Method for producing fluorinated organic compounds

Abstract

To provide a method for producing a fluorinated olefin suitable for commercialization of CF3CF=CH2 (1234yf).SOLUTION: Provided is a method in which a feedstock material such as CCl2=CClCH2Cl is fluorinated to synthesize a compound such as CF3CCl=CH2 with a selectivity of 80 to 96%, CF3CCl=CH2 being converted to CF3CFClCH3 (244 isomer) using SbCl5 as a catalyst, and then selectively converted to 1234yf by a vapor-phase catalytic reaction using activated carbon as a catalyst, wherein, for the first step, a mixture of Cr2O3 and FeCl3 / C is used as a catalyst to achieve a high selectivity of 96% for CF3CCl=CH2, in the second step, SbCl5 / C is used as a selective catalyst for converting 1233xf to the 244 isomer CF3CFClCH3, and an intermediate is isolated, purified by distillation, and used in a subsequent step without further purification to a purity level exceeding about 95%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Background of the Invention (1) Field of the invention The present invention relates to a novel process for preparing fluorinated organic compounds, and more particularly to a process for producing fluorinated olefins. [Background technology]

[0002] (2) Description of related technology Hydrofluorocarbons (HFCs), particularly hydrofluoroalkenes such as tetrafluoropropenes (2,3,3,3-tetrafluoro-1-propene (including HFO-1234yf) and 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze)), have been disclosed to be effective coolants, fire extinguishing agents, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particle removal fluids, carrier fluids, buffing and abrasives, displacement drying agents, and heavy-duty circulating hydraulic fluids. Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which can harm the Earth's ozone layer, HFCs do not contain chlorine and therefore do not require ozone layer treatment.

[0003] Several methods for preparing hydrofluoroalkenes are known. For example, U.S. Patent No. 4,900,874 (Ihara et al.) describes a method for making fluorine-containing olefins by contacting hydrogen gas with a fluorinated alcohol. While this is considered a relatively high-yield method for commercial-scale production, handling hydrogen gas at high temperatures poses difficult safety issues. In addition, the cost of producing hydrogen gas, such as building an on-site hydrogen plant, can be quite high in many situations.

[0004] U.S. Patent No. 2,931,840 (Marquis) describes a method for making fluorine-containing olefins by high-temperature pyrolysis of methyl chloride and tetrafluoroethylene or chlorodifluoromethane. This is a relatively low-yield process, and a large amount of the organic starting material is converted into unwanted and / or insignificant by-products in this process.

[0005] The preparation of HFO-1234yf from trifluoroacetylacetone and sulfur tetrafluoride has been described. See Banks et al., Journal of Fluorine Chemistry, Vol. 82, Issue 2, pp. 171-174 (1997). Also, U.S. Patent No. 5,162,594 (Krespan) discloses a process in which tetrafluoroethylene is reacted with another ethylene fluoride in the liquid phase to produce a polyfluoroolefin product. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 4,900,874 [Patent Document 2] U.S. Patent No. 2,931,840 [Patent Document 3] U.S. Patent No. 5,162,594 [Non-patent literature]

[0007] [Non-Patent Document 1] Banks et al., Journal of Fluorine Chemistry, Vol. 82, Iss. 2, pp. 171-174 (1997) Summary of the Invention

[0008] Abstract Applicant preferably provides a compound of formula (I): C(X) m CCl(Y) n C(X) m (I) with at least one compound of formula (II) CF3CF=CHZ (II) wherein each X, Y, and Z is independently H, F, Cl, I, or Br, each m is independently 1, 2, or 3, and n is 0 or 1. As used herein and throughout, and unless otherwise specifically indicated, the term "converting step" includes direct converting steps (e.g., in a single reaction or under essentially one set of reaction conditions, examples of which are described hereinafter) and indirect converting steps (e.g., by more than one reaction or using more than one set of reaction conditions).

[0009] In certain preferred embodiments of the present invention, compounds of formula (I) include compounds where n is 0, each X is independently H or Cl, and Z is H. Such preferred embodiments include compounds of formula (IA): C(X)2=CClC(X)3(IA) with at least one C3 alkene according to formula (II) CF3CF=CHZ (II) wherein each X is independently H or Cl. Preferably, the one or more compounds of formula (IA) is tetrachloropropene, even more preferably selected from the group consisting of CH2=CClCCl3, CCl2=CClCH2Cl, CHCl=CClCCl2H, and combinations thereof.

[0010] In certain preferred embodiments of the present invention, compounds of formula (I) include compounds where n is 0 and the terminal saturated carbon has three F substituents. Such preferred embodiments include compounds of formula (IAA): C(X)2=CClCF3(IAA) with at least one C3 alkene according to formula (II) CF3CF=CHZ (II) wherein each X is independently H or Cl. Preferably, the compound or compounds of formula (IAA) are trifluoropropenes. A preferred trifluoropropene of the present invention is CH═CClCF (HCFC-1223xf).

[0011] In certain preferred embodiments, compounds of formula (I) include compounds where n is 1 and each X and Y is independently H, F, or Cl. Such embodiments include compounds of formula (IB): C(X)3CClYC(X)3(IB) At least one C3 alkane of formula (II) CF3CF=CHZ (II) wherein each X and Y is independently H, F, or Cl. In certain preferred embodiments, the compound of formula (IB) has at least two halogens on one terminal carbon and at least two hydrogen atoms on the other terminal carbon. Preferably, the compound of formula (IB) contains at least four halogen substituents, and even more preferably at least five halogen substituents. In certain highly preferred embodiments, the converting process of the present invention comprises converting a compound of formula (IB) where Y is F and all three Xs on one terminal carbon are F. Preferably, the compound of formula (IB) is a pentahalogenated propane, preferably having at least four fluorine substituents. Even more preferably, the pentahalogenated propane of formula (IB) includes chlorotetrafluoropropane (C3H3F4Cl), including all isomers thereof, such as 1,1,1, These include tetrafluorinated, monochlorinated propanes, including 2-tetrafluoro-2-chloropropane and 1-chloro-1,3,3,3-tetrafluoropropane (HFC-244fa). Other preferred pentahalogenated compounds of formula (IB) include CHClCHClCCl, CHClCClCHCl, CHClCHClCHCl. ​​Of course, combinations of compounds of formula (I) may be used, including combinations of compounds of formula (IA), (IAA), and (IB).

