Lewis Acid Catalyzed Synthesis of 1,2-Bis(perfluoroalkyl)ethylene

Abstract

The method for producing fluoroolefins comprises the step of reacting a compound R f The method includes contacting CH═CHF with a fluorinated ethylene compound of formula (2), CX₁X₂═CX₃X₄, in the presence of a Lewis acid catalyst. f is C1~C 10 In the compound of formula (2), X1, X2, X3, and X4 are each independently H, Cl, or F, and at least one of X1, X2, X3, and X4 is F. The resulting composition contains a compound R of formula (3): f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 In the compound of formula (3), X5, X6, X7, X8, X9, X 10 , X 11 , and X 12 are each independently H, Cl, or F, n is an integer of 0 or 1, and the total number of H, Cl, and F corresponds to the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2).

Description

Technical Field

[0001] This application claims the benefit of U.S. Patent Application No. 62 / 835,714, filed Apr. 18, 2019, the disclosure of which is incorporated herein by reference in its entirety as part of this specification.

[0002] (Field of the Invention) The present invention relates to the production of fluorinated alkene compounds.

Background Art

[0003] There is interest in low-temperature heat utilization (i.e., heat at temperatures below about 300° C.). Such heat may be extracted from various commercial, industrial, or natural sources. The increase in the temperature of available heat by a high-temperature mechanical compression heat pump (HTHP) and the conversion of available heat to mechanical power or electricity by an organic Rankine cycle (ORC), which match the heating requirements, are two promising approaches for utilizing low-temperature heat.

[0004] ORC and HTHP require the use of a working fluid. Working fluids with high global warming potential (GWP) currently commonly used in HTHP and ORC (e.g., HFC-245fa) have been previously referenced, but there is a need for more environmentally sustainable working fluids for HTHP and ORC. More specifically, there is a need for low-GWP working fluids having a boiling point above about 50° C., which are particularly suitable for converting available heat to power at temperatures close to or exceeding 200 degrees Celsius (hereinafter “° C.”) in this specification and for heating from available heat at low temperatures to temperatures close to 200° C. Even more specifically, low-GWP working fluids having a boiling point close to the boiling point of ethanol (78.4° C.) may be advantageous as substitutes for ethanol in ORC systems for heavy-duty vehicles (e.g., trucks), particularly in Europe. Such liquids may also be used as solvents and heat transfer fluids for various applications, including liquid immersion cooling and phase change cooling (e.g., for electronic devices including cooling of data centers).

[0005] For example, fluoroalkenes such as F23E(C2F5CH=CHC3F7) can be prepared using a four-step process that includes a substantial hydrogenation / dehydrogenation process and starting from an F-heptene-3 starting material. However, this process is very time-consuming and is based on relatively expensive starting materials (F-heptene is made using the reaction of hexafluoropropene (HFP) and 2 moles of tetrafluoroethane (TFE)).

[0006] International Publication No. 2008 / 057513 describes a process for the preparation of internal dihydrofluoroolefins of the formula RCH=CHC2F5. This process includes reacting RCH=CHF [wherein R is selected from perfluoroalkyl groups having 1 to 10 carbon atoms, and the alkyl group is any of fluorinated olefins that are an n-alkyl chain, a sec-alkyl chain, or an iso-alkyl chain] with tetrafluoroethylene in the liquid phase in the presence of antimony pentafluoride (SbF5), removing the Lewis acid catalyst, and isolating the dihydrofluoroolefin. The disclosure of International Publication No. 2008 / 057513 is incorporated herein by reference in its entirety.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Means for Solving the Problems

[0008] One embodiment of the present invention is Formula (1), R f CH=CHF(1) [wherein R f is C1 to C 10which is a perfluorinated alkyl group or a polyfluorinated alkyl group] with a compound of Formula (2), CX1X2=CX3X4(2) [wherein X1, 2, X3, and X4 are each independently H, Cl, or F, and at least one of X1, X2, X3, and X4 is F] with a fluorinated ethylene compound of Formula (3), R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(3) [wherein X5, X6, X7, X8, X9, X 10 , X 11 , and X 12 are each independently H, Cl, or F, and n is an integer of 0 or 1] contacting in the presence of a Lewis acid catalyst in an amount sufficient to form a composition comprising a compound of X5, X6, X7, X8, X9, X 10 , X 11 , and X 12 wherein the total number of each of H, Cl, and F represented by is the same as the total number of each of H, Cl, and F provided by the fluorinated ethylene compound of Formula (2), relates to a method for producing a fluoroolefin.

