Catalytic synthesis of fluorinated alkenes and fluorinated alkene compositions

Abstract

The method for producing fluoroolefins is to prepare a compound of formula (1), R f The method comprises contacting CX1=CHCF3 with a fluorinated ethylene compound of formula (2), CX2X3=CX4X5, in the presence of a catalyst. f is a straight or branched chain C1-C 10 is a perfluorinated alkyl group, and X1 is H, Br, Cl, or F. In the compound of formula (2), X2, X3, X4, and X5 are each independently H, Br, Cl, or F, and at least three of X2, X3, X4, and X5 are F. The resulting composition comprises a compound of formula (3), R f (CF2) n CX6=CH(CF2) m CX7X8CFX9X 10 In the compound of formula (3), X6, X7, X8, X9, and X 10 are each independently H, Br, Cl, or F, and the total number of H, Br, Cl, and F corresponds to the total number of H, Br, Cl, and F provided by the compound of formula (1) and the compound of formula (2).

Description

[Technical field]

[0001] (Reference to Related Application) This application claims the benefit of U.S. Patent Application No. 62 / 945388, filed December 9, 2019. The disclosure of U.S. Patent Application No. 62 / 945388 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present invention relates to the preparation of fluorinated alkene compounds and fluorinated alkene compositions. [Background technology]

[0003] Uncertainty in energy supplies and prices, and a growing public awareness of the environmental impacts of fossil fuel extraction, transportation, and use, have led to a resurgence of interest in utilizing low-temperature heat (i.e., heat at temperatures below about 300° C.). Such heat may be derived from a variety of commercial, industrial, or natural sources. Increasing the temperature of available heat to meet heating requirements with high temperature mechanical compression heat pumps (HTHPs) and converting available heat to mechanical or electrical power with Organic Rankine Cycles (ORCs) are two promising approaches to utilizing low-temperature heat.

[0004] ORC and HTHP require the use of working fluids. Currently, working fluids with high global warming potentials (GWP) commonly used in HTHP and ORC (e.g., HFC-245fa) have come under increasing scrutiny to date, culminating in the landmark HFC amendment to the Montreal Protocol recently agreed in Kigali, Rwanda. Clearly, there is a growing need for more environmentally sustainable working fluids for HTHP and ORC, especially given that environmental sustainability is a major motivation for low-temperature heat utilization. More specifically, there is a need for low-GWP working fluids with boiling points above about 50 degrees Celsius (hereafter referred to as "°C") that are particularly suitable for converting heat available at temperatures approaching or exceeding 200°C into power, and for heating at temperatures approaching 200°C from heat available at lower temperatures.

[0005] Other applications include direct contact with current carrying components. These fluids typically exhibit very low dielectric constants, meaning that they do not conduct heat and therefore can provide heat transfer in a variety of applications including immersion cooling and phase change cooling (e.g., cooling electronic devices, including data center cooling). Additional applications exist as insulating gases due to the very low dielectric constant values. Inherently, the dielectric constant of a fluid when it is liquid has also been found to exhibit an even lower dielectric constant in the gas phase.

[0006] These fluids are also used in general heat transfer applications that may utilize forced convection and / or phase change as the mechanism for transferring heat from a hot source to a cold source or vice versa (from cold source to hot source). Applications may include heat pipes, refrigeration, and / or any convective heat transfer system.

[0007] These fluids can also be used as solvents to remove contaminants or particles from a given surface or structure, as carrier fluids onto which a desired product is deposited and then evaporates, and even as media for fire extinguishing agents, as flame retardants to inhibit or replace chemical reactions.

[0008] Fluoroalkenes, such as HFO-163-12mczz(C 2 F 5 CH=CHC 3 F 7 ) can be prepared using a four-step preparation involving successive hydrogenation / dehydrofluorination processes using F-heptene-3 starting material, however this process is time consuming and based on a relatively expensive starting material (F-heptene is made using the reaction of hexafluoropropene (HFP) and two moles of tetrafluoroethene (TFE)).

[0009] WO 2008 / 057513 describes a compound of the formula RCH=CHC 2 F 5 This process describes a process for the preparation of internal dihydrofluoroolefins, RCH=CHF, where R is selected from perfluoroalkyl groups having 1-10 carbon atoms, the alkyl groups being either n-alkyl chains, sec-alkyl chains, or iso-alkyl chains, in the liquid phase, by the addition of tetrafluoroethylene and antimony pentafluoride (SbF). 5 The method includes reacting in the presence of a Lewis acid catalyst, removing the Lewis acid catalyst, and isolating the dihydrofluoroolefin. The disclosure of WO 2008 / 057513 is incorporated herein by reference. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] U.S. Patent Application No. 62 / 945388 [Patent Document 2] International Publication No. 2008 / 057513 Summary of the Invention [Means for solving the problem]

[0011] In one embodiment, the method for producing a fluoroolefin comprises the steps of: f CX 1 =CHCF 3 (1) [where R f is a straight or branched chain C 1 ~C 10 is a perfluorinated or polyfluorinated alkyl group, 1 is H, Br, Cl, or F], 2 X 3 =CX 4 X 5 In the compound of formula (2), X 2 , X 3 , X 4 , and X 5 are each independently H, Br, Cl, or F, and X 2 , X 3 , X 4 , and X 5 At least three of are F. The contacting step comprises contacting a compound of formula (3) R f (CF 2 ) n CX 6 =CH(CF 2 ) m CX 7 X 8 CFX 9 X 10 The reaction is carried out in the presence of a sufficient amount of a catalyst to form a composition comprising a compound of formula (3). In the compound of formula (3), n is an integer from 0 to 10, and m is an integer from 1 to 10. In the compound of formula (3), X 6 , X 7 , X 8 , X 9 , and X 10 are each independently H, Br, Cl, or F; X 6 , X7 , X 8 , and X 9 The total number of H, Br, Cl, and F represented by the formula (1) and the formula (2) is 1 , X 2 , X 3 , X 4 , and X 5 The total number of H, Br, Cl, and F is the same as that provided by

[0012] The present invention includes the following aspects and embodiments. In one embodiment, disclosed herein is a method for producing a fluoroolefin. The method described herein comprises preparing a fluoroolefin of formula (1) R f CX 1 =CHCF 3 (1) [where R f is a straight or branched chain C 1 ~C 10 is a perfluorinated or polyfluorinated alkyl group, 1 is H, Cl, or F], 2 X 3 =CX 4 X 5 In the compound of formula (2), X 2 , X 3 , X 4 , and X 5 are each independently H, Cl, or F, and X 2 , X 3 , X 4 , and X 5 At least three of are F. The contacting step comprises contacting a compound of formula (3) R f (CF 2 ) n CX 6 =CH(CF 2 ) m CX 7 X 8 CFX 9 X 10 (3), wherein n is an integer from 0 to 10, m is an integer from 1 to 10, and X 6, X 7 , X 8 , X 9 , and X 10 are each independently H, Cl, or F; X 6 , X 7 , X 8 , X 9 , and X 10 The total number of H, Cl, and F represented by X in formula (1) and formula (2) is 1 , X 2 , X 3 , X 4 , and X 5 The total number of H, Cl, and F is the same as that provided by

[0013] According to any of the foregoing embodiments, the present specification provides a method for producing a compound comprising the steps of: f But CF 3 , C 2 F 5 , C 3 F 7 ,I C 3 F 7 , C 4 F 9 , C 5 F 11 ,I C 5 F 11 , C 6 F 13 , and iC 6 F 13 Also disclosed is a method selected from the group consisting of:

