preparing fluorine-containing dichloroalkene R1CCl=CClR2 by addition reaction of fluorine-containing acetylene R1C≡CR2 and chlorine.

[0013] In the formula:

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

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

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

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

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

[0019] In step one, the fluorination catalyst Cs-Cu-Ca-F is prepared by the following method:

[0020] In step 101, calcium oxalate and polyethylene glycol are dissolved in ethylene glycol, and the mixture is refluxed under stirring, and then filtered to obtain a solid, which is washed with deionized water until neutral, and then dried to obtain a calcium oxide precursor.

[0021] In step 102, the calcium oxide precursor obtained in step 101 is dissolved in water to obtain a calcium oxide precursor aqueous solution, hydrofluoric acid is added dropwise into the calcium oxide precursor aqueous solution, and then filtered to obtain a solid, which is washed with water until neutral, and then dried, and then calcined to obtain a calcium fluoride carrier.

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

[0023] In step one, the reaction temperature of the gas-phase dehydrochlorination reaction is 300-400℃, and the contact time is 10-30s.

[0024] In step two, the reaction temperature of the addition reaction is 0-50℃.

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

[0026] Specifically, the boiling range of the fluorodichloroalkene is 40-100℃; the dielectric constant of the fluorodichloroalkene is less than 5; and the GWP value of the fluorodichloroalkene is less than 500. 100

[0027] Preferably, the boiling range of the fluorodichloroalkene is 60-800℃; the dielectric constant of the fluorodichloroalkene is less than 2.5; and the GWP value of the fluorodichloroalkene is less than 150. 100

[0028] ​​Specifically, the fluorine-containing monochloroalkene R1CCl=CHR2 is CFCI=CHCI, 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 fluorine-containing monochloroalkene R1CCl=CHR2 is CFCI=CHCI, 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.

[0030] Preferably, the fluorine-containing dichloroalkene R1CCl=CClR2 is CFCI=CHCI (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 application also protects a fluorine-containing dichloroalkene, characterized in that the structure of the fluorine-containing dichloroalkene is R1CCl=CClR2.

[0032] In the formula, R1 is -H, -CF3, -CHF2, -CH2F or -CH3; R2 is -F, -CF3, -CHF2 or -CH2F.

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

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

[0035] Further, the fluorine-containing dichloroalkene is prepared by the preparation method of the fluorine-containing dichloroalkene as described above.

[0036] The present application also protects the use of the fluorine-containing dichloroalkene as described above as electronic coolant.

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

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

[0039] (II) In the present application, the catalyst Cs-Cu-Ca-F is suitable for the preparation of fluorine-containing alkyne by dehydrochlorination of halogenated fluoroalkene under gas phase condition, especially for the preparation of fluorine-containing alkyne by selective dehydrochlorination.

[0040] (III) The fluorine-containing dichloroalkene R1CCl=CClR2 prepared in the present application has good stability, low dielectric constant and good insulation performance as electronic coolant by optimizing the symmetrical arrangement of chlorine atoms.

[0041] (IV) The fluorine-containing dichloroalkene R1CCl=CClR2 prepared in the present application has good stability, low dielectric constant and good insulation performance as electronic coolant by optimizing the symmetrical arrangement of chlorine atoms.

[0042] The specific content of the present application is further explained and described in detail in combination with the following examples. DETAILED DESCRIPTION

[0043] It should be noted that all raw materials and reagents in the present application, unless otherwise specified, are all known raw materials and reagents in the prior art, which can be obtained from commercial channels. All experimental methods in the present application, unless otherwise specified, are conventional methods.

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

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

[0046] In the present application, the fluorine-containing dichloroalkene R1CCl=CClR2 as electronic coolant is applied to the heat transfer working medium of the immersed two-phase cooling system in the field of network base station, microprocessor, power transformer, circuit board semiconductor device or chemical reactor.

[0047] The fluorine-containing dichloroalkene as electronic coolant carries out relevant property tests, and the specific items are as follows:

[0048] In the thermal stability test of the present application, a certain amount of electronic coolant is added to a glass bottle with a bottle plug that can withstand pressure, and continuously stirred at 80℃ for 1000 hours. The fluorine-containing dichloroalkene can inhibit its continuous deterioration due to the presence of hydrogen atoms, thereby improving its thermal stability. The ODP value is obtained by establishing LINL and AER ozone depletion models for calculation and simulation. 100The values are obtained by the relative rate experiment method. The dielectric constant is obtained by using a microwave network analyzer (1 kHz).