[0009] Another embodiment of the present invention is wherein the compound of Formula (1) comprises CF3CH=CHF (1234ze), and the composition comprises 1,1,1,4,4,5,5,5 - octafluoropent - 2 - ene, 3CH=CHC2F5 (F12E), including the aforementioned embodiment.

[0010] Another embodiment of the present invention is wherein the fluorinated ethylene of Formula (2) comprises CF2=CF2 (TFE), The composition includes 1,1,1,4,4,5,5,5 - octafluoropent - 2 - ene, 3CH=CHC2F5 (F12E), including the foregoing embodiments.

[0011] Another embodiment of the present invention is The compound of formula (1) includes CF3CH=CHF (1234ze), The fluorinated ethylene of formula (2) includes CF2=CF2 (TFE), The composition includes 1,1,1,4,4,5,5,5 - octafluoropent - 2 - ene, 3CH=CHC2F5 (F12E), including the foregoing embodiments.

[0012] Another embodiment of the present invention includes any combination of the foregoing embodiments, including a molar ratio of (TFE):(1234ze) where the sufficient amount is 0.01:1 to 5:1.

[0013] Another embodiment of the present invention includes any combination of the foregoing embodiments, including a molar ratio of (TFE):(1234ze) where the sufficient amount is 0.1:1 to 2:1.

[0014] Another embodiment of the present invention includes any combination of the foregoing embodiments, including a molar ratio of the compound of formula (2) to the compound of formula (1) where the sufficient amount is 0.01:1 to 5:1.

[0015] Another embodiment of the present invention includes any combination of the foregoing embodiments, where the composition further includes 1,1,1,2,2,5,5,6,6,7,7,7 - dodecafluorohept - 2 - ene, C3F7CH=CHC2F5 (F23E).

[0016] Another embodiment of the present invention includes any combination of the foregoing embodiments, where the composition further includes 4 - chloro - 1,1,1,4,5,5,5 - heptafluoropent - 2 - ene, CF3CH=CHCFClCF3 and 5 - chloro - 1,1,1,4,4,5,5 - heptafluoropent - 2 - ene, CF3CH=CHCF2CF2Cl.

[0017] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the composition further comprises at least one of a diluent and a solvent.

[0018] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the solvent is a perfluorinated saturated compound.

[0019] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the perfluorinated saturated compound is selected from the group consisting of perfluoropentane, perfluorohexane, a cyclic dimer of hexafluoropropene (a mixture of perfluoro-1,2-dimethylcyclobutane and perfluoro-1,3-dimethylcyclobutane), and combinations thereof.

[0020] Another embodiment of the present invention is wherein the fluorinated ethylene of formula (2) includes CClF=CF2 (CTFE), and the composition includes 4-chloro-1,1,1,4,5,5,5-heptafluoropent-2-ene, CF3CH=CHCClFCF3 or 5-chloro-1,1,1,4,4,5,5-heptafluoropent-2-ene, CF3CH=CHCF2CClF2, and any combination of the foregoing embodiments.

[0021] Another embodiment of the present invention is wherein the catalyst includes aluminum chloride (AlCl3) or a compound of formula (4), AlCl x F3- x [wherein x = 0.01 to 0.5], and any combination of the foregoing embodiments.

[0022] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the catalyst includes aluminum chloride (AlCl3).

[0023] Another embodiment of the present invention is that R f is a C2-C 10 perfluorinated alkyl group, and any combination of the foregoing embodiments.

[0024] Another embodiment of the present invention is R f is CF3, C2F5, C3F7, iC3F7, C4F9, C5F 11 , i-C5F 11 , C6F 13 or i-C6F 13 and includes any combination of the foregoing embodiments.

[0025] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the contacting step is performed at sub-ambient temperature or ambient temperature.

[0026] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the reaction is carried out under autogenic pressure.

[0027] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the reaction is carried out at 0.1 to 300 psig.

[0028] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the reaction is carried out in a closed system.

[0029] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the contacting step is performed at a temperature of -50 °C to 50 °C.

[0030] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the catalyst is aluminum chloride (AlCl3) or aluminum fluoride chloride AlCl x F3- x (ACF) with x = 0.01 to 0.5.