[0014] According to any of the foregoing embodiments, the present disclosure provides a compound of formula (1) comprising 4 F 9 CH=CHCF 3 , (CF 3 ) 2 CFCH=CHCF 3 , C.F. 3 CH=CFCF 3 , or CF 3 CH=CClCF 3 and the compound of formula (3) is 4 F 9 CH=CHCF 2 CFClCF 3 , C4 F 9 CH=CHCF 2 CF 2 CF 2 Cl, (CF 3 ) 2 CFCH=CHCF 2 CFClCF 3 , (CF 3 ) 2 CFCH=CHCF 2 CF 2 CF 2 Cl, C 2 F 5 CH=CHC 2 F 5 , C 2 F 5 CF=CHCFClCF 3 , C 2 F 5 CF=CHCF 2 CF 2 Cl or C 3 F 7 CH=CClCF 3 Also disclosed is a method comprising:

[0015] According to any of the foregoing embodiments, the present specification provides a method for preparing a fluorinated ethylene of formula (2) comprising the step of: 2 =CF 2 , CFCl=CF 2 , CFCl=CFCl, CFH=CF 2 (HFO-1123), CFH=CFH(HFO-1132), and CF 2 =CH 2 (VF2), and the composition comprises at least one of C 4 F 9 CH=CHCF 2 CFClCF 3 , C 4 F 9 CH=CHCF 2 CF 2 CF 2 Cl, (CF 3 ) 2 CFCH=CHCF 2 CFClCF 3 , (CF 3 ) 2 CFCH=CHCF 2 CF2 CF 2 Cl, C 2 F 5 CH=CHC 2 F 5 , C 2 F 5 CF=CHCFClCF 3 , C 2 F 5 CF=CHCF 2 CF 2 Cl or C 3 F 7 CH=CClCF 3 , and C.F. 3 CF=CHCFClCF 2 Also disclosed are methods comprising at least one member selected from the group consisting of Cl.

[0016] Also disclosed herein, according to any of the foregoing embodiments, is a method, wherein the sufficient amount comprises a molar ratio of (TFE):compound of Formula (1) that is 0.01:1 to 5:1.

[0017] Also disclosed herein, according to any of the foregoing embodiments, is a method, wherein the sufficient amount comprises a molar ratio of (TFE):compound of Formula (1) that is from 0.1:1 to 2:1.

[0018] According to any of the aforementioned embodiments, also disclosed herein is a method, wherein the aforementioned sufficient amount comprises a molar ratio of the compound of Formula (2) to the compound of Formula (1) that is 0.01:1 to 5:1.

[0019] Also disclosed herein, according to any of the preceding embodiments, is a method, wherein the composition further comprises a solvent.

[0020] Also disclosed herein, according to any of the preceding embodiments, is a method, wherein the solvent is a perfluorinated saturated compound.

[0021] According to any of the preceding embodiments, also disclosed herein is a method, wherein the perfluorinated saturated compound is selected from the group consisting of perfluoropentane, perfluorohexane, cyclic dimers of hexafluoropropene (a mixture of perfluoro-1,2-dimethylcyclobutane and perfluoro-1,3-dimethylcyclobutane), and combinations thereof.

[0022] According to any of the foregoing embodiments, the present invention provides a catalyst comprising antimony pentafluoride (SbF 5 ) or a compound of formula (4), SbCl x F 5-x Also disclosed are methods that include: [wherein x=0.01 to 0.5].

[0023] According to any of the foregoing embodiments, the present invention relates to a catalyst comprising aluminum chloride (AlCl 3 ), antimony pentafluoride (SbF 5 ), or aluminum fluoride chloride AlCl x F 3-x Also disclosed is a method comprising: Also disclosed is a method comprising:

[0024] According to any of the foregoing embodiments, the present specification provides a method for producing a compound comprising the steps of: f But linear or branched chain C 2 ~C 10 Also disclosed are methods in which the alkyl groups are perfluorinated.

[0025] According to any of the foregoing embodiments, the present specification provides a method for producing a compound comprising the steps of: f But CF 3 , C 2 F 5 , C 3 F 7 ,I C 3 F 7 , C 4 F 9 , C 5 F 11 ,I C 5 F 11 , C 6 F 13 , or iC 6 F 13 Also disclosed is a method,

[0026] Also disclosed herein, according to any of the preceding embodiments, is a method, wherein the contacting step occurs at sub-ambient or ambient temperature.

[0027] According to any of the foregoing embodiments, also disclosed herein is a method, wherein the reaction is carried out under autogenous pressure.

[0028] According to any of the preceding embodiments, also disclosed herein is a method, wherein the reaction is carried out at 0.1 to 300 psig.

[0029] According to any of the foregoing embodiments, also disclosed herein is a method, wherein the reaction is carried out in a closed system.

[0030] Also disclosed herein, according to any of the preceding embodiments, is a method, wherein the contacting step is carried out at a temperature between -50°C and 50°C.

[0031] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition formed by any of the foregoing methods.

[0032] According to any of the foregoing embodiments, also disclosed herein is a method for transferring heat from an electronic component, comprising providing an immersion cell having at least one electronic component and introducing a composition of the present invention into the immersion cell, wherein the composition at least partially immerses the electronic component.

[0033] Also disclosed herein, in accordance with any of the foregoing embodiments, is a method for transferring heat from an electronic component, including at least one of an automobile battery, a computer, or a server.

[0034] According to any of the foregoing embodiments, also disclosed herein is the use of the composition of the present invention for removing heat from an electronic component.

[0035] The embodiments of the invention can be used alone or in combination with each other. Other features and advantages of the present invention will become apparent from the following more detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. [Brief description of the drawings]

[0036] [Figure 1] FIG. 1 illustrates one embodiment of the present invention in which the composition of the present invention is used in an immersion cooling system. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] A one-step synthesis for the production of fluorinated alkenes is provided that overcomes the limitations mentioned above.

[0038] For example, compared to concepts that do not include one or more of the features disclosed herein, embodiments of the present disclosure provide a one-step synthesis for the production of fluorinated alkenes. More specifically, the present disclosure provides a one-step synthesis for the production of fluorinated alkenes having perfluorinated alkyl chains. The resulting fluorinated alkenes are non-conductive and exhibit low liquid viscosity. Embodiments of the present disclosure include compositions that have an Ozone Depletion Potential (ODP) of 0, are non-flammable (as measured according to ASTM E681), and have a GWP of less than 150, less than 10, and in some cases less than about 1.

[0039] The process may be carried out in any reactor suitable for gas phase fluorination reactions. The reactor is fabricated from materials that are resistant to the reactants used. The reactor may be constructed from materials that are resistant to the corrosive effects of hydrogen fluoride, such as, for example, stainless steel, Hastelloy®, Inconel®, Monel®, gold or gold-plated materials, or quartz. The reaction may be carried out batchwise, continuously, semi-continuously, or a combination thereof. Suitable reactors include batch reactors and tubular reactors.

[0040] In one embodiment, the compound of formula (1), R f CX 1 =CHCF 3 (1) [In the formula, R f is a straight or branched chain C 1 ~C 10 is a perfluorinated alkyl group, X 1 is H, Br, Cl, or F, The mixture is charged into a reactor, heated, and reacted in the presence of a catalyst with the reaction product of formula (2): CX 2 X 3 =CX 4 X 5 (2) [X in the formula 2 , X 3 , X 4 , and X 5 are each independently H, Br, Cl, or F; X 2 , X 3 , X 4 , and X 5 at least three of which are F.

