Hydrofluoroolefin compounds, methods of making and using the same

Abstract

The application provides a hydrofluoroalkene compound and a preparation method and application thereof, and belongs to the technical field of temperature control working medium. Five hydrofluoroalkene compounds are provided, the hydrofluoroalkene compounds have excellent environmental protection (ODP value is 0, and GWP value is less than 20), high insulation performance (voltage resistance > 40KV / mm), low dielectric constant (1.8-2.2), no flash point, excellent low-temperature resistance (pour point < -80 DEG C), and excellent material compatibility, and do not react chemically and dissolve, swell with most materials, and fully meet the requirements of temperature control working medium. In addition, the application provides a preparation and purification method of the intermediates and final products of the above-mentioned hydrofluoroalkene compounds, the obtained hydrofluoroalkene compounds are stable in quality, excellent in performance, have excellent heat dissipation and temperature control performance, and can play a role in energy saving and consumption reduction.

Description

Technical Field

[0001] This invention relates to the field of temperature-controlled working fluid technology, specifically to hydrofluoroolefin compounds, their preparation methods, and applications. Background Technology

[0002] Hydrofluoroolefins (R) f -CH=CH-R' f Hydrofluoroolefins (HFCs) have zero ODP and low GWP, offering environmental advantages. Compared to perfluoroolefins (PFOs), HFCs exhibit better structural stability, with carbon-carbon double bonds less prone to displacement and acidification. Furthermore, this type of HFC has lower dielectric properties, making it promising for immersion cooling applications in semiconductors and data centers.

[0003] In the existing technology, the molecular formula is C6H2F 10 Three non-terminated hydrofluoroolefins—(E)-1,1,1,4,5,5,5-heptafluoro-4-trifluoromethyl-2-pentene (HFO-153-10mzzy), (E)-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (HFO-153-10mzz), and (E)-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153-10mczz)—possess boiling points of approximately 50 °C (at atmospheric pressure) and relative permittivity of approximately 2.0, making them potential candidate working fluids for gas-liquid two-phase immersion cooling (2PIC) systems. However, the preparation processes for these hydrofluoroolefins are cumbersome, the raw materials are difficult to obtain, the costs are high, and the yields are poor, which limits their further application.

[0004] In addition, the prior art also discloses a class of fluorinated cyclic olefins with the following structural formula: Wherein, R1 is F or a perfluoroalkyl group, R2 is a perfluoroalkyl group, and the perfluoroalkyl group is -C. x F 2x+1 x is a natural number, and n = 1, 2, 3, 4, 5, 6, 7. However, the raw materials for the preparation of such fluorinated cyclic olefins are scarce and the cost is high; moreover, when used as a single-phase immersion coolant, it is easy to degrade and release perfluorinated fragment groups with more than 5 carbon atoms, causing environmental pollution.

[0005] Therefore, seeking novel, environmentally friendly hydrofluoroolefins with excellent temperature control and heat dissipation properties is of great significance to the field of electronic devices. Summary of the Invention

[0006] In view of this, the purpose of this invention is to provide a class of hydrofluoroolefin compounds, their preparation methods, and applications. The hydrofluoroolefin compounds provided by this invention have advantages in efficient temperature control, heat dissipation, and environmental friendliness, and can play a role in energy conservation and consumption reduction.

[0007] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a class of hydrofluoroolefin compounds, wherein the molecular formula of the hydrofluoroolefin compounds is C7H2F. 12 It has the structure shown in any one of Equations 1 to 5: Equation 1: CF3CF2CF2CF2CH=CHCF3 Equation 2: CF3CF2CF(CF3)CH=CHCF3; (CF3)2CFCF2CH=CHCF3 Equation 3; Equation 4: CF3CF2CH=CHCF2CF2CF3; Equation 5: CF3CF2CH=CHCF(CF3)2

[0008] Preferably, the hydrofluoroolefin compound comprises a cis or trans isomer having the structure shown in any one of Formulas 1 to 5.

[0009] Preferably, the hydrofluoroolefin compound has an ODP value of 0 and a GWP value of <20; The dielectric constant of the hydrofluoroolefin compound is <2.2 at 1 kHz. The hydrofluoroolefin compound is non-flammable and has no flash point; The pour point of the hydrofluoroolefin compound is < -80°C; The voltage withstand capability of the hydrofluoroolefin compound is >40KV / mm.

[0010] This invention provides a method for preparing the above-mentioned hydrofluoroolefin compound, comprising the following steps: Perfluoroiodoalkanes undergo free radical addition reactions with fluorinated alkenes to yield intermediates; The intermediate was mixed with an alkaline solution and subjected to an elimination reaction to obtain a hydrofluoroolefin compound. When preparing CF3CF2CF2CF2CH=CHCF3 having the structure shown in Formula 1, the perfluoroiodoalkane is CF3CF2CF2CF2I, and the fluorinated olefin is trifluoropropylene (CF3CH=CH2). When preparing CF3CF2CF(CF3)CH=CHCF3 having the structure shown in Formula 2, the perfluoroiodoalkane is CF3CF2CFICF3, and the fluorinated olefin is trifluoropropylene (CF3CH=CH2). When preparing (CF3)2CFCF2CH=CHCF3 having the structure shown in Formula 3, the perfluoroiodoalkane is (CF3)2CFCF2I, and the fluorinated olefin is trifluoropropylene (CF3CH=CH2). When preparing CF3CF2CH=CHCF2CF2CF3 having the structure shown in Formula 4, the perfluoroiodoalkane is CF3CF2CF2I, and the fluorinated olefin is pentafluorobutene (CF3CF2CH=CH2). When preparing CF3CF2CH=CHCF(CF3)2 having the structure shown in Formula 5, the perfluoroiodoalkane is (CF3)2CFI, and the fluorinated olefin is pentafluorobutene (CF3CF2CH=CH2).

[0011] Preferably, the molar ratio of the perfluoroiodoalkane to the fluorinated olefin is 10~20:1; The free radical addition reaction is carried out at a temperature of 180~220℃ for 4~10h.