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

[0050] The following gives specific examples of the present application, and it should be noted that the present application is not limited to the following specific examples, and any equivalent variations made on the basis of the technical solutions of the present application fall within the protection scope of the present application.

[0051] Example 1:

[0052] The present example gives a preparation method of a fluorination catalyst Cs-Cu-Ca-F, and 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, 0.9 mol of calcium oxalate and 0.3 mol of polyethylene glycol-8000 are dissolved in 100 mL of ethylene glycol, and the mixture is treated by refluxing under stirring at 120℃ for 8 h, and then the solid is extracted by filtration, and then the solid is washed to neutral with deionized water, and then the solid is dried at 150℃ for 12 h to obtain a calcium oxide precursor.

[0054] Step 102, the calcium oxide precursor is dissolved in 100 mL of distilled water to form a solution, and 3.6 mol of hydrofluoric acid is slowly added dropwise into the aqueous solution of the calcium oxide precursor, and then the solid is extracted by filtration, and then the solid is washed to neutral with deionized water, and then the solid is dried at 100℃ for 12 h, and then the precursor is calcined in a muffle furnace at 550℃ for 6 h to obtain a calcium fluoride carrier.

[0055] Step 103, 0.09 mol of cesium nitrate and 0.01 mol of copper sulfate are respectively dissolved in 100 mL of distilled water to form solutions, and then the calcium fluoride carrier is added, and then the mixture is soaked for 10 h, and then the mixture is dried at 100℃ for 12 h or more, and then the precursor is calcined in a muffle furnace at 500℃ for 12 h to obtain the 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 is used as a gas phase dehydrochlorination catalyst, 30 mL of the gas phase dehydrochlorination catalyst is loaded into a fixed bed tubular reactor with a tube diameter of Φ38 mm, CFCl=CH2 is passed through the catalyst bed at a reaction temperature of 300℃, the residence time is 30 s, and after the reaction for 4 h, the product is analyzed by gas chromatography after removing HCl and HF by water washing and alkali washing, the conversion rate of CFCl=CH2 is 68.5%, and the selectivity of CF≡CH is 84.8%.

[0058] The above-mentioned product was separated and purified to obtain a sample with a purity of 99.5%, which was analyzed by NMR.

[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 proves that the product obtained is CF≡CH.

[0064] Example 2:

[0065] This embodiment provides a method for preparing a fluorinated catalyst Cs-Cu-Ca-F, specifically a fluorinated catalyst consisting of 0.15Cs-0.05Cu-0.80Ca-F. The method includes the following steps:

[0066] Step 101: Dissolve 0.8 mol of calcium carbonate and 0.4 mol of polyethylene glycol-8000 in 100 mL of ethylene glycol, reflux at 120 °C for 6 h with stirring, filter to obtain solid, wash with deionized water until neutral, and then dry at 150 °C for 12 h to obtain calcium oxide precursor.

[0067] Step 102: Dissolve the calcium oxide precursor in 100 mL of distilled water to prepare a solution. Slowly add 3.2 mol of hydrofluoric acid to the calcium oxide precursor aqueous solution. Filter the solution to obtain a solid. Wash the solid with deionized water until neutral. Dry the solid at 100 °C for 10 h. Then calcine the solid in a muffle furnace at 400 °C for 12 h to obtain a calcium fluoride carrier.

[0068] Step 103: Dissolve 0.15 mol cesium nitrate and 0.05 mol copper sulfate in 100 mL of distilled water to prepare solutions, then add calcium fluoride support, impregnate for 24 h, dry at 100 °C for more than 12 h, and then calcine the precursor in a muffle furnace at 600 °C for 6 h to obtain the fluorination catalyst 0.15Cs-0.05Cu-0.80Ca-F.