[0041] The temperature and pressure of the reactor are controlled in the presence of a catalyst according to equation (3): R f (CF 2 ) n CX 6 =CH(CF 2 ) m CX 7 X 8 CFX 9 X 10 (3) [In the formula, n is an integer of 0 to 10, m is an integer from 1 to 10; X 6 , X 7 , X 8 , X 9 , and X 10 are each independently H, Br, Cl, or F; X 6 , X 7 , X 8 , X9 , and X 10 The total number of H, Br, Cl, and F represented by the formula (1) and the formula (2) is 1 , X 2 , X 3 , X 4 , and X 5 The total number of H, Br, Cl, and F is maintained at a level sufficient to provide for the formation of a composition comprising a compound having a formula:

[0042] In some embodiments, the number of carbons present in Formula (3) is the sum of the number of carbons present in Formula (1) and Formula (2). In some embodiments, the reaction product of Formula (3) can be further reacted with a compound of Formula (1) and / or Formula (2) to produce a second compound of Formula (3), where the number of carbons present in the second compound of Formula (3) is the sum of the number of carbons present in the first Formula (3) product plus the number of carbons in Formula (2).

[0043] In some embodiments, the ratio of compounds of formula (1) to compounds of formula (2) is about 1:1, and in some cases, is from about 1:1 to about 1:2. When the ratio of compounds of formula (1) to compounds of formula (2) is greater than about 1:1, the number of compounds of formula (3) increases, as does the number of carbon atoms present in the compounds of formula (3).

[0044] In some embodiments, the compound of formula (1) is 4 F 9 CH=CHCF 3 (CF 3 ) 2 CFCH=CHCF 3 , C.F. 3 CH=CFCF 3 (HFO-1327), or CF 3 CH=CClCF 3 (HFO-1326). In one embodiment, the compound of formula (1) is CF 3 In some embodiments, R fmay be a linear or branched perfluorinated alkyl group or a polyfluorinated alkyl group. In some embodiments, R f CF 3 , C 2 F 5 , C 3 F 7 ,I C 3 F 7 , C 4 F 9 , C 5 F 11 ,I C 5 F 11 , C 6 F 13 , or iC 6 F 13 It could be.

[0045] In some embodiments, the fluorinated ethylene of formula (2) is tetrafluoro-ethene, CF 2 =CF 2 (TFE), or CFCl=CF 2 (1-chloro-1,2,2-trifluoro-ethene or CTFE). In one embodiment, the fluorinated ethylene of formula (2) is tetrafluoro-ethene, CF 2 =CF 2 In another embodiment, the fluorinated ethylene of formula (2) comprises CTFE. When CTFE is used as the compound of formula (2), formula (3) comprises two isomers.

[0046] In one embodiment, the compound of formula (1) is CF 3 CH=CFCF 3 (HFO-1327), and the fluorinated ethylene of formula (2) is CF 2 =CF 2 (TFE) included. CF 3 CH=CFCF 3 (HFO-1327) and CF 2 =CF 2 As a result of the reaction with (TFE), C 2 F 5 CH=CHC 2 F 5A composition may be formed comprising (HFO-153-10mczz).

[0047] C 2 F 5 CH=CHC 2 F 5 (HFO-153-10mczz) can be isolated and optionally purified prior to use. 2 F 5 CH=CHC 2 F 5 Suitable uses of (HFO-153-10mczz) include, but are not limited to, working fluids in systems utilizing thermodynamic cycles, reaction intermediates, heat transfer fluids with or without phase changes, and solvents.

[0048] In some embodiments, the fluorinated ethylene of formula (2) may comprise multiple compounds of formula (2). The resulting compound of formula (3) may comprise multiple compounds of formula (3). In one embodiment, the fluorinated ethylene of formula (2) is tetrafluoro-ethene, CF 2 =CF 2 (TFE) and 1-chloro-1,2,2-trifluoroethene. The number of compounds of formula (3) and the number of carbons present in each compound of formula (3) varies as a function of the ratio of compounds of formula (1) to compounds of formula (2).

[0049] In some embodiments, the resulting compound of formula (3) is 2 F 5 CH=CFC 2 F 5 (HFO-152-11mcyz), CF 3 CF=CHCF 2 CF 2 CF 3 (HFO-152-11myz), C 4 F 9 CH=CHCF 2 CFClCF 3 , C 4 F 9 CH=CHCF 2 CF 2 CF 2 Cl, (CF 3 )2 CFCH=CHCF 2 CFClCF 3 , (CF 3 ) 2 CFCH=CHCF 2 CF 2 CF 2 Cl, C 2 F 5 CH=CHC 2 F 5 , C 2 F 5 CF=CHCFClCF 3 , C 2 F 5 CF=CHCF 2 CF 2 Cl, C 2 F 5 CF=CHCFClCF 2 Cl, C 3 F 7 CH=CClCF 3 and mixtures thereof. In some embodiments, the compound of formula (3) is 2 F 5 CF = CHCCl(CF 3 )CF 2 CF 3 It may be present in a composition further comprising 2 F 5 CF = CHCCl(CF 3 )CF 2 CF 3 may be formed as a result of the reaction of a compound of formula (3) above with a compound of formula (2).

[0050] In some embodiments, the compound of formula (2) and the compound of formula (1) are contacted in amounts to obtain a molar ratio of 0.01:1 to 5:1. In one embodiment, the compound of formula (2) and the compound of formula (1) are contacted in amounts to obtain a molar ratio of (2):(1) that is 0.1:1 to 2:1. In one embodiment, the compound of formula (2) and the compound of formula (1) are contacted in amounts to obtain a molar ratio of (2):(1) that is 1:1 to 2:1. In one embodiment, the compound of formula (2) is (TFE) and the compound of formula (1) is CF 3 CH=CFCF 3(HFO-1327).

[0051] The reaction can be carried out under atmospheric or elevated pressure in a closed system. The catalyst is preferably a Lewis acid, including, for example, at least one of aluminum chloride, antimony chloride, and the like. In some embodiments, the Lewis acid is a strong Lewis acid. In one embodiment, the catalyst is antimony pentafluoride (SbF 5 ), Aluminum fluoride chloride AlCl x F 3-x , or aluminum bromofluoride AlBr x F 3-x In some embodiments, x can be an integer from 1 to 3. In some embodiments, x can be from 0.01 to 0.5. Any suitable amount of catalyst can be used, and the amount can range from about 0.5 to about 20 mol %, from about 1 to about 15 mol %, and in some cases from about 5 to 10 mol % of the compound of formula (1) and the compound of formula (2).

[0052] Additional suitable strong Lewis acids can be found in (Chemical Reviews, 1996, v. 96, pp. 3269-3301; a list of strong Lewis acids is provided on page 3271), the disclosure of which is incorporated herein by reference. In some embodiments, the reaction mixture is heated to subambient or ambient temperatures. In some embodiments, the reaction mixture is heated to a temperature between -50°C and 50°C. In one embodiment, the reaction mixture is heated to a temperature between -50°C and 25°C. In some embodiments, the reaction is carried out at a reaction pressure between 0.1 pounds per square inch gauge (psig) and 300 pounds per square inch gauge (psig). In some embodiments, the reaction is carried out under autogenous pressure.