[0012] Preferably, the alkaline solution comprises an inorganic base and a solvent, wherein the alkaline substance is KOH and / or NaOH, and the solvent comprises one or more of the following: quaternary ammonium salt aqueous solution, tertiary amine aqueous solution, alcohol-aqueous solution, and cyclic crown ether aqueous solution; The mass concentration of the alkaline solution is 25-50%; The elimination reaction is carried out at a temperature of 30~100℃ for 1~3 hours.

[0013] Preferably, the preparation method of CF3CF2CF1CF3 and (CF3)2CFCF2I includes the following steps: Trifluoroiodomethane (CF3I), hexafluoropropylene (CF3CF=CF2) and a free radical catalyst are mixed and subjected to a pre-addition reaction to obtain a pre-addition reaction solution, wherein the pre-addition reaction solution includes CF3CF2CFFICF3 and (CF3)2CFCF2I. The pre-addition reaction solution was separated by distillation to obtain CF3CF2CFICF3 and (CF3)2CFCF2I, respectively.

[0014] Preferably, the molar ratio of trifluoroiodomethane (CF3I), hexafluoropropylene (CF3CF=CF2), and the free radical catalyst is (4~10):1:0.1; The temperature of the pre-addition reaction is 120~180℃, and the pressure is 0~6MPa.

[0015] Preferably, after the elimination reaction, the method further includes post-treatment of the resulting elimination reaction solution, the post-treatment including the following steps: The elimination reaction solution was washed with water and separated, and the organic phase was collected to obtain crude product A; The crude product A was mixed with an alcoholic solution of acetic acid and zinc to carry out a deiodination reduction reaction. After washing with water and separating the liquid, the organic phase was collected to obtain the crude product B. The crude product B was subjected to distillation to obtain a pure hydrofluoroolefin compound with a purity ≥99%.

[0016] This invention provides the application of the above-mentioned hydrofluoroolefin compounds in temperature-controlled working fluids.

[0017] This invention provides a class of hydrofluoroolefin compounds having the following structure: molecular formula C7H2F 12 It includes five structures (including cis and trans isomers): CF3CF2CF2CF2CH=CHCF3, CF3CF2CF(CF3)CH=CHCF3, (CF3)2CFCF2CH=CHCF3, CF3CF2CH=CHCF2CF2CF3, and (CF3)2CFCH=CHCF2CF3. This hydrofluoroolefin compound exhibits excellent environmental friendliness (ODP value of 0, GWP value of less than 20), high insulation performance (withstand voltage > 40KV / mm), low dielectric constant (1.8~2.2), non-flammability and no flash point, excellent low-temperature resistance (pour point < -80℃), and excellent material compatibility. It does not chemically react with most materials, nor does it exhibit dissolution or swelling effects. It fully meets the requirements for temperature control working fluids and can be used as a low-temperature shock working fluid for chips and electronic components, as well as an immersion liquid cooling working fluid for high-power heat sources. It can also be used as a temperature control fluid for equipment in semiconductor chip manufacturing and chip testing equipment, demonstrating excellent heat dissipation and temperature control performance, and outstanding energy-saving and consumption-reducing effects. Compared with commercially available perfluoropolyether HT series products (GWP > 5000) and commercially available 3M-7000 series products (GWP value between 59 and 700), it has a greater environmental advantage.

[0018] This invention provides a method for preparing the aforementioned hydrofluoroolefin compounds. The method uses perfluoroiodoalkane and fluorinated olefin as raw materials. The perfluoroiodoalkane and fluorinated olefin undergo a free radical addition reaction to obtain an intermediate. This intermediate is then mixed with an alkaline solution and subjected to an elimination reaction to obtain the hydrofluoroolefin compound. The raw materials used in this invention are widely available and inexpensive. It does not use toxic heavy metal catalysts, thus possessing the advantages of being green and environmentally friendly. The overall yield of the obtained hydrofluoroolefin compounds can reach 80-85%.

[0019] Furthermore, the preparation method of the present invention also has the following beneficial effects: (1) By controlling the feed ratio of raw materials, the present invention reduces the generation of by-products, and the excess raw materials can be recycled, so that the utilization rate of raw materials can reach 99%, which can effectively reduce production costs.

[0020] (2) This invention provides a purification method for crude hydrofluoroolefin compounds. The residual raw materials in the crude product can be reacted with an alcoholic solution of zinc and degraded into low-boiling-point gaseous substances, which can be removed by natural volatilization or distillation. The process is simple and can improve the purity of the final product. After distillation, the purity of the crude product can reach more than 99.9% or even higher. Attached Figure Description

[0021] Figure 1 The NMR fluorine spectrum of CF3CF2CF2CF2CH=CHCF3 obtained in Example 1; Figure 2 The image shows the 1H NMR spectrum of CF3CF2CF2CF2CH=CHCF3 obtained in Example 1. Detailed Implementation

[0022] This invention provides a hydrofluoroolefin compound with the molecular formula C7H2F. 12 It has the structure shown in any one of Equations 1 to 5: Equation 1: CF3CF2CF2CF2CH=CHCF3 Equation 2: CF3CF2CF(CF3)CH=CHCF3; (CF3)2CFCF2CH=CHCF3 Equation 3; Equation 4: CF3CF2CH=CHCF2CF2CF3; Equation 5: CF3CF2CH=CHCF(CF3)2

[0023] In this invention, the hydrofluoroolefin compound comprises a cis or trans isomer having the structure shown in any one of Formulas 1 to 5.

[0024] In this invention, the hydrofluoroolefin compound has an ODP value of 0 and a GWP value of <20. The dielectric constant of the hydrofluoroolefin compound is <2.2 at 1 kHz. The hydrofluoroolefin compound is non-flammable and has no flash point; The hydrofluoroolefin compound has a pour point of <-80℃, a voltage withstand capability of >40KV / mm, and is a colorless and transparent liquid.

[0025] This invention provides a method for preparing the above-mentioned hydrofluoroolefin compound, comprising the following steps: Perfluoroiodoalkanes undergo free radical addition reactions with fluorinated alkenes to yield intermediates; The intermediate was mixed with an alkaline solution and subjected to an elimination reaction to obtain a hydrofluoroolefin compound.