[0069] Response 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 Φ 38 mm, CF3CCl=CH2 was passed through the catalyst bed at a reaction temperature of 400°C, the residence time was 10 s, after 4 h of reaction, the product was analyzed by gas chromatography after removal of HCl by water washing and alkali washing, the conversion rate of CF3CCl=CH2 was 76.5%, and the selectivity of CF3C≡CH was 94.6%.

[0071] The product above was separated and purified to obtain a sample with a purity of 99.5%, which was detected by nuclear magnetic resonance:

[0072] 1 H NMR (500 MHz, Chloroform-d) δ 2.45 (s, 1H).

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

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

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

[0076] Example 3:

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

[0078] Step 101, 0.85 mol of calcium carbonate and 0.5 mol of polyethylene glycol-8000 were dissolved in 100 mL of ethylene glycol, and the mixture was treated by refluxing at 120°C under stirring for 6 h, then the solid was extracted by filtration, washed with deionized water until neutral, and then dried at 150°C for 12 h to obtain a calcium oxide precursor.

[0079] Step 102, calcium oxide precursor was dissolved in 100 mL distilled water to form a solution, 3.4 mol ammonium fluoride solution was slowly added into the calcium oxide precursor aqueous solution, and then the solid was obtained by filtration, washed with deionized water until neutral, and then dried at 100°C for 10 h, and then the precursor was calcined at 500°C in a muffle furnace for 8 h to obtain the calcium fluoride carrier.

[0080] Step 103, 0.12 mol cesium nitrate and 0.03 mol copper sulfate were respectively dissolved in 100 mL distilled water to form a solution, and then the calcium fluoride carrier was added, and then immersed for 20 h, and then dried at 100°C for 12 h or more, and then the precursor was calcined at 550°C in a muffle furnace for 8 h to obtain the 0.12Cs-0.03Cu-0.85Ca-F catalyst.

[0081] Reaction evaluation:

[0082] The fluorinated 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 in a fixed bed tubular reactor with a pipe diameter of Φ38 mm, CF3CH2CCl=CH2 passed through the catalyst bed at a reaction temperature of 350°C, the residence time was 20 s, and after reaction for 4 h, the product was analyzed by gas chromatography after water washing and alkali washing to remove HCl, the conversion rate of CF3CH2CCl=CH2 was 78.1%, and the selectivity of CF3CH2C≡CH was 96.3%.

[0083] The product above was separated and purified to obtain a sample with a purity of 99.5%, which was detected by nuclear magnetic resonance:

[0084] 1 H NMR (500 MHz, Chloroform-d) δ 3.37 (qd, J = 9.0, 3.0 Hz, 2H), 2.65 (t, J = 3.0 Hz, 1H).

[0085] 13 C NMR (125 MHz, Chloroform-d) δ 120.89 (qdd, J = 268.1, 6.9, 1.1 Hz), 78.20 (d, J = 8.0 Hz), 72.18 (pd, J = 3.8, 1.2 Hz), 24.17-22.37 (m).

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

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

[0088] Examples 4-13:

[0089] This example gives a method for preparing a fluorine-containing alkyne, which uses the fluorination catalyst 0.12Cs-0.03Cu-0.85Ca-F prepared in Example 3 to prepare a fluorine-containing alkyne by gas-phase dehydrochlorination. The method for preparing a fluorine-containing alkyne in Examples 4 to 13 is substantially the same as the method for preparing a fluorine-containing alkyne in Example 3, except that the starting material fluorine-containing monochloroalkene used in Examples 4 to 13 is different.

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

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

[0092]

[0093]

[0094] Example 14:

[0095] This example gives a method for preparing a fluorine-containing dichloroalkene, which adds 0.2 mol of CF≡CH prepared in Example 1 to a 150 ml stainless steel high-pressure reaction vessel with stirring, and then introduces 0.1 mol of Cl2 after the reaction temperature is raised to 50°C and stirring is started. The reaction pressure is maintained at 0.5 MPa, and the reaction is carried out for 6 h. The reaction is stopped by cooling, and the product is analyzed by gas chromatography. The conversion of CF≡CH is 49.8%, and the selectivity of CFCl=CHCl is 98.5%.

[0096] The product is separated and purified as described above to obtain a sample with a purity of 99.9%, which is detected by nuclear magnetic resonance:

[0097] 1 H NMR (500 MHz, Chloroform-d) δ 5.91 (d, J = 52.4 Hz, 1H).