[0053] In some embodiments, the formation of the compound of formula (3) may be carried out in the presence of a solvent. In some embodiments, the solvent comprises at least one of the reaction products (e.g., at least one compound of formula (3)), at least one starting material (e.g., at least one of the compounds of formula (1) or (2)), or a perfluorinated saturated compound. In some embodiments, the perfluorinated saturated compound may comprise perfluoropentane, perfluorohexane, cyclic dimers of hexafluoropropene (a mixture of perfluoro-1,2-dimethylcyclobutane and perfluoro-1,3-dimethylcyclobutane), and combinations thereof. The amount of solvent varies as a function of the volume of the reactor and the ratio of the compound of formula (1) to the compound of formula (2) used to obtain the compound of formula (3).

[0054] The compounds of formula (3) may be used in a number of applications for the transfer of heat, for example as heat transfer fluids. In one embodiment, the compounds of formula (3) may be used to transfer heat from an article. The article may be contacted with a heat transfer medium comprising at least one compound of formula (3). The compositions of the present invention may have a heat of vaporization in the range of about 80 to about 150 kJ / kg, about 90 to about 140 kJ / kg, and in some cases about 100 to about 130 kJ / kg, calculated using the Clausius-Clapeyron equation.

[0055] The compounds of formula (3) can be used in a variety of applications, for example as working fluids. The working fluid provides a medium for transporting heat or for generating power through mechanical means by expansion. The working fluid is typically in a liquid state in a first region. The working fluid absorbs heat in the first region, vaporizes, and travels to a second region having a lower temperature where it condenses. The working fluid is typically returned to the first region after condensation, allowing the heat transfer cycle to repeat. The working fluid can be used in conjunction with compression systems, expansion systems, pumps, or passive evaporative cooling such as heat pipes or thermosiphons.

[0056] Compounds of formula (3) may also be used as solvents in a variety of applications such as cleaning (vapor degreasing, solvent stripping) or as carrier fluids for the deposition or removal of soluble compounds.

[0057] In use, the working fluid in the first region is exposed to a higher (first) temperature and the working fluid is vaporized, absorbing thermal energy. The vaporized working fluid travels to a second region that is at a lower (second) temperature than the first region. The working fluid condenses in the second region, releasing thermal energy that is transported out of the system. The working fluid is then returned to the first region. The working fluid typically travels in a cyclical fashion between the first and second regions, transporting thermal energy between the first and second regions.

[0058] The working fluid is selected to undergo a phase transition from a liquid to a gaseous state over a desired operating temperature range of a system, such as, for example, a heat pipe or thermosiphon. In some embodiments, the composition of the working fluid comprises one or more compounds of formula (3). In some embodiments, the working fluid is selected from the group consisting of 151-12mcyE, HFO-153-10mczz, HFO-153-10mzz, HFO-153-10mzzy, 151-12mcyZ, CF 3 CH=CHCF 2 CF 2 Cl, CF 3 CH=CHCF 2 CF 2 CF 2 Cl, CF 3 CH=CHCF 2 CFClCF 3 , C.F. 3 CH=CHCFClCF 3 , 153-10ze, R-1214xbE, F1214YA, C 2 F 5 CH=CFC 2 F 5 ,BrCF 2 CF 2 CH=CH 2, R-1214xbZ, or R-1233yd(Z). In some embodiments, the operating temperature is at least 0° C., at least 10° C., at least 20° C., at least 30° C., at least 40° C., at least 50° C., less than 75° C., less than 70° C., less than 65° C., less than 60° C., less than 55° C., or combinations thereof.

[0059] The ability of a working fluid to transport heat is related to the working fluid's heat of vaporization. The greater the working fluid's heat of vaporization, the greater the amount of energy it absorbs, transports across the heat pipe during vaporization, and releases during condensation. In some embodiments, the compound of formula (3) may exhibit a heat of vaporization of at least about 80 kJ / kg.

[0060] The working fluid may also be selected based at least in part on additional material properties. Because the working fluid condenses and returns to the first region, a working fluid having a lower viscosity flows more easily between the two regions. In some embodiments, the compound of formula (3) may exhibit a lower viscosity than water at the same temperature over the operating temperature range. In some embodiments, the compound of formula (3) exhibits a viscosity of less than 0.5 centipoise at 55°C. The compositions of the present invention may have a dynamic viscosity ranging from about 0.001 to about 3 centipoise, from about 0.1 to about 2, and in some cases from about 0.15 to about 1.5, as determined by ASTM D445 at a temperature of 55°C.

[0061] Compounds of formula (3) as working fluids for heat transfer applications may be selected based at least in part on the surface tension exhibited by the material. For example, in heat pipe applications, working fluids exhibiting high surface tension may be more easily transported between hot and cold regions. In some embodiments, the selection of wick materials may increase the rate at which condensed working fluid is returned to the hot region of the heat pipe. In some embodiments, the working fluid may exhibit a lower surface tension than water at the same temperature over the operating temperature range. In some embodiments, compounds of formula (3) exhibit a surface tension of less than 64.5 dynes / cm at 70°C, less than 66.3 dynes / cm at 60°C, and / or less than 67.9 dynes / cm at 50°C.

[0062] The working fluid may also be selected based at least in part on other thermodynamic properties of the material. A working fluid that exhibits a lower specific heat and / or a lower thermal conductivity than water at the same temperature may enhance energy transport between the hot and cold regions of the heat pipe. In some embodiments, the working fluid may exhibit a specific heat of less than about 4.2 J / g·K. In some embodiments, the compound of formula (3) may exhibit a thermal conductivity of less than about 0.6 W / m·K at 20° C.

[0063] The working fluid may also be selected to exhibit a dielectric constant suitable for electrical applications. In general, materials exhibiting a low dielectric constant enhance the electrical insulation of electrical components immersed therein. Examples of such electrical components include, for example, automobile batteries, computers, and servers, where the dielectric constant is less than about 2.5. In some embodiments, the dielectric constant of the working fluid is less than about 8 over its operating frequency range (0-20 GHz). Suitable dielectric working fluids include compounds of formula (3) and mixtures thereof having a dielectric constant of less than 7.3, less than 5.5, less than 5.0, less than 4.0, less than 3.5, less than 2.7, less than 2.5, less than 2.0, less than 1.9, less than 1.8, or less than 1.5 over the operating frequency range (0-20 GHz). Other embodiments include compounds and mixtures thereof having a dielectric constant greater than about 1.0 and less than about 8.0, greater than about 2.0 and less than about 7.3, greater than about 2.5 and less than about 5.5, or greater than about 3.5 and less than about 5.0.

[0064] Examples of compounds of formula (3) are shown in Table 1.

[0065] [Table 1] * Measured using ASTM D924 ** Calculated using conventional methods known in the art.