[0031] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein the catalyst includes aluminum chloride (AlCl3).

[0032] Another embodiment of the present invention includes any combination of the foregoing embodiments, wherein at least one of the diluent and the solvent includes the reaction product formed by the contacting step.

[0033] One embodiment of the present invention comprises: The present invention relates to a method for producing a fluoroolefin, comprising the step of contacting CF3CH=CHF (1234ze) with CF2=CF2 (TFE) in the presence of a catalyst in an amount sufficient to form a composition comprising 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-2-ene, C3F7CH=CHC2F5 (F23E).

[0034] Further embodiments of the present invention include any combination of the preceding embodiments, wherein the contacting step is carried out at a temperature between -10°C and 50°C.

[0035] Further embodiments of the invention include any combination of the preceding embodiments, wherein the composition further comprises 1,1,1,4,4,5,5,5-octafluoropent-2-ene, CF3CH=CHC2F5 (F12E).

[0036] Further embodiments of the invention include any combination of the preceding embodiments, wherein the composition further comprises 4-chloro-1,1,1,4,5,5,5-heptafluoropent-2-ene, CFCH=CHCFClCF, and 5-chloro-1,1,1,4,4,5,5-heptafluoropent-2-ene, CFCH=CHCFCFCl.

[0037] Further embodiments of the present invention include any combination of the preceding embodiments, wherein the composition further comprises at least one of a diluent and a solvent.

[0038] Another embodiment of the present invention includes any combination of the preceding embodiments, wherein the solvent is a perfluorinated saturated compound.

[0039] Another embodiment of the invention includes any combination of the preceding embodiments, 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.

[0040] Another embodiment of the present invention includes any combination of the foregoing embodiments, including a molar ratio of (TFE):(1234ze) where the sufficient amount is from 0.1:1 to 5:1.

[0041] Another embodiment of the present invention includes any combination of the foregoing embodiments, including a molar ratio of (TFE):(1234ze) where the sufficient amount is from 0.1:1 to 2:1.

[0042] Another embodiment of the present invention includes any combination of the foregoing embodiments, where the contacting step is performed at sub-ambient temperature or ambient temperature.

[0043] Another embodiment of the present invention includes any combination of the foregoing embodiments, where the reaction is carried out under autogenous pressure.

[0044] Another embodiment of the present invention includes any combination of the foregoing embodiments, where the reaction is carried out at 0.1 to 300 psig.

[0045] Another embodiment of the present invention includes any combination of the foregoing embodiments, where the reaction is carried out in a closed system.

[0046] Another embodiment of the present invention includes any combination of the foregoing embodiments, where the catalyst includes aluminum chloride (AlCl3).

[0047] Another embodiment of the present invention includes any combination of the foregoing embodiments, where at least one diluent and solvent includes the reaction product formed by the contacting step.

[0048] One embodiment of the present invention relates to a method for producing a fluoro-oligomer, including a step of heating CF3CH=CHF (1234ze) in the presence of a catalyst at a temperature and pressure sufficient to form a composition containing CF3CH=CHCH(CF3)CF2H.

[0049] Another embodiment of the present invention is that the catalyst is aluminum chloride (AlCl3) or aluminum fluoride chloride AlCl x F3- x (ACF) in any combination of the aforementioned embodiments.

[0050] In one embodiment, a method for producing a fluoroolefin comprises contacting a compound R of formula (1) f CH=CHF with a fluorinated ethylene compound CX1X2=CX3X4 of formula (2). In the compound of formula (1), R f is a C1-C 10 perfluorinated alkyl group. In the compound of formula (2), X1, X2, X3, and X4 are each independently H, Cl, or F, and at least one of X1, X2, X3, and X4 is F. The contacting step is carried out in the presence of a Lewis acid catalyst in an amount sufficient to form a composition comprising a compound R of formula (3) f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F under conditions sufficient to form a composition comprising F. In the compound of formula (3), X5, X6, X7, X8, X9, X 10 , X 11 , and X 12 are each independently H, Cl, or F, and the total number of H, Cl, and F represented by X5, X6, X7, X8, X9, X 10 , X 11 , and X 12 is the same as the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2).

[0051] In another embodiment, a method for producing a fluoroolefin comprises contacting CF3CH=CHF (1234ze) and CF2=CF2 in the presence of a catalyst in an amount sufficient to form a composition comprising 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-2-ene, C3F7CH=CHC2F5 (F23E).