[0012] In certain preferred embodiments, converting a compound of formula (I) to at least one compound of formula (II) comprises directly converting a compound of formula (I). In other embodiments, converting a compound of formula (I) to at least one compound of formula (II) comprises indirectly converting a compound of formula (I).

[0013] An example of an indirect conversion embodiment includes converting a compound of formula (IA) to a compound of formula (IAA), then converting said compound of formula (IAA) to a compound of formula (IB), and then converting formula (IB) to a compound of formula (II). In a more specific indirect conversion embodiment, the step of converting a compound of formula (I) comprises providing at least one monochlorotrifluoropropene according to formula (IAA), preferably CF3CCl=CH2 (HFO-1233xf), and reacting said monochlorotrifluoropropene under conditions effective to produce at least one monochlorotetrafluoropropane according to formula (IB), preferably CF3CFClCH3 (HFC-244bb), which is then preferably exposed to reaction conditions effective to produce at least one compound according to formula (II), preferably HFO-1234yf. In a preferred embodiment, the exposing step comprises carrying out one or more of the reactions in the gas phase in the presence of a catalyst, preferably a metal-based catalyst. Examples of such preferred conversion steps are disclosed more fully hereinafter. Of course, it is contemplated within the broad scope of the present invention that any compound of formula (I) may be converted, directly or indirectly, to a compound of formula (II) in view of the teachings contained herein.

[0014] In certain preferred embodiments, the converting step comprises exposing a compound of formula (I), preferably formula (IA), (IAA) or formula (IB), to one or more sets of reaction conditions effective to produce at least one compound according to formula (II). In certain embodiments, the exposing step comprises exposing said one or more compounds of formula (IA) or (IAA) to chlorofluoropropane, more preferably a compound of formula (IBB): CF3CClFC(X)3 formula (IBB) wherein each X is independently F, Cl, or H. In a preferred embodiment, at least one of X in formula (IBB) is H, and even more preferably, all three X are H.

[0015] Preferred conversion steps of the present invention are preferably carried out under conditions that include the use of one or more reactants effective to provide a conversion rate of Formula (I) of at least about 50%, more preferably at least about 75%, and even more preferably at least about 90%. In certain preferred embodiments, the conversion rate is at least about 95%, and more preferably at least about 97%. Furthermore, in certain preferred embodiments, the step of converting a compound of Formula (I) to produce a compound of Formula (II) is carried out under conditions effective to provide a yield of Formula (II) of at least about 75%, more preferably at least about 85%, and even more preferably at least about 90%. In certain preferred embodiments, a yield of about 95% or greater is achieved. DETAILED DESCRIPTION OF THE INVENTION

[0016] Detailed Description of the Preferred Embodiments One advantageous aspect of the present invention is that it enables the production of desired fluoroolefins, preferably C3 fluoroolefins, using relatively high conversion and high selectivity reactions. Furthermore, in certain preferred embodiments, the process of the present invention enables the production of desired fluoroolefins, directly or indirectly, from relatively attractive starting materials. For example, 2-chloro,2,3,3,3-tetrafluoropropane is a compound that may be an advantageous starting material in certain embodiments because such products are relatively easy to handle.

[0017] Preferably, the compound of formula (I) is exposed to reaction conditions effective to produce a reaction product comprising one or more of the desired fluoroolefins, preferably one or more compounds of formula (II). While it is contemplated that the exposing step in certain embodiments may be effectively carried out in a single reaction step and / or under a single set of reaction conditions, as described above, it is preferred in many embodiments that the conversion process comprises a series of reaction steps or conditions. In one preferred embodiment of the present invention, the conversion process comprises: (a) reacting a compound of formula (I) other than a compound of formula (IAA), preferably other than a compound of formula (IA), in a gas-phase and / or liquid-phase reaction in the presence of at least a first catalyst to produce at least one compound of formula (IAA), such as a monochlorotrifluoropropene, preferably HFO-1233xf; (b) reacting at least one monochlorotrifluoropropene compound in the gas-phase and / or liquid-phase, preferably in the presence of at least one catalyst, preferably in the presence of a second catalyst different from the first catalyst, to produce at least one compound of formula (IB), even more preferably a compound of formula (IBB), such as monochlorotetrafluoropropane; and (c) reacting the compound of formula (IB) in the gas-phase and / or liquid-phase to produce the desired HFO, preferably HFO-1234yf. Each preferred reaction process is described in detail below, with the headings used for convenience and not necessarily by way of limitation.

[0018] I. Fluorination of Compounds of Formula I(A) One preferred reaction process according to the present invention may be illustrated by these reactions in which a compound of formula (IA) is fluorinated to produce a compound of formula (IAA). In certain preferred embodiments, particularly those in which the compound of formula (IA) comprises C(X)═CClC(X) (where each X is independently H or Cl), the conversion process of the present invention comprises first reacting the compound by fluorinating the compound, preferably with HF, in the vapor phase to produce at least a trifluorinated HFO, such as HFO-1223xf. Preferably, this vapor phase reaction is at least partially catalyzed.

[0019] Preferred fluorination of compounds of formula (IA) is preferably carried out under conditions effective to provide a conversion of formula (IA) of at least about 50%, more preferably at least about 75%, and even more preferably at least about 90%. In certain preferred embodiments, the conversion is at least about 95%, and more preferably at least about 97%. Furthermore, in certain preferred embodiments, conversion of compounds of formula (IA) comprises reacting such compounds under conditions effective to produce at least one compound of formula (IAA), e.g., monochlorotrifluoropropene (preferably, CF3CCl=CH2(HFO-1233xf)), with a selectivity of at least about 50%, more preferably at least about 70%, more preferably at least about 80%, and even more preferably at least about 90%, with a selectivity of about 95% or greater being achieved in some embodiments.

[0020] In general, it is contemplated that the fluorination reaction step can be carried out in the liquid phase, or in the vapor phase, or in a combination of the vapor and liquid phases, and the reaction can be carried out batchwise, continuously, or a combination thereof.