[0066] Additional additives may be added to the working fluid. Suitable additives include linear hydrocarbons, linear halocarbons, cyclic hydrocarbons, cyclic halocarbons, heptafluorocyclopentane, alcohols (e.g., methanol, ethanol, isopropanol), ethers, halogenated ethers, ketones, and halogenated ketones. Examples of suitable additives include pentane (boiling point 36° C.), hexane (69° C.), heptane (98° C.), octane (125° C.), cyclopentane (49° C.), cyclohexane (80° C.), cycloheptane (118° C.), methylcyclobutane (39° C.), methylcyclopentane (72° C.), diethyl ether (35° C.), diisopropyl ether (boiling point 69° C.), C 4 F 9 OCH 3 (CAS 163702-07-6), C 4 F 9 OCH 2 CH 3 (CAS 163702-05-4), iC 4 F 9 OCH 2 CH 3 (CAS 163702-06-5), (CF 3 ) 2 CFCF(OCH 3 )CF 2 CF 3 (73DE, CAS 132182-92-4), C 3 F 7 OCH 3 (CAS 375-03-1), (CF 3 ) 2 CFCF(OCH 2 CH 3 )CF 2 CF 2 CF 3(HFE 7500, CAS 297730-93-9), 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)pentane (HFE 7600, CAS 870778-34-0), furan,2,3,3,4,4-pentafluorotetrahydro-5-methoxy-2,5-bis[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-(HFE 7700), [CAS 812-05-4], and 1,1,1,2,4,4,5,5,5-nonafluoro-(2-trifluoromethyl)-3-pentanone (Novec 1230, CAS 756-13-8). These additives typically have a greater GWP than the compounds of formula (3) of the present invention and compositions containing compounds of formula (3). The amount of additive will vary depending on the desired GWP of the working fluid.

[0067] While the compositions of the present invention can be used as a dielectric working fluid in any suitable submersion cooling system, one suitable submersion cooling system is shown in FIG. 1. Referring now to FIG. 1, FIG. 1 shows a submersion cooling unit 100. The submersion cooling system 100 includes a submersion cell 110 that defines an internal cavity 120. An electronic component 130 to be cooled can be disposed within the internal cavity 120. A dielectric working fluid 140 of the present invention is provided to the internal cavity 120 to partially fill the internal cavity 120. The dielectric working fluid 140 at least partially submerges the electronic component 130. In some embodiments, the dielectric working fluid 140 substantially submerges the electronic component 130. In one embodiment, the dielectric working fluid 140 completely submerges the electronic component 130. A condensing coil 150 is additionally present within the internal cavity 120. The condensing coil 150 can be spatially located above at least a portion of the dielectric working fluid 140.

[0068] During operation, heat generated by the electrical components 130 heats the dielectric working fluid 140, vaporizing a portion of the dielectric working fluid 140. The vaporized dielectric working fluid 140 contacts the condensing coil 150 above the dielectric working fluid 140 and transfers thermal energy to the condensing coil 150, thereby allowing the condensed dielectric working fluid 140 to descend into the dielectric working fluid 140 below. The thermal energy transferred to the condensing coil 150 is transported out of the submerged cell 110 and released into the environment via the heat exchanger 160.

[0069] The following examples are provided to illustrate certain aspects of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0070] A typical example for the formation of a compound of formula (3) is shown below.

[0071] Example 1 Reaction of HFO-1327 with tetrafluoroethylene (TFE) catalyzed by SbF5

[0072] [ka]

[0073] In a 400 mL Hastelloy shaker tube, add 10 g (0.046 mol) of SbF 5 The shaker tube was cooled in dry ice, evacuated, and charged with 65 g (0.36 mol) of HFO-1327 (CF 3 CH=CFCF 3 ) and 40 g (0.4 mol) tetrafluoroethylene (TFE). The tube was placed in an explosion-proof wall, warmed to ambient temperature, and stirred for 16 h. 100 mL of water was poured into the shaker tube, the tube was cooled on ice, degassed, and the contents were removed. The organic layer was separated and diluted with MgSO 4The crude product was dried over 100° C. and filtered to give 102 g of crude product, which was fractionated to give a fraction of 80 g (79% yield) (boiling point 47-48° C.). 3 CF 2 CF=CHCF 2 CF 3 and CF 3 CF=CHCF 2 CF 3 The fraction was identified as a 90:10 mixture with (the purity of this fraction was >99.5%). EC 2 F 5 CH=CFC 2 F 5 1 H Nuclear Magnetic Resonance (NMR) (CDCl) 3 ):5.83(dt,29.3,12.2Hz)ppm 19 F NMR (CDCl 3 ): -83.96(3F, td, 6.2, 2.1Hz), -86.06(3F, dt, 5.7, 2.0Hz), -110.83(1F, m), -113.48(2F, ddq, 22.9, 12.2, 2.1Hz), -122.75(2F, dq, 12.9, 2.0Hz)ppm E-CF 3 CF=CHCF 2 CF 2 CF 3 19 F NMR (CDCl 3 ):-74.03(3F, dt, 9.4, 1.5Hz), -80.64(3F, t, 9.3Hz), -110.78(1F, m), -114.86(2F, m), -128.06(2F, d, 6.4Hz)ppm 1 H NMR (CDCl 3 ):6.74(1H, m), 6.91(1H, m)ppm MS (m / z, mixture of isomers): 282 (M + , C 6 HF 11 + )

[0074] Example 2 SbF 5 Reaction of HFO-1327 with chlorotrifluoroethylene catalyzed by

[0075] [ka]

[0076] In a 25 mL round-bottom flask, add 5 g (0.023 mol) of SbF 5 The flask was equipped with a dry ice condenser connected to a cold trap (-78°C), a thermocouple well, a gas inlet tube, and a magnetic stir bar. 3 CH=CFCF 3 was slowly added to the flask with vigorous stirring at a temperature of +2-5°C. The reaction mixture was treated with CFCl=CF 2 (Chlorotrifluoroethylene, CTFE, 6 g, 0.051 mol) was added slowly over 30 minutes and the reaction mixture was allowed to warm to ambient temperature overnight. The next morning, the reaction flask was cooled with regular ice and the CTFE collected in the cold trap was added to the reaction mixture and the reaction continued. The temperature was allowed to rise to 18°C ​​over 10 hours. At this point, the reaction mixture was dumped into 100 mL of ice water and the organic layer was separated, washed with water and added with MgSO 4 The mixture was dried over 100° C. and filtered to give 20 g of crude product, which was fractionated to give a 14 g (83% yield) fraction (boiling point 74-76° C.). 2 F 5 CH=CFCF 2 CF 2 Cl and EC 2 F 5 CH=CFCFClCF 3 It was identified as a mixture of 51:49 and 51:51. C 2 F 5 CH=CFCF 2 CF 2 Cl: 19 F NMR (CDCl 3): -70.78(2F, m), -85.82(3F(m), -108.68(1F, m), -113.27(2F, ddq, 23.0, 12.0, 2.3Hz), -118.10(2F, dtt, 12.2, 5.0, 2.3Hz)ppm 1 H NMR (CDCl 3 ):5.7~6.0(m)ppm C 2 F 5 CH=CFCFClCF 3 : 19 F NMR (CDCl 3 ): -80.55(3F, t, 7.5Hz), -85.82(3F, m), -104.99(1F, m), -113.02(1F, dq, 23.5, 10.8Hz), -133.43(1F, m)ppm 1 H NMR (CDCl 3 ):5.7~6.0(m)ppm GC / MS (z / e, mixture of isomers): 298 (M + , C 6 HClF 10 + )

[0077] Example 3 SbF 5 Reaction of HFO-153-10mzzy (F13iE) with TFE catalyzed by

[0078] [ka]