[0052] In another embodiment, a method of manufacturing a fluoro-oligomer includes heating CF3CH=CHF (1234ze) in the presence of a catalyst at a temperature and pressure sufficient to form a composition comprising CF3CH=CHCH(CF3)CF2H.

[0053] One embodiment of the present invention relates to a composition formed by any combination of the aforementioned methods.

[0054] This embodiment 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 that illustrate the principles of the invention by way of example.

Mode for Carrying Out the Invention

[0055] Provide a one-step synthesis for the production of fluorinated alkenes.

[0056] For example, compared to a concept that does 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 a perfluorinated alkyl chain.

[0057] This approach may be carried out in any reactor suitable for a gas-phase fluorination reaction. The reactor is made of a material resistant to the reactants used. The reactor may be composed of a material resistant to the corrosive effects of hydrogen fluoride, such as stainless steel, Hastelloy®, Inconel®, Monel®, gold, or a gold wire or quartz. The reaction may be batch, continuous, semi-continuous, or a combination thereof. Suitable reactors include batch reaction vessels and tubular reactors.

[0058] In one embodiment, formula (1), R f CH=CHF(1) [wherein R f is C1-C10 a compound which is a perfluorinated alkyl group, is charged into a reactor and heated, and in the presence of a catalyst, formula (2), CX1X2=CX3X4(2) [wherein X1, X2, X3, and X4 are each independently H, Cl, or F, and at least one of X1, X2, X3, and X4 is F] is contacted with a fluorinated ethylene compound.

[0059] The temperature and pressure of the reactor are adjusted in the presence of a Lewis acid catalyst according to formula (3), R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(3) [wherein X5, X6, X7, X8, X9, X 10 , X 11 , and X 12 are each independently H, Cl, or F, and n is an integer of 0 or 1] and contains a compound, X5, X6, X7, X8, X9, X 10 , X 11 , and X 12 The total number of H, Cl, and F represented by each is maintained at a level sufficient to cause the formation of a composition that is the same as the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2).

[0060] In some embodiments, the compound of formula (1) includes 1,3,3,3-tetrafluoro-1-propene, CF3CH=CHF (1234ze). In one embodiment, the compound of formula (1) includes CF3CH=CHF (1234ze). In some embodiments, R f may be a linear or branched perfluorinated alkyl group or polyfluorinated alkyl group. In some embodiments, R f is CF3, C2F5, C3F7, iC3F7, C4F9, C5F 11 , i-C5F 11 , C6F 13or i-C6F 13 may also be used.

[0061] In some embodiments, the fluorinated ethylene of formula (2) comprises at least one of tetrafluoro-ethene, CF2=CF2 or CFCl=CF2 (1-chloro-1,2,2-trifluoro-ethene), CF2=CH2 (1,1-difluoro-ethene), CH2=CHF (1-fluoro-ethene), CF2=CCl2 (1,1-dichloro-2,2-difluoro-ethene), CFCl=CFC (1,2-chloro-1,2-difluoro-ethene). In one embodiment, the fluorinated ethylene of formula (2) comprises tetrafluoro-ethene CF2=CF2.

[0062] In one embodiment, the compound of formula (1) comprises CF3CH=CHF (1234ze), and the fluorinated ethylene of formula (2) comprises CF2=CF2. Reaction of CF3CH=CHF (1234ze) and CF2=CF2 (TFE) may result in the formation of a composition comprising 1,1,1,4,4,5,5,5-octafluoropent-2-ene, CF3CH=CHC2F5 (F12E).

[0063] If necessary, 1,1,1,4,4,5,5,5-octafluoropent-2-ene may be isolated and optionally purified before use. Suitable uses of 1,1,1,4,4,5,5,5-octafluoropent-2-ene include, but are not limited to, working fluids in systems utilizing thermodynamic cycles, reaction intermediates, refrigerants, heat transfer fluids with or without phase change, and solvents.

[0064] In some embodiments, the fluorinated ethylene of formula (2) may comprise a number of compounds of formula (2). The resulting compound of formula (3) may comprise a number of compounds of formula (3). In one embodiment, the fluorinated ethylene of formula (2) may comprise tetrafluoro-ethene CF2=CF2 (TFE) and 1-chloro-1,2,2-trifluoro-ethene. In a further embodiment, the compound of formula (1) may comprise CF3CH=CHF (1234ze).