[0021] For embodiments in which the reaction involves a liquid-phase reaction, the reaction can be catalytic or non-catalytic. Preferably, a catalytic method is used. Lewis acid catalysts, such as metal halide catalysts including antimony halides, tin halides, thallium halides, iron halides, and combinations of two or more thereof, are preferred in some embodiments. Metal chlorides and metal fluorides are particularly preferred. Examples of particularly preferred catalysts of this type include SbCl5, SbCl3, SbF5, SnCl4, TiCl4, FeCl3, and combinations of two or more thereof.

[0022] In a preferred vapor-phase fluorination of a compound of Formula (I), preferably a compound of Formula (IA), the reaction is at least partially catalyzed and is preferably conducted in a continuous manner by introducing a stream containing a compound of Formula (I), preferably Formula (IA), into one or more reaction vessels, such as a tubular reactor. In a preferred embodiment, the stream containing a compound of Formula (I), preferably Formula (IA), is preheated to a temperature of about 80°C to about 400°C, more preferably about 150°C to about 400°C, and in some embodiments, preferably about 300°C, and introduced into a reaction vessel (preferably a tubular reactor) maintained at the desired temperature, preferably about 80°C to about 700°C, more preferably about 90°C to about 600°C, even more preferably, in some embodiments, about 400°C to about 600°C, and more preferably about 450°C to about 600°C, where it is preferably contacted with a catalyst and a fluorinating agent, such as HF.

[0023] Preferably, the vessel is made of a corrosion resistant material such as Hastelloy, Inconel, Monel and / or a fluoropolymer liner. Preferably the vessel contains a fixed or fluidized catalyst bed packed with catalyst, e.g., a suitable fluorination catalyst, together with suitable means to ensure that the reaction mixture is maintained within the desired reaction temperature range.

[0024] It is therefore contemplated that the fluorination reaction step may be carried out using a wide range of process parameters and conditions in view of the overall teachings contained herein. However, in certain embodiments, the reaction step comprises a gas-phase reaction, preferably in the presence of a catalyst, even more preferably a chromium-based catalyst (e.g., a Cr2O3 catalyst), an iron-based catalyst (e.g., FeCl3 on carbon (referred to herein for convenience as FeCl3 / C)), or a combination thereof. In a preferred embodiment, the catalyst is a combination of two of the aforementioned catalysts, and the reaction vessel comprises a chromium-based catalyst in a first zone and an iron-based catalyst in a second zone. The reaction temperature in the chromium-based catalyzed reaction is preferably maintained at a temperature of about 200°C to about 600°C, even more preferably about 250°C to about 500°C. The reaction temperature in the iron-based catalyzed reaction zone is preferably maintained at a temperature of about 80°C to about 300°C, even more preferably about 100°C to about 250°C.

[0025] It is generally contemplated that a wide range of reaction pressures may be used for the fluorination reaction, again depending on relevant factors such as the particular catalyst used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric, or under vacuum, and in some preferred embodiments is from 6.8 to 1378.9 kPa (about 1 to about 200 psia), and in some embodiments, from 6.8 to 827.3 kPa (about 1 to about 120 psia).

[0026] In some embodiments, an inert diluent gas, such as nitrogen, may be used in combination with other reactor feeds. The amount of catalyst used may vary depending on the particular parameters present in each embodiment.

[0027] II. Fluorination of Compounds of Formula I(AA) The compound of formula (IAA), preferably the compound prepared as described above, is then preferably subjected to a further fluorination reaction to produce a compound of formula (IB), such as HCFC-244. Preferably, this gas phase reaction is at least partially catalyzed.

[0028] The fluorination of the compound of formula (IAA) is preferably carried out under conditions effective to provide a conversion of formula (IAA) of at least about 40%, more preferably at least about 50%, and even more preferably at least about 60%. Moreover, in certain preferred embodiments, the conversion of the compound of formula (IA) comprises reacting such compound under conditions effective to produce at least one monochlorotetrafluoropropane, preferably HCFC-244, at a selectivity of at least about 70%, more preferably at least about 80%, and even more preferably at least about 85%, with selectivities of about 90% or greater being achieved in certain embodiments.

[0029] In general, it is contemplated that the fluorination reaction step can be carried out in the liquid phase, or in the vapor phase, or in a combination of the vapor and liquid phases, and that the reaction can be carried out batchwise, continuously, or a combination thereof.

[0030] For embodiments in which the reaction involves a liquid-phase reaction, the reaction can be catalytic or non-catalytic. Preferably, a catalytic method is used. Lewis acid catalysts, such as metal halide catalysts including antimony halides, tin halides, thallium halides, iron halides, and combinations of two or more thereof, are preferred in some embodiments. Metal chlorides and metal fluorides are particularly preferred. Examples of particularly preferred catalysts of this type include SbCl5, SbCl3, SbF5, SnCl4, TiCl4, FeCl3, and combinations of two or more thereof.

[0031] In a preferred vapor-phase fluorination of a compound of Formula (IAA), the reaction is at least partially catalyzed and is preferably conducted in a continuous manner by introducing a stream containing a compound of Formula (IAA) into one or more reaction vessels, such as a tubular reactor. In certain preferred embodiments, the stream containing a compound of Formula (I), preferably Formula (IAA), is preheated to a temperature of about 50°C to about 400°C, and in certain embodiments, preferably about 80°C. In other embodiments, the stream containing a compound of Formula (I), preferably Formula (IAA), is preferably preheated to a temperature of about 150°C to about 400°C, and preferably about 300°C. After preheating, the stream is then preferably introduced into a reaction vessel (preferably a tubular reactor) maintained at the desired temperature, preferably about 50°C to about 250°C, more preferably about 50°C to about 150°C, where it is preferably contacted with a catalyst and a fluorinating agent, such as HF.

[0032] Preferably, the vessel is made of a corrosion resistant material such as Hastelloy, Inconel, Monel and / or a fluoropolymer liner. Preferably the vessel contains a fixed or fluidized catalyst bed packed with catalyst, e.g., a suitable fluorination catalyst, together with suitable means for ensuring that the reaction mixture is maintained within approximately the desired reaction temperature range.