[0079] In a shaker tube (200 mL), add 5 g (0.02 mol) of antimony pentafluoride (SbF 5 The reaction vessel was cooled with dry ice, evacuated, and charged with 95 g (0.36 mol) of (CF 3 ) 2 CFCH=CHCF 3(HFO-153-10mzzy) was added to the reactor followed by 40 g (0.4 mol) of TFE. The reactor was held at 20°C for 12 hours. Within the first hour of starting the reaction, a pressure drop occurred (from 120 psi to 5 psi) and the internal temperature rose sharply to 30°C. The shaker tube was vented and the liquid reaction mixture was transferred to a glass bottle. The reaction mixture was slowly poured into 500 ml of ice water (to allow cooling) and the residual SbF 5 The organic layer was separated and washed with water (100 mL x 2), then with MgSO 4 The mixture was dried over low heat. The amount of HFO-153-10mzzy was in excess so that HFO-153-10mzzy served as both a solvent and a reactant, thereby promoting the formation of HFO-153-10mzzy. After filtration, 152 g of crude product was isolated. The crude material was analyzed by NMR, which showed a small amount of HFO-153-10mzzy, (CF 3 ) 2 CFCH=CHCF 2 CF 2 CF 3 , and only a few (CF 3 ) 2 CFCH=CHCF(C 2 F 5 ) 2 The crude material was shown to contain a ratio of 23:76.9:0.1. The crude material was fractionated at atmospheric pressure to give 100 g (76% yield) of E-(CF 3 ) 2 CFCH=CHCF 2 CF 2 CF 3 (Boiling point 92.2-92.5°C (see Table 4)) (purity about 99%) was obtained. The residue in the pot (4 g) was (CF 3 ) 2 CFCH=CHCF 2 CF 2 CF 3 And only a few (CF 3 ) 2 CFCH=CHCF(C 2 F 5 ) 2 It was found to be a mixture of these in a ratio of 85:15. E-(CF 3) 2 CFCH=CHCF 2 CF 2 CF 3 : 19 F NMR (CDCl 3 ): -76.88 (6F, d, 6.8Hz), -80.78 (3F, t, 9.0Hz), -115.05 (2F, quint., 9.0Hz), -128.01 (2F, s), -187.45 (1F, m)ppm. 1 H NMR (CDCl 3 ):6.46(m)ppm. MS(m / z): 364(M + , C 8 F 14 H 2 + ). (CF 3 ) 2 CFCH=CHCF(CF 2 CF 3 ) 2 : 19 F NMR (CDCl 3 ):-79.47(6F, d, 6.7Hz), -79.96(6F, d, 11.6Hz), -121.17(2F, A:B quartet., 298Hz), -122.23(2F, A:B quartet., 298Hz), -186.15(1F, m), -187.47(1F, m)ppm. 1 H NMR (CDCl 3 ):6.38(m)ppm. GC / MS(m / z): 464(M+, C 10 F 18 H 2 + ).

[0080] Example 4 SbF 5 The reaction of HFO-1326 with tetrafluoroethylene catalyzed by

[0081] [ka]

[0082] In a 400 mL Hastelloy shaker tube, 6 g (0.028 mol) of SbF 5 The shaker tube was cooled in dry ice, evacuated, and charged with 60 g (0.3 mol) of HCFO-1326 (CF 3 CH=CClCF 3 ) and 50 g (0.5 mol) tetrafluoroethylene (TFE). The tube was placed in an explosion-proof wall, warmed to ambient temperature, and stirred for 16 h. 100 mL of water was poured into the shaker tube, the tube was cooled on ice, degassed, and the contents were removed. The organic layer was separated and diluted with MgSO 4 After drying over 100° C. and filtration, 85 g of crude product was obtained, which was 50% HCFO-1326 and 37% CF 3 CCl=CHC 3 F 7 and 13% HCFO-1326 / TFE 1:2 adduct (GC / MS).

[0083] The crude reaction mixture was fractionated to give a 39 g (79% yield, 50% conversion of HCFO-1326) fraction (boiling point 80-86 °C) (E-CF 3 CCl=CHCF 2 CF 3 and Z-CF 3 CCl=CHCF 2 CF 3 A 65:35 mixture of 10 g of dimethylformamide (identified as a 65:35 mixture of 10 g of dimethylformamide and 10 g of dimethylformamide) was obtained along with 10 g of a higher boiling fraction (1:2 adduct, GC / MS). E-CF 3 CCl=CHC 3 F 7 : 19 F NMR (CDCl 3 ): -70.98(3F, s), -80.67(3F, t, 8.9Hz), -111.64(2F, sixt., 10.5Hz), -127.16(2F, q, 4.0Hz)ppm 1 H NMR (CDCl3 ):6.59(t, 12.3Hz)ppm Z-CF 3 CCl=CHC 3 F 7 : 19 F NMR (CDCl 3 ):-63.64(3F,tt,17.7,4.0Hz),-80.52(3F,t,10.5),-107.20(2F,m),-127.76(2F,s)ppm 1 H NMR (CDCl 3 ): 1 H NMR (CDCl 3 ):6.41(t, 14.5Hz)ppm GC / MS (m / z, mixture of isomers): 298 (M + , C 6 HClF 10 + ) 1:2の-C 2 F 5 CF = CHCCl (CF 3 )CF 2 CF 3 Additive form (main opposite body) (boiling point: 105~109℃ (estimated)). 19 F NMR (CDCl 3 ): -71.83 (3F, dm, 12.1Hz), -78.24 (3F, m), -83.96 (3F, dt, 6.1, 1.8Hz), -108.55 (1F, m), -115.92 (2F, AB quart., J d =296.7Hz), -122.32(2F, ddq, 13.0, 10.8, 2.1Hz)ppm 1 H NMR (CDCl 3 ):5.84(d, 27.6Hz)ppm GC / MS (m / z, mixture of isomers): 398 (M + , C 8 HClF 14 + )

[0084] (Example 5) Sb 5 によってcatalyst される、C4 F 9 CH=CHCF 3 Reaction of (F14E) with chlorotrifluoroethylene (CTFE)

[0085] [ka]

[0086] In a 50 mL round-bottom flask, add 5 g (0.023 mol) of SbF 5 The flask was then fitted with a dry ice condenser, a thermocouple well, a gas inlet tube, and a magnetic stir bar. The flask was cooled with regular ice and 23 g (0.073 mol) of C 4 F 9 CH=CHCF 3 was slowly added to the flask with vigorous stirring at a temperature of +2-5°C. The reaction mixture was treated with CFCl=CF 2 (Chlorotrifluoroethylene, CTFE, 7 g, 0.06 mol) was added slowly over 30 min and the reaction mixture was allowed to warm to ambient temperature over 3 h. It was dumped into 100 mL of ice water and the organic layer was separated, washed with water and added MgSO 4 The crude product was dried over 100 ml of ethyl acetate and filtered. 4 F 9 CH=CHCF 3 (conversion 67%) and 67% product. It was fractionated to give a 15 g fraction (boiling point 137-141°C) (converted C 4 F 9 CH=CHCF 3 The fraction was found to be 68% yield for EC 4 F 9 CH=CHCF 2 CF 2 CF 2 Cl and EC 4 F 9 CH=CHCF 2 CFClCF 3 It was identified as a mixture of (ratio 55:45). EC 4 F 9 CH=CHCF 2 CF2 CF 2 Cl: 19 F NMR (CDCl 3 ): -67.05(2F, t, 11.2Hz), -81.06(3F, m), -113.26(2F, m), -114.08(2F, m), -121.86(2F, s), -124.25(2F, m), -125.85(2F, m)ppm 1 H NMR (CDCl 3 ):6.40~6.62(m)ppm EC 4 F 9 CH=CHCF 2 CFClCF 3 19 F NMR (CDCl3): -76.81 (3F, q, 9.7Hz), -81.06 (3F, m), -109.61 (2F, q, 9.7Hz), -114.08 (2 F, m), -121.86 (2F, s), -124.25 (2F, m), -125.85 (2F, m), -138.51 (1F, sixt., 7.5Hz)ppm 1 H NMR (CDCl 3 ):6.40~6.62(m)ppm GC / MS (m / z, mixture of isomers): 430 (M + , C 9 H 2 ClF 15 + )