[0065] The obtained compound of formula (3) may contain 1,1,1,4,4,5,5,5 - octafluoropent - 2 - ene, CF3CH=CHC2F5 (F12E), and 4 - chloro - 1,1,1,4,5,5,5 - heptafluoropent - 2 - ene, CF3CH=CHCFClCF3 and / or 5 - chloro - 1,1,1,4,4,5,5 - heptafluoropent - 2 - ene, CF3CH=CHCF2CF2Cl, 4,5 - dichloro - 1,1,1,4,5,5 - hexafluoropent - 2 - ene, CF3CH=CHCFClCF2Cl, 1,1,1,5,5,5 - hexafluoropent - 2 - ene, CF3CH=CHCH2CF3. In an alternative embodiment, the compound of formula (3) may contain 4 - chloro - 1,1,1,4,5,5,5 - heptafluoropent - 2 - ene, CF3CH=CHCClFCF3 or 5 - chloro - 1,1,1,4,4,5,5 - heptafluoropent - 2 - ene, CF3CH=CHCF2CClF2.

[0066] According to the present invention, the molar ratio of the compound of formula (2) contacted to the compound of formula (1) can be used to control the ratio of the composition and the reaction product. In some embodiments, the compound of formula (2) and the compound of formula (1) are contacted in an amount such that a molar ratio of 0.01:1 to 5:1 is obtained. In one embodiment, the compound of formula (2) and the compound of formula (1) are contacted in an amount such that a molar ratio of (2):(1) of 0.1:1 to 2:1 is obtained. A contact molar ratio of about 1:1 can produce C5 compounds, and a molar ratio of about 2:1 can produce C7 compounds. Any desired ratio can be used, but a ratio of about 2:1 is useful. In one embodiment, the compound of formula (2) and the compound of formula (1) are contacted in an amount such that a molar ratio of (2):(1) of 1:1 to 2:1 is obtained. In one embodiment, the compound of formula (2) is (TFE) and the compound of formula (1) is (1234ze).

[0067] The reaction conditions and stoichiometry may be selected such that compounds of formula (3) such as 1,1,1,4,4,5,5,5 - octafluoropent - 2 - ene, CF3CH=CHC2F5 (F12E) as described above can act as reaction intermediates. In some embodiments, the fluorinated ethylene of formula (2) may be provided in a stoichiometric excess relative to the amount of the compound of formula (1). In some embodiments, one or more additional units of the compound of formula (2), such as (TFE), can react with 1,1,1,4,4,5,5,5 - octafluoropent - 2 - ene to form additional compounds of formula (3) having an extended carbon chain. In one embodiment, the composition containing the compound of formula (3) may include 1,1,1,2,2,5,5,6,6,7,7,7 - dodecafluorohept - 2 - ene, C3F7CH=CHC2F5 (F23E).

[0068] The reaction is typically carried out in a closed system. In some embodiments, the Lewis acid is a strong Lewis acid. In one embodiment, the catalyst is aluminum chloride (AlCl3), or antimony pentafluoride (SbF5), or aluminum fluoride chloride AlCl x F 3-x where x may be an integer from 1 to 3 for aluminum - based catalysts in some embodiments. In some embodiments, x may be from 0.01 to 0.5. The catalyst amount can range from about 0.1 to about 20 weight percent of the reaction mixture, in some cases about 1 to 15 weight percent, and in some cases about 5 to about 10 weight percent.

[0069] Additional suitable strong Lewis acids can be found in (Chemical Reviews, 1996, v.96, pp. 3269 - 3301; the list of strong Lewis acids is described on page 3271), the content of which is incorporated herein by reference. In some embodiments, the reaction mixture is heated to sub - ambient or ambient temperature. In some embodiments, the reaction mixture is heated to a temperature in the range of - 50 °C to 50 °C. In one embodiment, the reaction mixture is heated to a temperature in the range of - 50 °C to 25 °C. In some embodiments, the reaction is carried out at a reaction pressure of 0.1 pounds per square inch gauge (psig) to 300 pounds per square inch gauge (psig). In some embodiments, the reaction is carried out under autogenous pressure.