[0033] Thus, it is contemplated that the fluorination reaction step may be carried out using a wide range of process parameters and conditions in view of the overall teachings contained herein. However, in certain embodiments, the reaction step comprises a gas-phase reaction, preferably in the presence of a catalyst, even more preferably an Sb-based catalyst, such as about 50 wt. % SbCl / C. Other catalysts that may be used include about 3 to about 6 wt. % FeCl / C; SbF / C; about 20 wt. % SnCl / C; about 23 wt. % TiCl / C; and activated carbon. Preferably, the catalyst is a mixture of Cl and HF. Treatment includes SbCl5 / C.

[0034] In general, it is also contemplated that a wide range of reaction pressures may be used for the fluorination reaction, again depending on relevant factors such as the particular catalyst used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric, or under vacuum, and in some preferred embodiments is 6.8 to 1378.9 kPa (about 1 to about 200 psia), and more preferably in some embodiments is 6.8 to 827.3 kPa (about 1 to about 120 psia).

[0035] In some embodiments, an inert diluent gas, such as nitrogen, may be used in combination with other reactor feeds. The amount of catalyst used may vary depending on the particular parameters present in each embodiment.

[0036] III. Dehydrohalogenation of formula (IB) One preferred reaction process according to the present invention may be illustrated by these reactions in which a compound of formula (IB) is dehydrohalogenated to produce a compound of formula (II): In one preferred embodiment, a stream containing a compound of formula (IB), preferably formula (IBB), is preheated to a temperature of about 150°C to about 400°C, preferably about 350°C, and introduced into a reaction vessel maintained at about the desired temperature, preferably about 200°C to about 700°C, more preferably about 300°C to about 700°C, even more preferably about 300°C to about 450°C, and even more preferably in one embodiment about 350°C to about 450°C.

[0037] Preferably, the vessel is made of a corrosion-resistant material such as Hastelloy, Inconel, Monel and / or a fluoropolymer lining. Preferably, the vessel contains a fixed or fluidized catalyst bed packed with a catalyst, e.g., a suitable dehydrohalogenation catalyst, along with suitable means for heating the reaction mixture to about the desired reaction temperature.

[0038] It is therefore contemplated that the dehydrohalogenation reaction step may be carried out using a wide range of process parameters and conditions in view of the overall teachings contained herein. However, in certain embodiments, the reaction step comprises a gas-phase reaction, preferably in the presence of a catalyst, even more preferably a carbon- and / or metal-based catalyst, preferably activated carbon, nickel-based catalysts (e.g., Ni-mesh, etc.), and combinations thereof. Other catalysts and catalyst supports may be used, including palladium on carbon, palladium-based catalysts (including palladium on aluminum oxide), and it is expected that numerous other catalysts may be used in view of the teachings contained herein, depending on the requirements of a particular embodiment. Of course, two or more of any of these catalysts, or other catalysts not named herein, may be used in combination.

[0039] The vapor phase dehydrohalogenation reaction may be carried out, for example, by introducing the gaseous form of the compound of formula (IB) into a suitable reaction vessel or reactor. Preferably, the vessel is made of a corrosion-resistant material such as Hastelloy, Inconel, Monel, and / or a fluoropolymer lining. Preferably, the vessel contains a fixed or fluidized catalyst bed filled with a catalyst, for example, a suitable dehydrohalogenation catalyst, along with suitable means for heating the reaction mixture to about the desired reaction temperature.

[0040] Although it is contemplated that a wide range of reaction temperatures may be used depending on relevant factors such as the catalyst used and the most desired reaction product, generally, the reaction temperature for the dehydrohalogenation step is from about 200°C to about 800°C, more preferably from about 400°C to about 800°C, even more preferably from about 400°C to about 500°C, and more preferably, in some embodiments, from about 300°C to about 600°C. The temperature is preferably 00°C to about 500°C.

[0041] It is generally also contemplated that a wide range of reaction pressures may be used, again depending on relevant factors such as the particular catalyst used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric, or under vacuum, and in certain preferred embodiments is from about 1 to about 200 psia (6.8 to 1378.9 kPa), and even more preferably, in certain embodiments, from about 1 to about 120 psia (6.8 to 827.3 kPa).

[0042] In some embodiments, an inert diluent gas, such as nitrogen, may be used in combination with other reactor feeds. When such a diluent is used, it is generally preferred that the compound of Formula (I), preferably Formula (IB), comprise from about 50% to greater than about 99% by weight, based on the combined weight of the diluent and the compound of Formula (I).

[0043] The amount of catalyst used may vary depending on the particular parameters present in each embodiment. Preferably, in such dehydrohalogenation embodiments described in this section, the conversion of the compound of formula (IB) is at least about 60%, more preferably at least about 75%, and even more preferably at least about 90%. Preferably, in such embodiments, the selectivity to the compound of formula (II), preferably HFO-1234yf, is at least about 50%, more preferably at least about 70%, and even more preferably at least about 80%. [Example]

[0044] Further features of the present invention are provided in the following examples, which should not be construed as limiting the scope of the claims in any way.

[0045] Example 1 Preparation of CH2=CClCH2Cl (2,3-dichloro-1-propene) from CH2ClCHClCH2Cl Approximately 8,500 g of 1,2,3-trichloropropane and approximately 88.0 g of Aliquat 336 were charged into a 30-L glass vessel equipped with a TEFLON® shaft and stirring blade, heated with an internal TEFLON®-coated copper coil and a circulating coolant / heating bath, and equipped with a cooling condenser. The mixture was then heated to approximately 73°C with medium stirring. At this temperature, approximately 10,000 g of a 25 wt% NaOH / HO solution was added to the reactor from a separate container over a 2-hour period. The pH was maintained at approximately 14. After the addition, the progress of the reaction was monitored by GC and GC / MS. The conversion of 1,2,3-trichloropropane was approximately 97.5%, and the selectivity to CH═CClCH₂Cl was approximately 95.4%. After the designated reaction time, the mixture was cooled, and approximately 4.0 L of distilled, deionized water was added to the mixture. The mixture was stirred for approximately 10 minutes and allowed to separate. The bottom product (boiling point about 92.5° C.) was discharged and distilled to substantially isolate and purify the product. The crude product yield before distillation was about 6408 g (about 93% GC purity).