[0087] Example 6 SbF 5 Catalyzed by (CF 3 ) 2 CF 2 CH=CHCF 3 Reaction of with chlorotrifluoroethylene

[0088] [ka]

[0089] The reaction of HFO-153-10mzzy (F13iE) with CTFE was investigated using 5g (0.023mol) of SbF 5 The experiment was carried out using the setup described in the previous experiment. 30 g (0.11 mol) of HFO-153-10mzzy was added slowly to the flask under vigorous stirring at a temperature of +2-5°C. The reaction mixture was diluted with gaseous CFCl=CF 2 (Chlorotrifluoroethylene, CTFE, 13.5 g, 0.12 mol) was added slowly over 30 min while maintaining the temperature of the reaction mixture between 5-15 °C. The reaction mixture was maintained at ambient temperature for 3 h. It was dumped into 100 mL of ice water and the organic layer was separated, washed with water and added with MgSO 4 The crude reaction mixture was dried over ice and filtered. The crude reaction mixture was fractionated to give a 25 g (80% yield) fraction (boiling point 111-115°C) which was identified by NMR and GC / MS as (CF 3 ) 2 CFCH=CHCF 2 CF 2 CF 2 Cl and (CF 3 ) 2 CFCH=CHCF 2 CF 2 ClCF 3 It was identified as a mixture of (ratio 59:41). (CF 3 ) 2 CFCH=CHCF 2 CF 2 CF 2 Cl: 19 F NMR (CDCl 3 ): -67.54(2F, t, 11.0Hz), -76.54(6F, m), -113.00(2F, q, 10.3Hz), -122.06(2F, s), -187.19(1F, m)ppm 1 H NMR (CDCl 3 ):6.4~6.6(m)ppm (CF 3 ) 2 CFCH=CHCF 2 CFClCF 3 : 19F NMR (CDCl3): -76.54 (6F, m), -76.95 (3F, m), -109.44 (2F, sixt., 10.4Hz), -138.56 (1F, sixt., 7.6Hz), -187.19 (1F, m)ppm 1 H NMR(CDCl3): 5.7-6.0(m)ppm GC / MS (z / e, mixture of isomers): 380 (M + , C 8 H 2 ClF 13 + )

[0090] Example 7 SbF 5 Reaction of HFO-1438mzz(F12E) with CTFE catalyzed by

[0091] [ka]

[0092] The reaction of HFO-1438mzz with CTFE was investigated using 5 g (0.023 mol) of SbF 5 The experiment was carried out using the setup described in the previous experiment. 30 g (0.14 mol) of HFO-1438mzz was added slowly to the flask under vigorous stirring at a temperature of +2-5°C. The reaction mixture was treated with gaseous CFCl=CF 2 (Chlorotrifluoroethylene, CTFE, 16 g, 0.14 mol) was added slowly over 30 min. The reaction mixture was left overnight. It was dumped into 100 mL of ice water and the organic layer was separated, washed with water and added MgSO 4 The crude reaction mixture (30 g) was fractionated to give a 6 g (13% yield) fraction (boiling point 90-95° C.) which showed no EC 2 F 5 CH=CHCF 2 CF 2 CF 2 Cl and EC 2 F 5 CH=CHCF 2CF 2 ClCF 3 It was identified as a mixture of (60:40 ratio) E-CF 3 CF 2 CH=CHCF 2 CF 2 CF 2 Cl 19 F NMR (CDCl 3 ): -67.35(2F, t, 10.7Hz), -84.96(3F, m), -113.41(2F, q, 10.7Hz), -117.73(2F, m), -121.97(2F, s)ppm EC 2 F 5 CH=CHCF 2 CF 2 ClCF 3 19 F NMR (CDCl 3 ):-76.89(3F, m), -84.96(3F, m), -109.79(2F, m), -117.73(2F, m), -138.56(1F, m)ppm 1 H NMR (CDCl 3 , mixture of isomers): 6.37~6.64(m)ppm GC / MS (m / z, mixture of isomers): 330 (M + , C 7 H 2 ClF 11 + )

[0093] Example 8 SbF 5 The reaction of HFO-1327 with CFCl=CFCl (CFO-1112) catalyzed by

[0094] [ka]

[0095] The reaction of HFO-1327 with CFCl=CFCl was investigated using 5 g (0.023 mol) of SbF 5and 20g (0.11mol) of CF 3 CH=CFCF 3 The experiment was carried out using the setup described in the previous experiment. CFO-1112 was added slowly to the reaction mixture over 30 min with vigorous stirring at a temperature of +2-5 °C. The reaction mixture was kept at 5-18 °C for 2 h. It was dumped into 100 mL of ice water and the organic layer was separated, washed with water and added MgSO 4 The crude reaction mixture (32 g) was fractionated to give a fraction of 11 g (33% yield) with boiling point of 102-104° C. This fraction was found to be 100% pure by NMR and GC / MS. 2 F 5 CF=CHCFClCF 2 It was identified as a mixture of Cl. EC 2 F 5 CF=CHCFClCF 2 Cl, boiling point 102-104℃, yield 33% 19 F NMR (CDCl 3 ): -65.69(2F, AB q., 173.0Hz), -85.74(3F, dt, 5.6, 2.7Hz), -103.66(1F, m), -112.98(2F, AB q., 278.8Hz), -126.53(1F, dt, 18.9, 10.5Hz)ppm 1 H NMR (CDCl 3 ):5.70(dt,30.4,11.6Hz)ppm GC / MS(m / z):314(M + , C 6 HCl 2 F 9 + ).

[0096] Although the present invention has been described with reference to one or more embodiments, it will be understood by those skilled in the art that various changes can be made without departing from the scope of the invention and that equivalents can be substituted for its elements. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope of the invention. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but the invention is intended to include all embodiments falling within the scope of the appended claims. In addition, all numerical values ​​specified in the detailed description should be interpreted as if both exact and approximate values ​​were explicitly specified. The main inventions described in this specification are listed below. (I) A process for producing a fluoroolefin, comprising the steps of: Formula (1) R f CX 1 =CHCF 3 (1) [In the formula, R f is a straight or branched chain C 1 ~C 10 are perfluorinated or polyfluorinated alkyl groups, X 1 is H, Br, Cl, or F. The compounds constituting Formula (2) CX 2 X 3 =CX 4 X 5 (2) [In the formula, X 2 , X 3 , X 4 , and X 5 are each independently H, Br, Cl, or F; X 2 , X 3 , X 4 , and X 5 At least three of the The fluorinated ethylene compounds that make up Formula (3) Rf (CF 2 ) n CX 6 =CH(CF 2 ) m CX 7 X 8 CFX 9 X 10 (3) [In the formula, n is an integer of 0 to 10, m is an integer from 1 to 10; X 6 , X 7 , X 8 , X 9 , and X 10 are each independently H, Br, Cl, or F; X 6 , X 7 , X 8 , X 9 , and X 10 The total number of H, Br, Cl, and F represented by the formula (1) and the formula (2) is 1 , X 2 , X 3 , X 4 , and X 5