[0026] Unless otherwise specified, all raw materials used in this invention are commercially available.

[0027] Specifically, the preparation method of CF3CF2CF2CF2CH=CHCF3 with the structure shown in Formula 1 includes the following steps: (1) A first radical addition reaction is carried out between nonafluorobutyl iodoalkane (CF3CF2CF2CF2I) and trifluoropropylene (CF3CH=CH2) to obtain the first intermediate C4F9CH2CHICF3 (1,1,1,4,4,5,5,6,6,7,7,7-dodecano-2-iodoheptane or 2H,3H,3H'-dodecano-2-iodoheptane). In this invention, the reaction formula for the first radical addition reaction is: CF3CF2CF2CF2I+CF3CH=CH2→CF3CF2CF2CF2CH2CHICF3; In this invention, the molar ratio of CF3CF2CF2CF2I to trifluoropropylene (CF3CH=CH2) is preferably 10-20:1, specifically 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, or 10:1. Under this molar ratio, the byproduct content can be controlled to ≤0.5%. As a specific embodiment of this invention, to ensure that the conversion rate of trifluoropropylene (CF3CH=CH2) to the target intermediate is >99%, the preferred molar ratio is 10:1, 12:1, 15:1, 18:1, or 20:1.

[0028] In this invention, the preferred temperature for the first free radical addition reaction is 180~220℃, specifically 180℃, 182℃, 184℃, 185℃, 188℃, 190℃, 192℃, 193℃, 194℃, 195℃, 198℃, 200℃, 202℃, 204℃, 205℃, 206℃, 208℃, 210℃, 212℃, 215℃, 216℃, 218℃, and 220℃; the preferred time for the first free radical addition reaction is 4~10 hours, specifically 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, and 10 hours. In this invention, the reaction pressure is observed, and the reaction is considered complete when the pressure remains constant for 3 consecutive hours. As a specific embodiment of the present invention, the preferred conditions for the first free radical addition reaction are: 180℃ / 10h, 200℃ / 6h, 215℃ / 4h or 220℃ / 4h.

[0029] To steer the reaction in a direction more favorable to obtaining the intermediate and reduce the content of byproducts, nonafluorobutyl iodide (CF3CF2CF2CF2I) is added in excess. Therefore, after the first radical addition reaction, the present invention preferably performs distillation on the resulting first radical addition reaction solution to extract the excess nonafluorobutyl iodide (CF3CF2CF2CF2I), which can be recycled for subsequent feed reactions without wasting raw materials. Through the distillation, the present invention ensures that the content of nonafluorobutyl iodide (CF3CF2CF2CF2I) in the intermediate (2H,3H,3H'-dodecano-2-iodoheptane) is ≤0.5%.

[0030] (2) The first intermediate C4F9CH2CHICF3 is mixed with an alkaline solution to undergo a first elimination reaction, yielding crude CF3CF2CF2CF2CH=CHCF3. In this invention, the reaction formula for the first elimination reaction is: C4F9CH2CHICF3+ alkaline system → CF3CF2CF2CF2CH=CHCF3; In this invention, the alkaline solution preferably comprises an inorganic base and a solvent. The alkaline substance is KOH and / or NaOH, and the solvent comprises one or more of the following: quaternary ammonium salt aqueous solution, tertiary amine aqueous solution, alcohol-water solution, and cyclic crown ether aqueous solution. In this invention, the quaternary ammonium salt preferably comprises benzyltrimethylammonium chloride or tetrabutylammonium bromide, and the mass concentration of the quaternary ammonium salt aqueous solution is preferably 3-10%, more preferably 5-8%. The tertiary amine preferably comprises one or more of triethylamine, tripropylamine, and tributylamine, and the mass concentration of the tertiary amine aqueous solution is preferably 3-15%, more preferably 5-10%. The alcohol in the alcohol-water solution is preferably one or more of methanol, ethanol, and isopropanol. The mass concentration of the cyclic crown ether in the cyclic crown ether solution is preferably 3-10%, more preferably 5-8%. In this invention, the mass concentration of the inorganic base in the alkaline solution is preferably 25-50%, more preferably 30-40%.

[0031] As a specific embodiment of the present invention, the alkaline solution is preferably a KOH / quaternary ammonium salt aqueous solution (KOH-benzyltrimethylammonium chloride aqueous solution, KOH-tetrabutylammonium bromide aqueous solution) or a KOH / water-alcohol solution (KOH-water-methanol solution, KOH-water-isopropanol solution).

[0032] This invention eliminates HI through a first elimination reaction. In this invention, the volume ratio of the first intermediate to the alkaline solution is preferably 1:1~5, more preferably 1:2~4; the temperature of the first elimination reaction is preferably 30~100℃, specifically 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 32℃, 36℃, 42℃, 46℃, 48℃, 52℃, 54℃, 56℃, 58℃, 62℃. The temperatures are 64℃, 66℃, 68℃, 72℃, 74℃, 76℃, 78℃, 82℃, 84℃, 86℃, 88℃, 92℃, 94℃, 96℃, or 98℃. In this invention, the preferred time for the first elimination reaction is 1 to 3 hours, specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2.1 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.7 hours, 2.8 hours, or 2.9 hours.

[0033] Following the first elimination reaction, the process further includes post-treatment of the resulting elimination reaction solution, wherein the post-treatment preferably includes the following steps: The elimination reaction solution was washed with water and separated, and the organic phase was collected to obtain crude product A; The crude product A was mixed with an alcoholic solution of acetic acid and zinc to carry out a deiodination reduction reaction, and after washing with water and separation, crude product B was obtained. The crude product B was subjected to distillation to obtain a pure hydrofluoroolefin compound.

[0034] In this invention, the washing and separation are preferably performed as follows: the reaction solution after the elimination reaction is completed is washed with an equal volume of deionized water, and then allowed to stand for phase separation. The lower layer is the organic phase (crude product phase), and the upper layer is the aqueous phase. After separation, crude product A is obtained, which contains ≤0.5% perfluoroiodoalkane raw material.