[0046] Example 2 Preparation of HCCl2CCl2CH2Cl from CH2=CClCH2Cl Chlorine was bubbled into about 82.4 g of 2,3-dichloropropene at about 10 to about 30° C. with the aid of ice bath cooling until a pale yellow color persisted for about 45 minutes. The crude product, in the amount of about 130.4 g, consisted of about 93.6% CHClCClCHCl and about 2.6% 2,3-dichloropropene.

[0047] 500 g of CH2ClCCl2CH2Cl was charged to the photoreactor. A circulating cooling bath was used. The reactor jacket and the 450W UV lamp jacket were cooled to about 15°C. A total of about 150 g of chlorine was bubbled into the organic liquid over a period of about 2 hours. The crude product weighed about 591 g. GC analysis indicated a conversion of about 54.4% and a selectivity to the desired HClCClCHCl of about 87%. Distillation gave 99% pure HClCClCHCl.

[0048] Example 3 Preparation of CCl2=CClCH2Cl from HCCl2CCl2CH2Cl Aliquat-336® (approximately 0.26 g) and approximately 24.8 g of HClCClCHCl were rapidly stirred at room temperature while approximately 20 g of 25% aqueous NaOH was added over 19 minutes. Stirring was continued overnight before adding 30 mL of water and allowing the phases to separate. The lower organic phase, amounting to approximately 19.8 g, was approximately 97.5% pure CCl=CClCHCl by GC analysis (96% yield). Prior to fluorination, distillation was performed to remove any phase transfer catalyst (boiling point, approximately 69 to approximately 72°C at approximately 30 mmHg). H NMR: δ 4.41(s) ppm.

[0049] Example 4 Selective Catalytic Conversion of CCl2=CClCH2Cl to CF3CCl=CH2 (HFO-1233xf) in the Gas Phase A Monel tube gas-phase reactor, 558.8 mm (22 inches) long and 12.7 mm (1 / 2 inch) in diameter, is filled with approximately 120 cc of catalyst or a mixture of two catalysts. In the case of a mixture, the Cr2O3 catalyst is maintained in the bottom zone of the reactor at a constant temperature of approximately 270°C to 500°C, while the other catalyst, such as FeCl3 / C, is maintained in the middle and top zones of the reactor at a constant temperature of approximately 120°C to 220°C. The reactor is mounted inside a heater with three zones (top, middle, and bottom). The reactor temperature is read by a custom-made five-point thermocouple maintained inside the center of the reactor. The bottom of the reactor is connected to a preheater maintained at 300°C by electrical heating. Liquid HF is fed from a cylinder into the preheater at a constant flow rate of about 1 to about 1000 g per hour (g / h) through a needle valve, a liquid mass flow meter, and a research control valve. The HF cylinder is maintained at a constant pressure of 310.2 kPa (45 psig) by applying anhydrous N2 gas pressure into the cylinder headspace. About 10 to about 1000 g / h of CCl2=CClCH2Cl is fed as a liquid from the cylinder through a dip tube under N2 pressure of 310.2 kPa (45 psig). Organisms flow from the dip tube into the preheater (held at about 250°C) at a constant flow rate of 1 to 1000 g / h through a needle valve, a liquid mass flow meter, and a research control valve. Organisms are also fed as a gas while the cylinder containing the organisms is heated to about 220°C. Gas exiting the cylinder passes into the preheater through a needle valve and a mass flow control valve. The organic lines from the cylinders to the preheater are maintained at approximately 200°C by constant-temperature heat tracing and electrical heating elements. All feed cylinders are mounted on balances to monitor their weight by difference. The catalyst is dried at reaction temperature for approximately 8 hours and then pretreated with approximately 50 g / hr of HF at atmospheric pressure for approximately 6 hours, followed by an additional 6 hours under 50 psig (344.7 kPa) of HF pressure, before contacting with the organic feed containing CCl═CClCH₂Cl. The reaction is carried out at a constant reactor pressure of approximately 0 to 1034.2 kPa (approximately 0 to 150 psig) by controlling the reactor outlet gas flow rate with a separate research control valve.The gas exiting the reactor is analyzed by online GC and GC / MS connected via a hotbox valve arrangement to prevent condensation. The conversion of CCl₂=CClCH₂Cl is about 70% to about 100%, and the selectivity for 1233xf is about 80% to about 95%, respectively. The reactor outlet gas is passed through a scrubbing solution containing about 20% to about 60% by weight of KOH in water, and the product is then collected from a scrubber by trapping the outlet gas in a cylinder held in dry ice or liquid N₂. The product, 1233xf, is then substantially purified by distillation. The results are tabulated in Table 1.

[0050] [Table 1]

[0051] Examples 5A and 5B Liquid-phase catalytic fluorination of CF3CCl=CH2(1233xf) to CF3CFClCH3(244bb) with HF Example 5A About 327 g of HF, about 50 g of 1233xf, and about 75 g of SbCl5 were charged into a 1 L autoclave. The reaction mixture was stirred at about 80°C for about 3 hours under a pressure of 4274.7 kPa (about 620 psig). After the reaction, the reactor was cooled to about 0°C, and then about 300 ml of water was added slowly to the autoclave over a period of about 45 minutes. After the addition of water under stirring was completed, the reactor was cooled to room temperature, and then the overhead gas was collected separately. The CF3CFClCH3 yield was about 90% at a 1233xf conversion level of about 98%. Other major by-products were CF3CF2CH3 (2%) and an unidentified isomer of a C4 compound of the general formula C4H3Cl3F4 (8%).

[0052] Example 5B Approximately 327 g of HF, approximately 50 g of 1233xf, and approximately 75 g of SbCl were charged to a 1-L autoclave. The reaction mixture was stirred at approximately 80°C for approximately 3 hours under a pressure of 4309.2 kPa (approximately 625 psig). After the reaction, the reactor was cooled to approximately 45°C, and the overhead gas mixture was then passed through a column packed with sufficiently dried KF, NaF, or Al2O3 (350 g) maintained at approximately 80°C to remove HF from the gas stream. Gas exiting the column was collected in a cylinder maintained in a dry ice (-70°C) bath. The yield of CF3CFClCH3 was 87% at a 93% 1233xf conversion level. Other major by-products were CF3CF2CH3 (1%) and an unidentified isomer of a C4 compound of the general formula C4H3Cl3F4 (7%). The product, CF3CFClCH3, was isolated by distillation in 98% purity.