[0098] 13 C NMR (125 MHz, Chloroform-d) δ 144.79 (d, J = 252.1 Hz), 100.71 (d, J = 20.0 Hz).

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

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

[0101] Example 15:

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

[0103] The above-mentioned product was separated and purified to obtain a sample with a purity of 99.9%, which was analyzed by NMR.

[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 proves that the product obtained is CF3CCl=CHCl.

[0108] Example 16:

[0109] This embodiment provides a method for preparing fluorinated dichloroolefins. The method involves adding 0.15 mol of CF3CH2C≡CH obtained in Example 3 to a 150 ml stainless steel high-pressure reactor with a stirrer. The reaction temperature is 30°C. After stirring is started, 0.1 mol of Cl2 is introduced, and the reaction pressure is maintained at 0.5 MPa. The reaction is carried out for 9 hours, then cooled to stop the reaction. The product is analyzed by gas chromatography, and the conversion rate of CF3CH2C≡CH is 66.5%, and the selectivity of CF3CH2CCl=CHCl is 98.1%.

[0110] The above-mentioned product was separated and purified to obtain a sample with a purity of 99.9%, which was analyzed by NMR.

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

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

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

[0115] Examples 17-26:

[0116] This example gives a method for preparing a fluorine-containing dichloroalkene, which is basically the same as the method for preparing a fluorine-containing dichloroalkene in Example 16, with the only difference being that different fluorine-containing alkynes are used as the raw materials in Examples 17-26. The reaction results of Examples 17-26 are shown in Table 2.

[0117] Table 2 Reaction results of Examples 17-26

[0118]

[0119]

[0120] The fluorine-containing dichloroalkenes obtained according to Examples 14-26 are: CFCI=CHCI, CH3CC1=FC1, CF3CC1=FC1, CH2FCC1=CHCI, CHF2CC1=CHCI, CF3CC1=CHCI, CF3CC1=CC1CH3, CF3CC1=CC1CHF2, CF3CC1=CC1CH2F, CHF2CC1=CC1CHF2, CH2FCC1=CC1CH2F, CF3CH2CC1=CHCI and CF3CF2CC1=CHCI, and samples with a purity of 99.9% or higher were obtained by rectification separation.

[0121] Example 27:

[0122] This example gives an application of the fluorine-containing dichloroalkene CFCI=CHCI (E) as an electronic coolant, and properties tests of boiling point, stability, ODP value, GWP 100 value and dielectric constant. The test results and performance are shown in Tables 3 and 4.

[0123] Example 28:

[0124] This example gives the application of fluorine-containing dichloroalkene CH3CCl=CFCl (Z) as electronic coolant, to carry out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0125] Example 29:

[0126] This example gives the application of fluorine-containing dichloroalkene CH3CCl=CFCl (Z) as electronic coolant, to carry out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0127] Example 30:

[0128] This example gives the application of fluorine-containing dichloroalkene CH3CCl=CFCl (Z) as electronic coolant, to carry out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0129] Example 31:

[0130] This example gives the application of fluorine-containing dichloroalkene CH3CCl=CFCl (Z) as electronic coolant, to carry out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0131] Example 32:

[0132] This example gives the application of fluorine-containing dichloroalkene CH3CCl=CFCl (Z) as electronic coolant, to carry out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0133] Example 33:

[0134] This example gives the application of fluorine-containing dichloroalkene CH3CCl=CFCl (Z) as electronic coolant, to carry out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0135] Example 34:

[0136] This example gives the application of fluorine-containing dichloroalkene CH3CCl=CFCl (Z) as electronic coolant, to carry out the boiling point, stability, ODP value, GWP 100The boiling point, stability, ODP value, GWP value and dielectric constant of the fluorine-containing dichloroalkene CF3CCl=CH2(E) used as electronic coolant were tested. The test results and performance are shown in Table 3 and Table 4.