[0033] in the presence of a sufficient amount of a catalyst to form a composition comprising the compound of formula (I). (II) R f CF 3 , C 2 F 5 , C 3 F 7 ,I C 3 F 7 , C 4 F 9 , C 5 F 11 ,I C 5 F 11 , C 6 F 13 , and iC 6 F 13 The method according to (I), wherein the compound is selected from the group consisting of: (III) The compound of formula (1) is 4 F 9 CH=CHCF3 , (CF 3 ) 2 CFCH=CHCF 3 , C.F. 3 CH=CFCF 3 , and C.F. 3 CH=CClCF 3 and comprising at least one element selected from the group consisting of: The compound of formula (3) is 4 F 9 CH=CHCF 2 CFClCF 3 , C 4 F 9 CH=CHCF 2 CF 2 CF 2 Cl, (CF 3 ) 2 CFCH=CHCF 2 CFClCF 3 , (CF 3 ) 2 CFCH=CHCF 2 CF 2 CF 2 Cl, C 2 F 5 CH=CHC 2 F 5 , C 2 F 5 CF=CHCFClCF 3 , C 2 F 5 CF=CHCF 2 CF 2 Cl and C 3 F 7 CH=CClCF 3 The method according to (I), comprising at least one element selected from the group consisting of: (IV) The fluorinated ethylene of formula (2) is CF 2 =CF 2 , CFCl=CF 2 , CFCl=CFCl, CFH=CF 2 (HFO-1123), CFH=CFH(HFO-1132, and CF 2 =CH 2 (VF2), The composition is 4 F9 CH=CHCF 2 CFClCF 3 , C 4 F 9 CH=CHCF 2 CF 2 CF 2 Cl, (CF 3 ) 2 CFCH=CHCF 2 CFClCF 3 , (CF 3 ) 2 CFCH=CHCF 2 CF 2 CF 2 Cl, C 2 F 5 CH=CHC 2 F 5 , C 2 F 5 CF=CHCFClCF 3 , C 2 F 5 CF=CHCF 2 CF 2 Cl or C 3 F 7 CH=CClCF 3 , and C.F. 3 CF=CHCFClCF 2 The method according to (I), comprising at least one element selected from the group consisting of Cl. (V) The method of (I), wherein the sufficient amount comprises a molar ratio of fluoroethylene:the compound of formula (1) of from 0.01:1 to 5:1. (VI) The method of (V), wherein the sufficient amount comprises a molar ratio of fluoroethylene:the compound of formula (1) of from 0.1:1 to 2:1. (VII) The method according to (I), wherein the sufficient amount comprises a molar ratio of the compound of formula (2) to the compound of formula (1) of 0.01:1 to 5:1. (VIII) The method according to (I), wherein the composition further comprises a solvent. (IX) The method according to (VIII), wherein the solvent comprises a perfluorinated saturated compound. (X) The method according to (IX), wherein the perfluorinated saturated compound is selected from the group consisting of perfluoropentane, perfluorohexane, cyclic dimers of hexafluoropropene (a mixture of perfluoro-1,2-dimethylcyclobutane and perfluoro-1,3-dimethylcyclobutane), and combinations thereof. (XI) The catalyst is antimony pentafluoride (SbF 5 ), or formula (4) SbCl x F 5 - x [In the formula, x=0.01 to 0.5] The method according to (I), comprising the compound of formula (I): (XII) The catalyst is aluminum chloride (AlCl 3 ), antimony pentafluoride (SbF 5 ), and aluminum fluoride chloride (AlCl x F 3-x The method according to (XI), comprising at least one element selected from the group consisting of: (XIII) R f is a straight or branched chain C 2 ~C 10 The method of (I), comprising a perfluorinated alkyl group. (XIV) R f CF 3 , C 2 F 5 , C 3 F 7 ,I C 3 F 7 , C 4 F 9 , C 5 F 11 ,I C 5 F 11 , C 6 F 13 , or iC 6 F 13 The method according to (I), (XV) The method according to (I), wherein the contacting step is carried out at subambient or ambient temperature. (XVI) The method according to (I), wherein the reaction is carried out under autogenous pressure. (XVII) The method according to (I), wherein the reaction is carried out at 0.1 to 300 psig. (XVIII) The method according to (I), wherein the reaction is carried out in a closed system. (XIX) The method according to (I), wherein the contacting step is carried out at a temperature of -50°C to 50°C. (XX) A composition formed by the method according to (I). (XXI) A composition formed by the method according to (III). (XXII) A composition formed by the method according to (IV). (XXIII) A method for transferring heat from an electronic component, the method comprising: providing an immersion cell having at least one electronic component; and introducing a composition according to any one of (XX) to (XXII) into the immersion cell, wherein the composition at least partially immerses the electronic component. (XXIV) The method of (XXIII), wherein the electronic component comprises at least one of an automobile battery, a computer, or a server. (XXV) Use of the composition according to any one of (XX) to (XXII) for removing heat from an electronic component.

Claims

1. 1. A process for producing a fluoroolefin, comprising the steps of: Formula (1) R f CX 1 =CHCF 3 (1) [In the formula, R f is a straight or branched chain C 1 ~C 10 are perfluorinated or polyfluorinated alkyl groups, X 1 is H, Br, Cl, or F. The compounds constituting Formula (2) CX 2 X 3 =CX 4 X 5 (2) [In the formula, X 2 , X 3 , X 4 , and X 5 are each independently H, Br, Cl, or F; X 2 , X 3 , X 4 , and X 5 at least three of the fluorinated ethylenes of formula (2) are F, or the fluorinated ethylenes of formula (2) include at least one of CF 2 ═CF 2 , CFCl═CF 2 , CFCl═CFCl, CFH═CF 2 (HFO-1123), CFH═CFH (HFO-1132, and CF 2 ═CH 2 (VF2)). The fluorinated ethylene compound constituting the compound is Formula (3) R f (CF 2 ) n CX 6 =CH(CF 2 ) m CX 7 X 8 CFX 9 X 10 (3) [In the formula, n is an integer from 0 to 10, m is an integer from 1 to 10, X 6 , X 7 , X 8 , X 9 , and X 10 are each independently H, Br, Cl, or F; X 6 , X 7 , X 8 , X 9 , and X 10 The total number of H, Br, Cl, and F represented by X in formula (1) and formula (2) is 1 , X 2 , X 3 , X 4 , and X 5 The total number of H, Br, Cl, and F is the same as that provided by in the presence of a sufficient amount of a catalyst to form a composition comprising a compound of said compound of formula (1) comprises at least one member selected from the group consisting of C4F9CH=CHCF3, (CF3)2CFCH=CHCF3, CF3CH=CFCF3, and CF3CH=CClCF3; The method of claim 1, wherein the compound of formula (3) comprises at least one member selected from the group consisting of C4F9CH=CHCF2CFClCF3, C4F9CH=CHCF2CF2CF2Cl, (CF3)2CFCH=CHCF2CFClCF3, (CF3)2CFCH=CHCF2CF2CF2Cl, and C3F7CH=CClCF3.

2. 13. A composition formed by the method of claim 1.

3. 11. A method for transferring heat from an electronic component, comprising: providing an immersion cell having at least one electronic component; and introducing the composition of claim 2 into the immersion cell, wherein the composition at least partially immerses the electronic component.

4. 3. Use of the composition according to claim 2 for removing heat from electronic components.

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