[0070] In some embodiments, the formation of the compound of formula (3) may be carried out in the presence of at least one of a solvent or a diluent, depending on whether all the components of the reaction mixture are soluble. In some embodiments, the solvent or diluent is a perfluorinated saturated compound. In some embodiments, the perfluorinated saturated compound may include perfluoropentane, perfluorohexane, the cyclic dimer of hexafluoropropene (a mixture of perfluoro - 1,2 - dimethylcyclobutane and perfluoro - 1,3 - dimethylcyclobutane), and combinations thereof. Alternatively, the product of the reaction can be used as the reaction medium. The amount of at least one of the solvent or diluent can range from about 10 to about 50 volume percent, about 15 to 40 volume percent, and in some cases about 20 to 30 volume percent of the reaction vessel.

[0071] In a particular embodiment, at least one diluent or solvent comprises the reaction product formed by the step of contacting formulas (1) and (2). In a batch process, the residual portion of the reaction product in the reaction environment is left as it is. In a continuous process, the reaction product diluent or solvent can be supplied to the reaction environment by recycling some of the recovered reaction product, which is a particularly suitable technique for delivering the diluent or solvent to the reaction environment.

[0072] The compound of formula (3) may be used in a number of applications for the purpose of heat transfer, such as, for example, a heat transfer fluid or a refrigerant. In one embodiment, the compound 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).

[0073] In an alternative embodiment, the compound of formula (1) may be dimerized. The compound of formula (1) may be reacted with itself in the absence of the fluorinated ethylene compound of formula (2) in the presence of a catalyst such as, for example, antimony pentafluoride (SbF5). In some embodiments, the reaction may be carried out in the presence of a solvent. Suitable solvents include those described above.

[0074] In one example of an alternative embodiment, the dimer may be formed by reacting 1,3,3,3-tetrafluoro-1-propene, CF3CH=CHF (1234ze), as shown below.

[0075]

Chemical formula

[0076] In one embodiment of the present invention, the reaction is carried out in an environment that does not contain a compound having an OH group, or an environment that substantially does not contain it. Examples of such OH-containing compounds are hydrocarbon greases or oils and solvents having an OH group such as water or alcohol. Substantially free means that there are less than 50 ppm, less than 25 ppm and in some cases less than 10 ppm of OH-containing compounds present.

[0077] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises elements listed is not necessarily limited to only those elements, but may include other elements not expressly listed, or other elements associated with such composition, process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, the condition A or B is satisfied by any one of the following: namely, A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0078] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. In the context of a claim, such a phrase closes the claim to the inclusion of materials other than those recited, except for impurities ordinarily associated with the recited materials. When the phrase "consisting of" appears in a clause within the body of a claim rather than immediately following the preamble, the phrase limits only the elements set forth in that clause; other elements are not excluded from the scope of the claim as a whole.

[0079] The transitional phrase "consisting essentially of" is used to define a composition, method that includes materials, steps, features, ingredients, or elements in addition to those literally disclosed, provided that the additional materials, steps, features, ingredients, or elements do not materially affect the basic and novel characteristics of the claimed invention, particularly the manner of operation for achieving any desired result of the process of the present invention. The term "consisting essentially of" has an intermediate meaning between "comprising" and "consisting of."

[0080] When the applicant defines the invention or a part thereof using non - limiting terms such as "comprising", it should be readily understood that (unless otherwise specified) such description should be construed to also include inventions using the terms "consisting essentially of" or "consisting of".

[0081] Also, the use of "a" or "an" is for the purpose of describing the elements and components described in this specification. This is merely for convenience and is for giving the general meaning of the scope of the present invention. This description should be construed to include one or at least one, and the singular form also includes the plural form unless it is clear that the singular form has a different meaning.

[0082] The following examples are provided to illustrate specific embodiments of the present invention and do not limit the scope of the appended claims.

Example

[0083] Typical examples regarding the formation of the compound of formula (3) are shown below.

[0084] (Example 1) Reaction of HFO - 1234ze and chlorotrifluoroethylene catalyzed by SbF5

[0085]

Chemical formula

[0086] The ratio of CF3CH=CHCF2CF2Cl to CF3CH=CHCFClCF3 in the mixture of reaction products can vary. The ratio of the reaction products can be in the range of about 30:70, about 32:68, about 34:66, and in some cases about 36:64.