[0137] Example 35:

[0138] This example gives the application of fluorine-containing dichloroalkene CF3CCl=CClCH3(Z) as electronic coolant, the boiling point, stability, ODP value, GWP value and dielectric constant were tested. The test results and performance are shown in Table 3 and Table 4. 100 The boiling point, stability, ODP value, GWP value and dielectric constant of the fluorine-containing dichloroalkene CF3CCl=CH2(E) used as electronic coolant were tested. The test results and performance are shown in Table 3 and Table 4.

[0139] Example 36:

[0140] This example gives the application of fluorine-containing dichloroalkene CF3CCl=CClCH3(Z) as electronic coolant, the boiling point, stability, ODP value, GWP value and dielectric constant were tested. The test results and performance are shown in Table 3 and Table 4. 100 The boiling point, stability, ODP value, GWP value and dielectric constant of the fluorine-containing dichloroalkene CF3CCl=CH2(E) used as electronic coolant were tested. The test results and performance are shown in Table 3 and Table 4.

[0141] Example 37:

[0142] This example gives the application of fluorine-containing dichloroalkene CF3CCl=CClCH3(E) as electronic coolant, the boiling point, stability, ODP value, GWP value and dielectric constant were tested. The test results and performance are shown in Table 3 and Table 4. 100 The boiling point, stability, ODP value, GWP value and dielectric constant of the fluorine-containing dichloroalkene CF3CCl=CH2(E) used as electronic coolant were tested. The test results and performance are shown in Table 3 and Table 4.

[0143] Example 38:

[0144] This example gives the application of fluorine-containing dichloroalkene CF3CCl=CClCHF2(Z) as electronic coolant, the boiling point, stability, ODP value, GWP value and dielectric constant were tested. The test results and performance are shown in Table 3 and Table 4. 100 The boiling point, stability, ODP value, GWP value and dielectric constant of the fluorine-containing dichloroalkene CF3CCl=CH2(E) used as electronic coolant were tested. The test results and performance are shown in Table 3 and Table 4.

[0145] Example 39:

[0146] This example gives the application of fluorine-containing dichloroalkene CF3CCl=CClCHF2(E) as electronic coolant, the boiling point, stability, ODP value, GWP value and dielectric constant were tested. The test results and performance are shown in Table 3 and Table 4. 100 The boiling point, stability, ODP value, GWP value and dielectric constant of the fluorine-containing dichloroalkene CF3CCl=CH2(E) used as electronic coolant were tested. The test results and performance are shown in Table 3 and Table 4.

[0147] Example 40:

[0148] This example gives the application of fluorine-containing dichloroalkene CF3CCl=CClCH2F(Z) as electronic coolant, the boiling point, stability, ODP value, GWP value and dielectric constant were tested. The test results and performance are shown in Table 3 and Table 4. 100 The boiling point, stability, ODP value, GWP value and dielectric constant of the fluorine-containing dichloroalkene CF3CCl=CH2(E) used as electronic coolant were tested. The test results and performance are shown in Table 3 and Table 4.

[0149] Example 41:

[0150] This example gives the application of fluorine-containing dichloroalkene CF3CCl=CClCH2F (E) as electronic coolant, carries out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0151] Example 42:

[0152] This example gives the application of fluorine-containing dichloroalkene CF3CH2CCl=CHCl (E) as electronic coolant, carries out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0153] Example 43:

[0154] This example gives the application of fluorine-containing dichloroalkene CF3CF2CCl=CHCl (E) as electronic coolant, carries out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0155] Example 44:

[0156] This example gives the application of fluorine-containing dichloroalkene CF3CF2CCl=CHCl (Z) as electronic coolant, carries out the boiling point, stability, ODP value, GWP 100 value and dielectric constant property test. The test results and performance are shown in Table 3 and Table 4.

[0157] Performance test:

[0158] The fluorine-containing dichloroalkene electronic coolant in Example 27 to Example 44 is added to a glass bottle with a bottle plug that can withstand pressure, and continuously stirred at a temperature of 80℃ for 1000 hours. Then the purity before and after the test is tested by GC, as shown in Table 3, it is found that the change is small, therefore, the fluorine-containing dichloroalkene electronic coolant of the present application has excellent thermal stability.