[0035] In this invention, the reaction formula for the deiodination reduction reaction is: C4F9I + Zinc + Alcohol + HAc → CF3CF2CF2CHF2; In this invention, the small amount of residual perfluoroiodoalkane in the crude product A can react under activated zinc and alcohol solution conditions to become low-boiling-point fluorinated alkanes. After washing and separation with water, the lower organic phase is the crude product B. The low-boiling-point fluorinated alkanes can be completely removed by natural volatilization or distillation in a distillation column. In this invention, the alcohol is preferably methanol, ethanol, or isopropanol, and the zinc is preferably zinc powder. In this invention, the mass ratio of nonafluorobutyl iodoalkane, acetic acid, zinc, and alcohol in the crude product A is preferably 0.1:100:(40~100):(150~200). This invention ensures that the residual nonafluorobutyl iodoalkane can be completely removed by reaction using sufficient zinc granules.

[0036] In this invention, the deiodination reduction reaction is preferably carried out under stirring conditions, the stirring rate is preferably ≥300 rpm, the temperature of the deiodination reduction reaction is preferably 60°C, and the time is preferably 3 h.

[0037] In this invention, the distillation is preferably carried out under standard atmospheric pressure, and the distillation preferably collects the fraction at 77~79°C.

[0038] In this invention, the preparation method of CF3CF2CF(CF3)CH=CHCF3 having the structure described in Formula 2 includes the following steps: (1) CF3CF2CFICF3 is reacted with trifluoropropylene (CF3CH=CH2) by a second radical addition reaction to obtain a second intermediate; the reaction formula is: CF3CF2CFICF3+CF3CH=CH2→CF3CF2CF(CF3)CH2CHICF3; (2) The second intermediate is mixed with alkaline solution to carry out the second elimination reaction to obtain CF3CF2CF(CF3)CH=CHCF3. The reaction formula is: CF3CF2CF(CF3)CH2CHICF3 + alkaline system → CF3CF2CF(CF3)CH=CHCF3.

[0039] A method for preparing (CF3)2CFCF2CH=CHCF3 with the structure shown in Formula 3 includes the following steps: (1) The third radical addition reaction of (CF3)2CFCF2I with trifluoropropylene (CF3CH=CH2) yields the third intermediate; the reaction formula is: (CF3)2CFCF2I+CF3CH=CH2→(CF3)2CFCF2CH2CHICF3; (2) The third intermediate is mixed with alkaline solution to carry out the third elimination reaction to obtain (CF3)2CFCF2CH=CHCF3. The reaction formula is: (CF3)2CFCF2CH2CHICF3 + alkaline system → (CF3)2CFCF2CH=CHCF3.

[0040] In this invention, the preparation method of CF3CF2CF1CF3 and (CF3)2CFCF2I preferably includes the following steps: Trifluoroiodomethane (CF3I), hexafluoropropylene (CF3CF=CF2), and a free radical catalyst are mixed and subjected to a pre-addition reaction to obtain a pre-addition reaction solution, wherein the pre-addition reaction solution comprises CF3CF2CF1CF3 and (CF3)2CFCF2I. In this invention, the reaction formula for the pre-addition reaction is: CF3I + CF3CF = CF2 + free radical catalyst → CF3CF2CFICF3 + (CF3)2CFCF2I + byproduct; In this invention, the free radical catalyst preferably includes one or more of AIBN, ABVN, DTBP, LPO, BPO, and DCP, more preferably DTBP, AIBN, or BPO. In this invention, the molar ratio of trifluoroiodomethane, hexafluoropropylene, and the free radical catalyst is preferably (4~10):1:0.1, specifically 10:1:0.1, 8:1:0.1, 6:1:0.1, or 4:1:0.1. This invention ensures an excess of trifluoroiodomethane (CF3I), which reduces the content of byproducts and ensures that the target products are CF3CF2CF1CF3 and (CF3)2CFCF2I. The excess trifluoroiodomethane (CF3I) is purified by distillation, recovered, and recycled, improving utilization.

[0041] In this invention, the temperature of the pre-addition reaction is preferably 120~180℃, more preferably 140~160℃, the time is preferably 4~10h, more preferably 6~8h, and the pressure is preferably ≤6MPa. In this invention, the reaction is considered terminated when the pressure no longer decreases and remains stable for 3 consecutive hours. In this invention, the molar ratio of CF3CF2CF1CF3 to (CF3)2CFCF2I in the pre-addition reaction solution is preferably 92:8.

[0042] In this invention, the pre-addition reaction solution is separated by distillation to obtain CF3CF2CFICF3 and (CF3)2CFCF2I, respectively. In this invention, the density of CF3CF2CFICF3 is 2.01 g / cm³. 3 The boiling point is 65℃, and the density of (CF3)2CFCF2I is 2.12 g / cm³. 3 The boiling point is 63℃. This invention utilizes the difference in boiling points between the two substances to separate and purify them through distillation.

[0043] In this invention, the difference between the second radical addition reaction and the first radical addition reaction lies only in the starting materials. The molar ratio of perfluoroiodoalkane to fluorinated olefin, the temperature, time, and post-treatment of the second radical addition reaction are the same as those of the first radical addition reaction, and will not be repeated here.

[0044] In this invention, the difference between the second elimination reaction and the first elimination reaction lies only in the starting materials. The types of alkaline solution, the ratio of the second intermediate to the alkaline solution, the temperature, time, and post-treatment of the second elimination reaction are the same as those of the first elimination reaction, and will not be repeated here.

[0045] In this invention, the difference between the third radical addition reaction and the first radical addition reaction lies only in the starting materials. The molar ratio of perfluoroiodoalkane to fluorinated olefin, the temperature, time, and post-treatment of the third radical addition reaction are the same as those of the first radical addition reaction, and will not be repeated here.

[0046] In this invention, the difference between the third elimination reaction and the first elimination reaction lies only in the starting materials. The types of alkaline solution, the ratio of the third intermediate to the alkaline solution, the temperature, time, and post-treatment of the third elimination reaction are the same as those of the first elimination reaction, and will not be repeated here.