[0087] (Example 2) Reaction of HFO-1234ze with chlorotrifluoroethylene catalyzed by AlCl3

[0088] [Chemical formula] A 400 mL Hastelloy® stirring tube was charged with 12 g (0.09 mol) of anhydrous pulverized AlCl₃. The stirring tube was cooled with dry ice, evacuated, and charged with 75 g (0.66 mol) of HFO-1234ze and 75 g (0.64 mol) of chlorotrifluoroethylene (CTFE). The stirring tube was placed inside a barricade, warmed to ambient temperature, and continued to stir for 16 hours. The reactor was cooled using ice, vented, and 1 L of water was added to the liquid product. The organic layer was separated, dried over MgSO₄, filtered to obtain 148 g of a crude product. This was found to contain a mixture of 68% CF₃CH=CHCF₂CF₂Cl and CF₃CH=CHCFClCF₃ (the ratio of CF₃CH=CHCF₂CF₂Cl to CF₃CH=CHCFClCF₃ was 54:46) along with higher boiling point materials. The calculated yield of the C₅H₂ClF₇ fraction was 66%.

[0089] If necessary, the catalyst amount can be varied. The ratio of the reaction products of CF₃CH=CHCF₂CF₂Cl and CF₃CH=CHCFClCF₃ can range from about 64:36, about 62:38, and in some cases about 60:40.

[0090] Reaction of HFO-1234ze with SbF₅ (comparative example).

[0091] A 1 L Hastelloy® stirred reactor was charged with 11 g (0.05 mol) of SbF5, cooled with dry ice, pressurized with nitrogen to check for leaks, vented and evacuated, and 500 g (4.4 mol) of HFO1234ze was condensed in the reactor. This was allowed to return to ambient temperature, maintained at 25 - 30 °C for 12 hours, and water (100 mL) was injected into the reactor using a pump. The reactor was vented and opened, the reaction mixture was added to a separatory funnel containing 1 L of water, the organic layer was separated, dried over MgSO4, filtered to obtain 474 g of a crude product. This was further flash distilled to obtain 400 g of a crude product. Fractionation was carried out using a 36-inch glass column packed with Hastelloy® to obtain 350 g (70% yield) of a material with a boiling point of 86 - 87 °C, which was identified by NMR and GC / MS as E-CF3CH=CHCH(CF3)CF2H containing 3% of the Z-isomer. E-CF3CH=CHCH(CF3)CF2H: 19 19F NMR (CDCl3): -65.86 (3F, m), -67.47 (3F, m), -120.00 (1F, ddm, 300, 54.1 Hz), -123.60 (1F, ddm, 300, 54.1 Hz) ppm 1 1H NMR (CDCl3, mixed isomers): 6.06 (1H, m), 6.10 (1H, t, d, 54.1, 2.5 Hz), 6.33 (1H, m) ppm GC / MS (m / z): 228 (M + , C6H4F8 + )

[0092] (Example 3) Reaction of HFO-153-10ze and chlorotrifluoroethylene catalyzed by AlCl3

[0093]

Chemical formula

[0094] The ratio of the reaction products of C4F9CH=CHCF2CF2Cl and C4F9CH=CHCFClCF3 can be in the range of about 64:36, about 62:38, and in some cases about 60:40.

[0095] (Example 4) Reaction of HFO-1234ze with tetrafluoroethylene catalyzed by AlCl3

[0096] [Chemical formula] A 400 mL Hastelloy® stirring tube was charged with 5 g (0.038 mol) of anhydrous powdered AlCl3. The stirring tube was cooled with dry ice, evacuated, and charged with 60 g (0.52 mol) of HFO-1234ze and 50 g (0.5 mol) of tetrafluoroethylene (TFE). The stirring tube was placed inside a barricade and warmed to ambient temperature for 2 hours. An additional 50 g (0.5 mol) of TFE was charged and stirring was continued for 12 hours. The reactor was cooled with ice, vented, and 1 L of water was added to the liquid product (140 g). The organic layer was separated, dried over MgSO4, and filtered to obtain 130 g of crude product. This contained 65% of E-CF3CH=CHCF2CF3 (F12E) and 35% of E-C2F5CH=CHC3F7 (F23E). Fractionation was carried out using a 10-inch Vigreux column to obtain 46 g (yield 43%) of material identified as CF3CH=CHCF2CF3 (boiling point 29 - 30 °C) by GC / MS and NMR, and 28 g (yield 17%) of material with a boiling point of 70 - 74 °C (mainly 73 - 74 °C) identified as E-C2F5CH=CHC3F7 (purity 98%) by NMR and GC / MS. E-CF3CH=CHCF2CF3: 19 19F NMR (CDCl3): -66.30 (3F, dm, 4.1, 1.5 Hz), -85.07 (3F, m), -117.98 (2F, dm, 8.7, 2.3 Hz) ppm GC / MS (m / z): 214 (M + , C5H2F8 + ) 11H NMR (CDCl3): 6.46 (m) ppm E-C2F5CH=CHC3F7: 19 19F NMR (CDCl3): -80.66 (3F, t, 9.1 Hz), -85.07 (3F, m), -115.28 (2F, quint., 8.7 Hz), -117.88 (2F, dm, 8.5, 2.0 Hz), -127.88 (2F, s) ppm. 1 1H NMR (CDCl3): 6.46 (m) ppm GC / MS (m / z): 314 (M + , C7H2F 12 + )