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

[0160]

[0161]

[0162] The ODP value, GWP value and dielectric constant of the fluorine-containing dichloroalkene electronic coolant in Example 27 to Example 44 are shown in Table 4. 100 ​

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

[0164]

[0165]

[0166] As shown in Table 4, the fluorinated dichloroolefin electronic coolants in Examples 27 to 44, by introducing chlorine atoms into the C=C double bond structure, adjust the boiling point of the electronic coolant. Furthermore, the -CCl=CCl- double bond is easily broken and decomposed in the atmosphere, resulting in a low ODP value. Simultaneously, this reduces the GWP of the fluorinated electronic coolant. 100 This value significantly improves the environmental performance of fluorinated electronic coolants. Furthermore, the dielectric constant of the fluorinated electronic coolant is less than 3, meeting usage requirements.

[0167] Taking into account the GWP of fluorinated dichloroolefins 100 Based on the values ​​and dielectric constants, fluorinated dichloroolefins of the Zusammen isomer (trans isomer) were found to be more advantageous, with 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) being preferred.

Claims

1. A process for the preparation of a fluorine-containing dichloroolefin, characterized in that, The method comprises the following steps: Step one, fluorine-containing monochloroalkene R1CCl=CHR2 is prepared into fluorine-containing acetylene R1C≡CR2 through gas phase dehydrochlorination reaction; The gas phase dehydrochlorination catalyst of the gas phase dehydrochlorination reaction is fluorinated catalyst Cs-Cu-Ca-F; in the fluorinated catalyst Cs-Cu-Ca-F, the molar ratio of Cs, Cu and Ca is (0.9-1.5):(0.1-0.5):(8-9); In step one, the reaction temperature of the gas phase dehydrochlorination reaction is 300-400 DEG C, and the contact time is 10-30 s; Step two, fluorine-containing acetylene R1C≡CR2 is prepared into fluorine-containing dichloroalkene R1CCl=CClR2 through addition reaction with chlorine; In the formula: R1 is -H, -CF3, -CHF2, -CH2F or -CH3; R2 is -F, -CF3, -CHF2 or -CH2F; In step two, the reaction temperature of the addition reaction is 0-50 DEG C; the molar ratio of fluorine-containing acetylene R1C≡CR2 to chlorine is (1.2-2):

1.

2. The process for preparing a fluorine-containing dichloroolefin according to claim 1, wherein In step one, the preparation method of the fluorinated catalyst Cs-Cu-Ca-F is as follows: Step 101, calcium oxalate and polyethylene glycol are dissolved in ethylene glycol, treated under reflux with stirring, then the solid is extracted by filtration, the solid is washed to neutral with deionized water, then dried to obtain calcium oxide precursor; Step 102, the calcium oxide precursor prepared in step 101 is dissolved in water to prepare calcium oxide precursor aqueous solution, hydrofluoric acid is added dropwise into the calcium oxide precursor aqueous solution, then the solid is extracted by filtration, the solid is washed to neutral with water, then dried, and after calcination, calcium fluoride carrier is obtained; Step 103, cesium nitrate and copper sulfate are respectively dissolved in water to prepare solutions, then the calcium fluoride carrier obtained in step 102 is added, after impregnation, drying and calcination, fluorinated catalyst Cs-Cu-Ca-F is obtained.

3. The process for preparing a fluorine-containing dichloroolefin according to claim 1, wherein The boiling range of the fluorodichloroalkene is 40-100℃; the dielectric constant of the fluorodichloroalkene is less than 5; the GWP 100 value of the fluorodichloroalkene is less than 500.

4. The process for preparing a fluorine-containing dichloroolefin according to claim 3, wherein The boiling point of the fluorodichloroalkene is 60-800℃; the dielectric constant of the fluorodichloroalkene is less than 2.5; the GWP 100 value of the fluorodichloroalkene is less than 150.

5. The process for preparing a fluorine-containing dichloroolefin according to claim 1, wherein The fluorodichloroolefins R1CC1=CC1R2 are CFCl=CHCl ( E ), CH2FCC1=CHCl ( E ), CHF2CC1=CHCl ( E ), CF3CC1=CHCl ( E ), CF3CC1=CC1CH3 ( E ), CF3CC1=CC1CHF2 ( E ), CF3CC1=CC1CH2F ( E ) or CF3CH2CC1=CHCl ( E ).

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