[0047] In this invention, the preparation method of CF3CF2CH=CHCF2CF2CF3 having the structure shown in Formula 4 includes the following steps: CF3CF2CF2I was reacted with pentafluorobutene (CF3CF2CH=CH2) in a fourth radical addition reaction to give the fourth intermediate CF3CF2CHICH2CF2CF2CF3; The fourth intermediate CF3CF2CHICH2CF2CF2CF3 was mixed with an alkaline solution and subjected to a fourth elimination reaction to obtain CF3CF2CH=CHCF2CF2CF3. The relevant reaction formula is: CF3CF2CF2I+CF3CF2CH=CH2→CF3CF2CHICH2CF2CF2CF3+ (Alkaline system)→CF3CF2CH=CHCF2CF2CF3; In this invention, the difference between the fourth radical addition reaction and the first radical addition reaction lies only in the starting materials. The molar ratio of perfluoroiodoalkane to fluorinated olefin, the temperature, time, and post-treatment of the fourth radical addition reaction are the same as those of the first radical addition reaction, and will not be repeated here.

[0048] In this invention, the difference between the fourth elimination reaction and the first elimination reaction lies only in the starting materials. The types of alkaline solution, the ratio of the fourth intermediate to the alkaline solution, the temperature, time, and post-treatment of the fourth elimination reaction are the same as those of the first elimination reaction, and will not be repeated here.

[0049] In this invention, the preparation method of CF3CF2CH=CHCF(CF3)2 having the structure shown in Formula 5 includes the following steps: (CF3)2CFI was reacted with pentafluorobutene (CF3CF2CH=CH2) by a fifth radical addition reaction to give the fifth intermediate (CF3)2CFCH2CHICF2CF3; The fifth intermediate (CF3)2CFCH2CHICF2CF3 was mixed with an alkaline solution and subjected to a fifth elimination reaction to obtain CF3CF2CH=CHCF(CF3)2.

[0050] The relevant reaction formula is: (CF3)2CFI+CF3CF2CH=CH2→(CF3)2CFCH2CHICF2CF3+Alkaline system→CF3CF2CH=CHCF(CF3)2.

[0051] In this invention, the difference between the fifth radical addition reaction and the first radical addition reaction lies only in the starting materials. The molar ratio of perfluoroiodoalkane to fluorinated olefin, the temperature, time, and post-treatment of the fifth radical addition reaction are the same as those of the first radical addition reaction, and will not be repeated here.

[0052] In this invention, the difference between the fifth elimination reaction and the first elimination reaction lies only in the starting materials. The types of alkaline solution, the ratio of the fifth intermediate to the alkaline solution, the temperature, time, and post-treatment of the fifth elimination reaction are the same as those of the first elimination reaction, and will not be repeated here.

[0053] This invention provides the application of the aforementioned hydrofluoroolefin compounds in temperature-controlled working fluids. In this invention, the preferred application areas of the temperature-controlled working fluid are servers, data centers, energy storage, semiconductor manufacturing, charging equipment, or thermal management of new energy vehicles. In this invention, the hydrofluoroolefin compounds are preferably used in immersion liquid cooling or non-contact temperature-controlled carrier fluids.

[0054] The following detailed description, in conjunction with embodiments, illustrates the hydrofluoroolefin compounds, their preparation methods, and applications provided by the present invention. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0055] Example 1 Preparation of CF3CF2CF2CF2CH=CHCF3 (2H,3H-dodecano-2-heptene) S1: In a high-temperature and high-pressure reactor, the raw materials nonafluorobutyl iodoalkane (C4F9I) and trifluoropropylene (CF3CH=CH2) are added to react and the intermediate is obtained: 1,1,1,4,4,5,5,6,6,7,7,7-dodecano-2-iodoheptane (CF3CHICH2C4F9).

[0056] The by-product content and intermediate yield under different feed ratios and reaction conditions are shown in Table 1, and the by-product content and intermediate yield under the comparative conditions are shown in Table 2. Table 1. Byproduct content and intermediate yield under different feed ratios and reaction conditions.

[0057] Table 2. Byproduct content and intermediate yield under comparative conditions.

[0058] In Tables 1 and 2, the intermediate yields are calculated based on the amount of trifluoropropylene converted into the target intermediate, with very little of the starting material not participating in the reaction.

[0059] Comparing Tables 1 and 2, it can be seen that to increase the yield of the target intermediate, a sufficient excess of nonafluorobutyl iodide is necessary. An excess of nonafluorobutyl iodide can inhibit the formation of byproducts.

[0060] S2: Distillation to extract excess unreacted raw material: nonafluorobutyl iodoalkane (C4F9I).

[0061] To steer the reaction in a direction more favorable to obtaining the intermediate and reduce the content of byproducts, nonafluorobutyl iodide is added in excess during the initial feed. The reaction solution is distilled to extract the excess nonafluorobutyl iodide, which can then be reused in subsequent feed reactions, thus avoiding waste of raw materials. After distillation, the content of nonafluorobutyl iodide in the intermediate (2H,3H,3H'-dodecano-2-iodoheptane) is ≤0.5%. The nonafluorobutyl iodide content in the intermediates after distillation in schemes 11-15 is shown in Table 3.

[0062] Table 3. Content of nonafluorobutyl iodine in intermediates after distillation of schemes 11-15

[0063] S3: The intermediate from step S2 undergoes an elimination reaction in an alkaline system to eliminate HI. After washing with water and separating the liquid, crude product A is obtained. Reaction formula: C4F9CH2CHICF3 + alkaline system → CF3CF2CF2CF2CH=CHCF3.

[0064] The alkaline systems used were: 35% KOH-3% benzyltrimethylammonium chloride aqueous solution, 35% KOH-3% tetrabutylammonium bromide aqueous solution, 30% KOH-water-50% methanol solution, and 30% KOH-water-50% isopropanol solution.

[0065] The conversion rates of intermediates under different alkaline systems and different elimination reaction conditions are shown in Table 4.

[0066] Table 4. Conversion rates of intermediates under different alkaline systems and elimination reaction conditions

[0067] As shown in Table 4, under the same alkaline conditions, the higher the temperature and the longer the reaction time, the higher the conversion rate of the intermediate. Under sufficient conditions of different alkaline systems, the intermediate exhibits a high conversion rate.