[0053] Example 6 Gas-phase catalytic fluorination of CF3CCl=CH2(1233xf) with HF to CF3CFClCH3(244bb) A 22-inch (1 / 2-inch diameter) Monel tube gas-phase reactor was loaded with approximately 120 cc of catalyst. The reactor was mounted inside a three-zone (top, middle, and bottom) heater. The reactor temperature was read with a custom-made five-point thermocouple held centered inside the reactor. The reactor inlet was connected to a preheater maintained at approximately 300°C by electrical heating. Organics (1233xf) were fed from a cylinder maintained at 70°C through a control valve, needle valve, and gas mass flow meter. The organics line to the preheater was heat traced and maintained at a constant temperature of approximately 73°C by electrical heating to avoid condensation. N2 was used as a diluent in some cases and was fed from a cylinder into the preheater through a control valve and mass flow control valve. All feed cylinders were mounted on a balance to monitor their weight by difference. The reaction was carried out at a constant reactor pressure of about 0 to about 100 psig (0 to 689.4 kPa) by controlling the reactor outlet gas flow rate with a separate research control valve. The gas mixture exiting the reactor was analyzed by online GC and GC / MS connected through a hot-box valve arrangement to prevent condensation. Using 120 cc of 50 wt.% SbCl / C as catalyst at about 65°C to about -85°C, with an HF flow rate of about 50 g / hr and an organic flow rate of about 15 g / hr, the conversion of 1233xf was about 50% to about 65%, and the selectivity to the 244 isomer (CFCFClCH) was about 90% to about 93%. CFCFCH was not observed under these reaction conditions. The catalyst was first heated at about 65°C with 50 g / hr of HF for about 2 hours, then heated at about 65°C with about 50 g / hr of HF and about 0.338 Pa. 3 The sample was pretreated with Cl2 at about 65°C for about 4 hours. After pretreatment, the sample was approximately 0.0845 Pa 3N2 / S (50 sccm) was flowed through the catalyst bed for approximately 40 minutes to sweep free chlorine from the catalyst surface prior to interaction with the organic feed (1233xf). Pretreatment is considered important for many embodiments of the present invention. The reactor outlet gas was flowed through a 20-60 wt% aqueous KOH wash solution, and then the product was collected by capturing the outlet gas from a scrubber into a cylinder held in dry ice or liquid N2. The product was then isolated by distillation. Four different activated carbons, e.g., Shirosaga, Calgon, Norit, and Aldrich, were used as catalysts at approximately 60 to approximately 150 °C: approximately 50 wt% SbCl5 / C, approximately 3 to approximately 6 wt% FeCl3 / C, 20 wt% SnCl4 / C, and approximately 23 wt% TiCl4 / C. Of all the catalysts used for this reaction, Cl2 and HF-pretreated SbCl5 / C were found to be overall preferred in terms of activity. The results using SbCl5 as the catalyst are shown in Table 2.

[0054] [Table 2]

[0055] Example 7 Conversion of CF3CFClCH3 to CF3CF=CH2 in the gas phase A 558.8 mm (22 inch) (12.7 mm (1 / 2 inch) diameter) Monel tube gas-phase reactor was loaded with 120 cc of catalyst. The reactor was mounted inside a three-zone (top, middle, and bottom) heater. The reactor temperature was read with a custom-made five-point thermocouple held centrally inside the reactor. The reactor inlet was connected to a preheater maintained at approximately 300°C by electrical heating. The organic (CFCFClCH) was fed from a cylinder maintained at approximately 65°C through a control valve, needle valve, and gas mass flow meter. The organic line to the preheater was heat traced and maintained at a constant temperature of approximately 65°C to approximately 70°C by electrical heating to avoid condensation. The feed cylinders were mounted on a balance to monitor their weight by difference. The reaction was carried out at a constant reactor pressure of 0 to 689.4 kPa (approximately 0 to approximately 100 psig) by controlling the reactor outlet gas flow rate with a separate research control valve. The gas mixture exiting the reactor was analyzed by online GC and GC / MS connected via a hot-box valve arrangement to prevent condensation. Depending on the reaction conditions, the conversion of CFCFClCH was approximately 98%, and the selectivity to HFO-1234yf was approximately 69% to approximately 86%. The product was collected by flowing the reactor outlet gas through an approximately 20% to approximately 60% aqueous KOH scrubbing solution and then trapping the outlet gas from a scrubber into a cylinder held in dry ice or liquid N. The product was then isolated by distillation. The results are tabulated in Table 3.

[0056] [Table 3]

[0057] Example 8 Selective Catalytic Conversion of CCl3CCl=CH2 to CF3CCl=CH2 (HFO-1233xf) in the Gas Phase A Monel tube gas-phase reactor, 558.8 mm (22 inches) long and 12.7 mm (1 / 2 inch) in diameter, was filled with 120 cc of catalyst or a mixture of two catalysts. In the case of a mixture, the Cr2O3 catalyst was maintained in the bottom zone of the reactor at a substantially constant temperature of about 270°C to 500°C, while the other catalyst, such as FeCl3 / C, was maintained in the middle and top zones of the reactor at a substantially constant temperature of about 120°C to 220°C. The reactor was mounted inside a heater with three zones (top, middle, and bottom). The reactor temperature was read with a custom-made five-point thermocouple held inside the center of the reactor. The bottom of the reactor was connected to a preheater maintained at about 300°C by electrical heating. Liquid HF was fed from a cylinder into the preheater at a substantially constant rate of about 1 to about 1000 g / hr through a needle valve, a liquid mass flow meter, and a research control valve. The HF cylinder was maintained at a substantially constant pressure of 310.2 kPa (about 45 psig) by applying anhydrous N2 gas pressure to the cylinder headspace. A feed rate of about 10 g / hr to about 1000 g / hr of CCl3CCl=CH2 was fed as a liquid from the cylinder through a dip tube under N2 pressure of 310.2 kPa (about 45 psig). Organisms flowed from the dip tube into the preheater (maintained at about 250°C) at a substantially constant rate of about 1 to about 1000 g / hr through a needle valve, a liquid mass flow meter, and a research control valve. Organisms were also fed as a gas while the cylinder containing the organisms was heated to about 220°C. The gaseous effluent from the cylinder passes through a needle valve and a mass flow control valve to a preheater. The organic line from the cylinder to the preheater was maintained at about 200°C by constant temperature heat tracing wrapping and electrical heating elements. All feed cylinders were placed on a balance to monitor their weight by difference. The catalyst was dried at reaction temperature for about 8 hours, then the organic feed, CCl3CCl=C Prior to contact with H2, the mixture was pretreated with approximately 50 g / hr of HF at atmospheric pressure for 6 hours, followed by 6 hours of HF pressure at approximately 50 psig (344.7 kPa). The reaction was carried out at a substantially constant reactor pressure of approximately 0 to 1034.2 kPa (approximately 0 to 150 psig) by controlling the reactor outlet gas flow rate with a separate research control valve. The gases exiting the reactor were analyzed by online GC and GC / MS connected via a hot-box valve arrangement to prevent condensation. The conversion of CCl3CCl=CH2 was approximately 90 to approximately 100%, and the selectivity to CF3CCl=CH2 (1233xf) was approximately 79%. The effluent also contained approximately 7.7% HFO-1243zf, approximately 1.3% 1232 isomers, and approximately 0.8% 1223, as well as unidentified by-products. The product was collected by flowing the reactor outlet gases through a 20-60 wt. % aqueous KOH scrubbing solution and then trapping the outlet gases from the scrubber in a cylinder held in dry ice or liquid N2. The product, 1233xf, was then substantially isolated by distillation. Using only the Cr2O3 catalyst, a selectivity of about 68% to 1233xf was achieved at a conversion level of about 79%.