[0097] If necessary, the amounts of E-CF3CH=CHCF2CF3 (F12E) and E-C2F5CH=CHC3F7 (F23E) in the reaction product mixture can be varied by changing the amounts of the reactants. The amounts of E-CF3CH=CHCF2CF3 (F12E) and E-C2F5CH=CHC3F7 (F23E) in the reaction product can vary from 1 wt%:100 wt%, 25 wt%:75 wt%, and in some cases about 50 wt%:50 wt%.

[0098] (Example 5) Reaction of HFO-1234ze and vinylidene fluoride catalyzed by AlCl3

[0099]

Chemical Structure

[0100] Reaction of HFO-1234yf and tetrafluoroethylene catalyzed by AlCl3 (comparative example).

[0101] The reaction of 5 g (0.038 mol) of anhydrous pulverized AlCl3, 115 g (1 mol) of HFO1234yf (CF3CF=CH2, HFO-1234ze) and 50 g of TFE was carried out as described above in a 400 mL Hastelloy® stirred tube at ambient temperature. No pressure drop was observed over a period of 16 hours and no liquid product was recovered after venting the stirred tube.

[0102] The ratio of E-CF3CH=CHCH2CF3 to Z-CF3CH=CHCH2CF3 in the product mixture was in the range of about 1 wt%:100 wt%, about 25 wt%:75 wt%, and in some cases about 50 wt%:50 wt%. This ratio can be varied by changing at least one of the ratio of reactants, additional solvent and temperature.

[0103] While the 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 equivalents can be used in place of its elements. Additionally, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from its essential scope. Accordingly, the invention is not limited to the particular embodiments disclosed as the best mode contemplated for carrying out the invention, but the invention is intended to include all embodiments within the scope of the appended claims. Additionally, all numerical values specified in the detailed description are to be interpreted as if both exact and approximate values were explicitly specified.

Claims

Claim 1 A method for producing a fluoroolefin, The method includes a step of contacting a compound of the general formula R f CH=CHF with a fluorinated ethylene compound in the presence of a Lewis acid catalyst. R f is CF 3 or C 4 F 9 and wherein the fluorinated ethylene compound is CFCl=CF2 or CH2=CF2, The Lewis acid includes aluminum chloride (AlCl 3 ), and The general formula R f The compound of CH=CHF and the fluorinated ethylene compound are the following compositions: R f is CF 3 and the fluorinated ethylene compound is CFCl=CF 2 in the case of, CF 3 CH=CHCF 2 CF 2 Cl and CF 3 CH=CHCFClCF 3 a mixture of; R f is CF 3 and the fluorinated ethylene compound is CH 2 =CF 2 in the case of, CF 3 CH=CHCH 2 CF 3 ; or R f is C 4 F 9 and the fluorinated ethylene compound is CFCl = CF 2 In the case of 4 F 9 CH = CHCF 2 CF 2 Cl and C 4 F 9 CH = CHCFClCF 3 mixture is an amount sufficient to form Method. Claim 2 The method according to claim 1, wherein the composition further comprises 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene (C 3 F 7 CH=CHC 2 F 5 ). Claim 3 The method according to claim 1, wherein the contacting step is carried out under autogenic pressure. Claim 4 The method according to claim 1, wherein the contacting step is carried out at 0.1 to 300 psig. Claim 5 The method according to claim 1, wherein the contacting step is carried out in a closed system. Claim 6 The method according to claim 1, wherein the contacting step is carried out at a temperature of -50°C to 50°C.

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