[0068] S4: After the reaction in step S3, the crude product A (taking the crude product obtained in Scheme 55 as an example) reacts with HAc, zinc granules, and an alcohol solution to remove a small amount of the raw material nonafluorobutyl iodide (C4F9I) from the crude product. The mass ratio of nonafluorobutyl iodide:HAc:zinc granules:alcohol in crude product A is 0.1:100:50~100:200. After the reaction is complete, the reaction solution is washed with water, and crude product B is obtained after separation. Reaction formula: C4F9I + Zinc + Alcohol + HAc → CF3CF2CF2CHF2. The content of nonafluorobutyl iodide in crude product A under different amounts of zinc granules is shown in Table 5. Table 5. Content of nonafluorobutyl iodoalkane in crude product A under different zinc granule dosages

[0069] In Table 5, "-" indicates that the gas chromatograph cannot detect it.

[0070] As can be seen from Table 5, the presence of sufficient zinc can completely remove residual nonafluorobutyl iodoalkane.

[0071] S5: The crude product B is purified by distillation to obtain the final product: 2H,3H-perfluoro2-heptene, with a purity ≥99%, which can be used as a temperature-controlled working fluid.

[0072] In step S5: Crude product B is purified by distillation under standard atmospheric pressure, and the fraction collected at 77-79℃ is used to obtain the final product: 2H,3H-dodecano-2-heptene (CF3CF2CF2CF2CH=CHCF3). A fraction sample is taken and placed in a quartz glass bottle, and irradiated with 254nm ultraviolet light for no less than 3 hours. No color change is observed; it remains colorless and transparent. The purpose of ultraviolet irradiation is to detect the presence of the raw material nonafluorobutyl iodoalkane (C4F9I). The absence of color change indicates its absence.

[0073] The NMR fluorine spectrum of CF3CF2CF2CF2CH=CHCF3 obtained in Example 1 is shown below. Figure 1 As shown, the proton NMR spectrum is as follows: Figure 2 As shown.

[0074] The physical properties of CF3CF2CF2CF2CH=CHCF3 obtained in Example 1 are shown in Table 6: Table 6 Physical properties of CF3CF2CF2CF2CH=CHCF3

[0075] Boiling point test: in accordance with national standard GB / T616-2006 "General Method for Determination of Boiling Point of Chemical Reagents"; Flash point test: in accordance with national standard GB / T261-2021 "Flash Point-Pinsky-Martin Closed Cup Method"; Density testing: in accordance with national standard GB / T29617 "Test Method for Liquid Density, Relative Density and API Specific Gravity Using Digital Densitometer"; Kinematic viscosity: According to national standard GB / T 265-88 "Determination of Kinematic Viscosity of Petroleum Products"; Pour point: According to national standard GB / T 3535-2025 "Determination of Pour Point of Petroleum Products"; Latent heat of vaporization: According to the national standard GB / T8017 "Determination of vapor pressure of petroleum products"; Thermal conductivity: determined according to the transient hot wire method, with reference to standard ASTM D7896; Specific heat capacity: Calculated according to the specific heat capacity definition formula: Q=Cp·m·δt (where Cp represents specific heat capacity, Q represents the heat absorbed or released, m represents the mass of the substance, and δt represents the temperature change). Breakdown voltage test: in accordance with national standard GB / T1408.1-2006 "Test Methods for Electrical Strength of Insulating Materials"; Dielectric constant test: according to national standard GB / T5654-2007 "Measurement of relative permittivity, dielectric loss factor and DC resistivity of liquid insulating materials".

[0076] The final product (2H,3H-dodecylfluoro-2-heptene) synthesized and purified through steps S1 to S5 fully meets the temperature control requirements for specific scenarios. It can be used as a low-temperature shock medium for chips and electronic components, as an immersion liquid cooling medium for high-power heat sources, and as a temperature control liquid for equipment in semiconductor chip manufacturing and chip testing equipment.

[0077] Example 2 Preparation of CF3CF2CF(CF3)CH=CHCF3 and (CF3)2CFCF2CH=CHCF3 (1) First, prepare perfluoroiodoalkane raw materials CF3CF2CFICF3 and (CF3)2CFCF2I. The reaction formula is: CF3I+CF3CF=CF2+ free radical catalyst→CF3CF2CFICF3+(CF3)2CFCF2I+ byproduct.

[0078] The molar ratios of trifluoroiodomethane (CF3I):hexafluoropropylene (CF3CF=CF2):free radical catalyst were set to 10:1:0.1, 8:1:0.1, 6:1:0.1, and 4:1:0.1, respectively. The free radical catalysts were DTBP, AIBN, and BPO. The reaction temperatures were set at 120–180 °C, the reaction times at 4–10 h, and the pressure at ≤6 MPa. The contents of CF3CF2CF1CF3 and (CF3)2CF2CF2I in the reactants under different raw material ratios and reaction conditions are shown in Table 7.

[0079] Table 7. Content of CF3CF2CF1F1CF3 and (CF3)2CF2CF2I in reactants under different raw material ratios and reaction conditions

[0080] As can be seen from Table 7, under the condition of sufficient excess of trifluoroiodomethane, the content of the target product is higher and the ratio of the target product is close to 92:8.

[0081] After the reaction is complete, the resulting product is a mixture. After removing excess trifluoroiodomethane, the ratio of CF3CF2CFFICF3 to (CF3)2CFCF2I is approximately 92:8. Utilizing the boiling point difference between CF3CF2CFFICF3 and (CF3)2CFCF2I, they can be separated and purified using a distillation column. The distillation column requires: structured packing with a high specific surface area, a theoretical plate number > 300, and a reflux ratio > 18.