[0058] Examples 9A to 9D Direct liquid-phase catalytic fluorination of CCl3CCl=CH2 to CF3CFClCH3 (244 isomer) with HF Example 9A Approximately 327 g of HF, approximately 50 g of CCl3CCl=CH2, and approximately 75 g of SbCl5 were charged to a 1 L autoclave. The reaction mixture was stirred at approximately 80°C for approximately 3 hours under a pressure of 4205.8 kPa (approximately 610 psig). After the reaction, the reactor was cooled to approximately 40°C, and then approximately 300 ml of water was slowly added to the autoclave over a period of approximately 45 minutes. After the addition of water under stirring was completed, the reactor was cooled to room temperature, and then the overhead gas was transferred to a separate collection cylinder. The yield of CF3CFClCH3 was approximately 89% at a CCl3CCl=CH2 conversion level of approximately 88%. Other major by-products were CF3CF2CH3 (2%) and an unidentified isomer of a C4 compound of the general formula C4H3Cl3F4 (8%).

[0059] Example 9B Approximately 327 g of HF, approximately 50 g of CCl3CCl=CH2, and approximately 75 g of SbCl5 were charged to a 1 L autoclave. The reaction mixture was stirred at approximately 100°C for approximately 3 hours under a pressure of 4722.9 kPa (approximately 685 psig). After the reaction, the reactor was cooled to approximately 40°C, and then approximately 300 ml of water was slowly added to the autoclave over a period of approximately 45 minutes. After the addition of water under stirring was completed, the reactor was cooled to room temperature, and then the overhead gas was transferred to a separate collection cylinder. The yield of CF3CFClCH3 was approximately 78% at a CCl3CCl=CH2 conversion level of approximately 100%. Other major by-products were CF3CF2CH3 (approximately 4%) and an unidentified isomer of a C4 compound of the general formula, C4H3Cl3F4 (approximately 13%).

[0060] Example 9C Approximately 327 g of HF, approximately 50 g of CCl3CCl=CH2, and approximately 75 g of SbCl5 were charged to a 1 L autoclave. The reaction mixture was stirred at approximately 125°C for approximately 6 hours under a pressure of 5688.1 kPa (approximately 825 psig). After the reaction, the reactor was cooled to approximately 40°C, and then approximately 300 ml of water was slowly added to the autoclave over a period of approximately 45 minutes. After the addition of water under stirring was completed, the reactor was cooled to approximately room temperature, and then the overhead gas was transferred to a separate collection cylinder. The major products were CF3CF2CH3 (approximately 53%) and CF3CFClCH3 (approximately 25%) at a CCl3CCl=CH2 conversion level of approximately 100%. Other major by-products were an unidentified isomer of a C4 compound of the general formula C4H3Cl3F4 (8%) and tar.

[0061] Example 9D Approximately 327 g of HF, approximately 50 g of CCl3CCl=CH2, and approximately 75 g of SbCl5 were charged to a 1-L autoclave. The reaction mixture was stirred at approximately 150°C for approximately 6 hours under a pressure of 5688.1 kPa (approximately 825 psig). After the reaction, the reactor was cooled to approximately 40°C, and then approximately 300 ml of water was slowly added to the autoclave over a period of approximately 45 minutes. After the addition of water under stirring was completed, the reactor was cooled to approximately room temperature, and then the overhead gas was transferred to a separate collection cylinder. The major products were CF3CF2CH3 (approximately 57%) and CF3CFClCH3 (approximately 15%), at a CCl3CCl=CH2 conversion level of approximately 100%. Other major by-products were an unidentified isomer of a C4 compound of the general formula C4H3Cl3F4 (approximately 11%) and tar.

[0062] Example 10 Catalytic conversion of CF3CF2CH3 to CF3CF=CH2 A 558.8 mm (22 inch) (12.7 mm (1 / 2 inch) diameter) Monel tube gas-phase reactor was loaded with 120 cc of catalyst. The reactor was mounted inside a three-zone (top, middle, and bottom) heater. The reactor temperature was read with a custom-made five-point thermocouple held centrally inside the reactor. The reactor inlet was connected to a preheater maintained at approximately 300°C by electrical heating. Organics (245 cb) were fed from a cylinder maintained at approximately 65°C through a control valve, needle valve, and gas mass flow meter. The organics line to the preheater was heat traced and maintained at a substantially constant temperature between approximately 65°C and approximately 70°C by electrical heating to avoid condensation. The feed cylinders were mounted on a balance to monitor their weight by difference. The reaction was carried out at a substantially constant reactor pressure of 0 to 689.4 kPa (about 0 to about 100 psig) by controlling the flow rate of the reactor outlet gas with a separate research control valve. The gas mixture exiting the reactor was analyzed by online GC and GC / MS connected via a hot-box valve arrangement to prevent condensation. Depending on the reaction conditions, the conversion of 245cb ranged from about 30% to about 70%, and the selectivity for 1234yf ranged from about 90% to about 100%. The product was collected by flowing the reactor outlet gas through a 20 to 60 wt% aqueous KOH scrubbing solution and then capturing the outlet gas from a scrubber into a cylinder held in dry ice or liquid N2. The product was then substantially isolated by distillation. The results are tabulated in Table 4.