[0082] (2) Preparation of CF3CF2(CF3)CFCH=CHCF3 The preparation of CF3CF2(CF3)CFCH=CHCF3 using CF3CF2CFFICF3 and trifluoropropylene (CF3CH=CH2) as raw materials is as follows: Preparation of intermediates via free radical addition reaction: 3.46 kg of CF3CF2CF1CF3 was added to a 5L high-temperature and high-pressure reactor under vacuum. The reactor was then cooled to <-5℃, and 96 g of trifluoropropylene CF3CH=CH2 (molar ratio 10:1) was introduced. The temperature was raised to 215℃ over 3 hours and maintained at 215℃ for 4 hours until the reactor pressure stopped decreasing. The temperature was then lowered to <25℃, and the reactor was opened to discharge the reaction solution, yielding 3.52 kg. The main reaction in this stage is: CF3CF2CFICF3+CF3CH=CH2→CF3CHICH2CF(CF3)CF2CF3(Reaction conditions: 215℃ / 4h)

[0083] The received reaction solution was purified by distillation in a distillation column to extract excess unreacted raw material, yielding 3.05 kg of raw material CF3CF2CFICF3. The bottom liquid of the distillation column was the intermediate product CF3CHICH2CF(CF3)CF2CF3, weighing 445 g. The intermediate yield was calculated to be 99.6%. The residual raw material CF3CF2CFICF3 was 0.2%.

[0084] Elimination reaction to prepare the target product CF3CF2(CF3)CFCH=CHCF3: 445g of the distilled intermediate was added to a 2L effective volume reactor, along with 300mL of 30% KOH aqueous solution and 300mL of methanol solution. The reactor was sealed and heated to 60℃ for 3h. After cooling and discharging, the product was washed with water, separated, filtered, and the lower organic phase was collected, which was the crude product CF3CF2(CF3)CFCH=CHCF3: 312g, with a calculated yield of 99.8%. The elimination reaction in this stage was: CF3CHICH2CF(CF3)CF2CF3 + KOH → CF3CF2(CF3)CFCH=CHCF3 + KI + H2O (reaction conditions: methanol solvent, 60℃ / 3h).

[0085] The post-processing of the crude product CF3CF2(CF3)CFCH=CHCF3 involved removing residual raw material CF3CF2CFICF3, which could cause the product to turn red. 312g of the crude product received in the previous step was added to a 5L reactor, followed by 1kg of glacial acetic acid, 450g of zinc, and 1.8kg of methanol. The reactor was sealed and heated to 60℃, and the mixture was stirred for 3 hours. After the reaction was complete, the product was cooled, washed with water, separated, filtered, and the lower organic product phase (302g) was collected. A sample was taken for gas chromatography to determine the content of the raw material CF3CF2CFICF3. The content was found to be below the detection limit. The reaction at this stage was: CF3CF2CFICF3 + Zn + HAc → CF3CF2CHFCF3 (reaction conditions: methanol solvent, 60℃ / 3h).

[0086] The received product phase (302g) was purified by distillation, removing the initial and final fractions, yielding a main fraction of 282g. A sample of the main fraction was taken for purity testing, which showed a purity of 99.7%. A 2mL sample was placed in a quartz glass bottle and irradiated under 254nm ultraviolet light for 3 hours. The bottle remained colorless and transparent, indicating the absence of residual perfluoroiodoalkane. This main fraction can be considered the final qualified product.

[0087] (3) Preparation of (CF3)2CFCF2CH=CHCF3 (CF3)2CFCF2I and trifluoropropylene were used as raw materials to prepare (CF3)2CFCF2CH=CHCF3. The specific method followed the same feeding reaction and post-treatment procedures and conditions as for the preparation of CF3CF2(CF3)CFCH=CHCF3. The final synthesized product was obtained.

[0088] The physical properties of CF3CF2CF(CF3)CH=CHCF3 and (CF3)2CFCF2CH=CHCF3 obtained in Example 2 are shown in Table 8.

[0089] Table 8 Physical properties of CF3CF2CF(CF3)CH=CHCF3 and (CF3)2CFCF2CH=CHCF3

[0090] Example 3 Preparation of CF3CF2CH=CHCF2CF2CF3 and CF3CF2CH=CHCF(CF3)2 (1) Using CF3CF2CF2I and pentafluorobutene as raw materials, CF3CF2CH=CHCF2CF2CF3 was prepared. The specific method was the same as that used in the preparation of CF3CF2(CF3)CFCH=CHCF3, with each step of the feeding reaction and the post-treatment conditions of the reaction solution. The final synthetic product can be obtained.

[0091] (2) Using (CF3)2CFI and pentafluorobutene as raw materials, CF3CF2CH=CHCF(CF3)2 is prepared. The specific method is the same as that for the preparation of CF3CF2(CF3)CFCH=CHCF3, including the feeding reaction and post-treatment conditions of each step of the reaction. The final synthetic product can be obtained.

[0092] The physical properties of CF3CF2CH=CHCF2CF2CF3 and CF3CF2CH=CHCF(CF3)2 are shown in Table 9.

[0093] Table 9 Physical properties of CF3CF2CH=CHCF2CF2CF3 and CF3CF2CH=CHCF(CF3)2

[0094] Material compatibility testing Material compatibility tests were conducted on the novel hydrofluoroolefin compounds prepared in the above embodiments: ①CF3CF2CF2CF2CH=CHCF3, ②CF3CF2CF(CF3)CH=CHCF3, ③(CF3)2CFCF2CH=CHCF3, ④CF3CF2CH=CHCF2CF2CF3, and ⑤CF3CF2CH=CHCF(CF3)2. The test samples were all selected from the scheme with the highest purity after distillation purification.

[0095] The test method is as follows: 50 mL of the purified substance after distillation is measured and placed in a 100 mL stainless steel hydrothermal reactor. Various types of materials are then added, and immersion tests are conducted at room temperature (25℃ / 168 h) and at high temperature (100℃ / 168 h). The criteria for judging compatibility are as follows: ☆- Excellent compatibility, with virtually no change in appearance, quality, or size; ○- Excellent compatibility, no change in appearance, and changes in weight and volume ≤1%; □ - Basically compatible, no change in appearance, with changes in weight and volume within the range of 1-3%; △ - Incompatible; appearance is significantly different; mass or volume is also different; mass or volume change > 3%; × - No, the material itself cannot withstand a high temperature of 100℃ for an extended period of time.