[0063] [Table 4]

[0064] While several particular embodiments of the present invention have thus been described, various changes, modifications, and improvements will readily occur to those skilled in the art. Such changes, modifications, and improvements made apparent by this disclosure, even if not expressly mentioned herein, are intended to be part of this description and are intended to be within the spirit and scope of the present invention. Accordingly, the foregoing description is by way of example only and not for purposes of limitation.

Claims

1. Formula (I) C(X) ｍ CCl(Y) ｎ C(X) ｍ (I) with at least one compound of formula (II) CF ３ CF=CHZ (II) wherein each X, Y and Z is independently H, F, Cl, I or Br, each m is independently 1, 2 or 3, and n is 0 or 1.

2. 2. The method of claim 1, wherein the at least one compound of formula (I) comprises a compound wherein n is 0, each X is independently H or Cl, and Z is H.

3. At least one compound of formula (I) has formula (IA): C(X) ２ =CClC(X) ３ (IA) 10. The method of claim 1, comprising a compound of the formula: wherein X is as specified in claim 1.

4. 4. The method of claim 3, wherein Z in the compound of formula (II) is H.

5. 4. The method of claim 3, wherein X is independently H or Cl.

6. 10. The method of claim 1, wherein the at least one compound of formula (I) comprises at least one tetrachloropropene.

7. At least one compound of formula (I) is CH ２ = CClCCl ３ , CCl ２ =CClCH ２ Cl, CHCl=CClCCl ２ H, and combinations thereof.

8. At least one compound of formula (I) is represented by formula (IAA): C(X) ２ =CClCF ３ (IAA) 10. The method of claim 1, comprising a compound of the formula: wherein X is as specified in claim 1.

9. 9. The method of claim 8, wherein each X in the compound of formula (IAA) is independently H or Cl.

10. At least one compound of formula (I) is CH ２ = CClCF ３ 2. The method of claim 1, comprising: (HCFC-1223xf).

11. At least one compound of formula (I) has formula (IB): C(X) ３ CClYC(X) ３ (IB) 10. The method of claim 1, comprising a compound of the formula: wherein X and Y are as specified in claim 1.

12. 12. The method of claim 11, wherein the compound of formula (IB) has at least two halogens on one terminal carbon and at least two hydrogen atoms on the other terminal carbon.

13. 13. The method of claim 12, wherein the at least one compound of formula (IB) comprises at least one propene having at least four halogen substituents.

14. 13. The method of claim 12, wherein the at least one compound of formula (IB) comprises at least one propene having at least five halogen substituents.

15. 13. The method of claim 12, wherein in at least one compound of formula (IB), Y is F and all three Xs on one terminal carbon are F.

16. The at least one compound of formula (IB) is selected from the group consisting of 1,1,1,2-tetrafluoro-2-chloropropane, 1-chloro-1,3,3,3-tetrafluoropropane (HFC-244fa), CH ２ ClCHClCCl ３ , CHCl ２ CCl ２ CH ２ Cl, CHCl ２ CHClCHCl ２ 13. The method of claim 12, wherein the hydroxyl group is selected from the group consisting of:

17. The compound of formula (I) is represented by formula (IA) C(X) ２ =CClC(X) ３ (IA) and said converting step comprises converting said compound of formula (IA) into at least one compound of formula (IAA): C(X) ２ =CClCF ３ (IAA) and then converting said compound of formula (IAA) into a compound of formula (IB) C(X) ３ CClYC(X) ３ (IB) wherein X and Y are each as specified in claim 1, and then converting the compound of formula (IB) to a compound of formula (II).

18. wherein the compound of formula (IAA) is reacted with CF under conditions effective to produce at least one monochlorotetrafluoropropane according to formula (IB). ３ CCl=CH ２ 18. The method of claim 17, comprising (HFO-1223xf).

19. The monochlorotetrafluoropropane according to formula (IB) is CF ３ CFClCH ３ (HFC-244fa).

20. The CF ３ CFClCH ３ 20. The method of claim 19, wherein (HFC-244fa) is exposed to reaction conditions effective to produce at least one compound according to formula (II) where Z is H.

21. 21. The method of claim 20, wherein the exposing step comprises at least one gas phase catalytic reaction.

22. 10. The method of claim 1, wherein said exposing step comprises reacting at least one compound of formula (I) (where n is 0) under conditions effective to produce at least one chlorofluoropropane.

23. The at least one chlorofluoropropane has formula (IBB): CF ３ CClFC(X) ３ (IBB) 23. The method of claim 22, wherein the compound is according to the formula: wherein each X is independently F, Cl, or H.

24. 24. The method of claim 23, wherein at least one X in formula (IBB) is H.

25. 25. The method of claim 24, wherein all three X in formula (IBB) are H.

26. Formula (I) C(X) ｍ CCl(Y) ｎ C(X) ｍ (I) and dissolving at least about 50% of said compounds in a solution of formula (II): CF3CF=CHZ (II) wherein each X, Y and Z is independently H, F, Cl, I or Br, each m is independently 1, 2 or 3, and n is 0 or 1.

27. 27. The method of claim 26, wherein said exposing step comprises exposing said compound of formula (I) to reaction conditions effective to convert at least about 90% of said compound to a compound of formula (II).

28. 27. The method of claim 26, wherein said exposing step comprises exposing said compound of formula (I) to reaction conditions effective to convert at least about 97% of said compound to a compound of formula (II).

29. 27. The method of claim 26, wherein said exposing step comprises exposing said compound of formula (I) to reaction conditions effective to obtain a yield of formula (II) of at least about 75%.

30. 27. The method of claim 26, wherein said exposing step comprises exposing said compound of formula (I) to reaction conditions effective to obtain a yield of formula (II) of at least about 90%.

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