[0096] The compatibility test results of the room temperature immersion test at 25℃ / 168h are shown in Table 10, and the compatibility test results of the high temperature immersion test at 100℃ / 168h are shown in Table 11.

[0097] Table 10 Compatibility test results of immersion at room temperature for 25℃ / 168h

[0098] Table 11 Compatibility test results of high-temperature immersion experiment at 100℃ / 168h

[0099] As can be seen from Tables 10 and 11, compounds ①, ②, ③, ④, and ⑤ all have excellent material compatibility, but exhibit a slight swelling effect on fluororubber seals, indicating slightly poor compatibility.

[0100] Energy consumption test Compounds ① and ⑤ from the "Material Compatibility Test" and commercially available 3M-7300 fluorinated liquid, 10L each, were placed in a liquid-cooled immersion heat dissipation simulator. The maximum power of the heat source in the simulator was 1.5kW. The simulator had a variable frequency cooling fan on top, which automatically turned on and adjusted its speed based on the temperature data of the liquid evaporating to the top. The simulator was run for 24 hours, and the total electrical energy consumed and the highest temperature reached by the heat source were recorded for energy consumption assessment. The test results are shown in Table 12. Table 12 Energy Consumption Test Results

[0101] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A hydrofluoroolefin compound, characterized in that, The molecular formula of the hydrofluoroolefin compound is C7H2F. 12 It has the structure shown in any one of Equations 1 to 5: Equation 1: CF3CF2CF2CF2CH=CHCF3 Equation 2: CF3CF2CF(CF3)CH=CHCF3; (CF3)2CFCF2CH=CHCF3 Equation 3; Equation 4: CF3CF2CH=CHCF2CF2CF3; Equation 5: CF3CF2CH=CHCF(CF3)2 2. The hydrofluoroolefin compound according to claim 1, characterized in that, The hydrofluoroolefin compound comprises a cis or trans isomer having the structure shown in any one of Formulas 1 to 5.

3. The hydrofluoroolefin compound according to claim 1 or 2, characterized in that, The hydrofluoroolefin compound has an ODP value of 0 and a GWP value of <20; The dielectric constant of the hydrofluoroolefin compound is <2.2 at 1 kHz. The hydrofluoroolefin compound is non-flammable and has no flash point; The pour point of the hydrofluoroolefin compound is < -80°C; The voltage withstand capability of the hydrofluoroolefin compound is >40KV / mm.

4. A method for preparing the hydrofluoroolefin compound according to any one of claims 1 to 3, characterized in that, Includes the following steps: Perfluoroiodoalkanes undergo free radical addition reactions with fluorinated alkenes to yield intermediates; The intermediate was mixed with an alkaline solution and subjected to an elimination reaction to obtain a hydrofluoroolefin compound. When preparing CF3CF2CF2CF2CH=CHCF3 having the structure shown in Formula 1, the perfluoroiodoalkane is CF3CF2CF2CF2I, and the fluorinated olefin is trifluoropropylene; When preparing CF3CF2CF(CF3)CH=CHCF3 having the structure shown in Formula 2, the perfluoroiodoalkane is CF3CF2CFICF3, and the fluorinated olefin is trifluoropropylene; When preparing (CF3)2CFCF2CH=CHCF3 having the structure shown in Formula 3, the perfluoroiodoalkane is (CF3)2CFCF2I, and the fluorinated olefin is trifluoropropylene; When preparing CF3CF2CH=CHCF2CF2CF3 having the structure shown in Formula 4, the perfluoroiodoalkane is CF3CF2CF2I, and the fluorinated olefin is pentafluorobutene; When preparing CF3CF2CH=CHCF(CF3)2 having the structure shown in Formula 5, the perfluoroiodoalkane is (CF3)2CFI, and the fluorinated olefin is pentafluorobutene.

5. The preparation method according to claim 4, characterized in that, The molar ratio of the perfluoroiodoalkane to the fluorinated olefin is 10~20:1; The free radical addition reaction is carried out at a temperature of 180~220℃ for 4~10h.

6. The preparation method according to claim 4, characterized in that, The alkaline solution comprises an inorganic base and a solvent, wherein the inorganic base is KOH and / or NaOH, and the solvent comprises one or more of the following: quaternary ammonium salt aqueous solution, tertiary amine aqueous solution, alcohol-aqueous solution, and cyclic crown ether aqueous solution; The mass concentration of the alkaline solution is 25-50%; The elimination reaction is carried out at a temperature of 30~100℃ for 1~3 hours.

7. The preparation method according to claim 4, characterized in that, The preparation method of CF3CF2CF1CF3 and (CF3)2CFCF2I includes the following steps: Trifluoroiodoformane, hexafluoropropylene and a free radical catalyst are mixed and subjected to a pre-addition reaction to obtain a pre-addition reaction solution, wherein the pre-addition reaction solution includes the target products: CF3CF2CFICF3 and (CF3)2CFCF2I. The pre-addition reaction solution was separated by distillation to obtain CF3CF2CFICF3 and (CF3)2CFCF2I, respectively.

8. The preparation method according to claim 7, characterized in that, The molar ratio of trifluoroiodomethane, hexafluoropropylene, and the free radical catalyst is (4~10):1:0.1; The temperature of the pre-addition reaction is 120~180℃, and the pressure is 0~6 MPa.

9. The preparation method according to claim 4, characterized in that, After the elimination reaction, the process further includes post-treatment of the resulting elimination reaction solution, which includes the following steps: The elimination reaction solution was washed with water and separated, and the organic phase was collected to obtain crude product A; The crude product A was mixed with an alcoholic solution of acetic acid and zinc to carry out a deiodination reduction reaction. After washing with water and separating the liquid, the organic phase was collected to obtain the crude product B. The crude product B is purified by distillation to obtain the pure hydrofluoroolefin compound with a purity ≥99%.

10. The application of the hydrofluoroolefin compound according to any one of claims 1 to 3 or the hydrofluoroolefin compound prepared by the preparation method according to any one of claims 4 to 9 in a temperature-controlled working fluid.

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