Abstract:
Disclosed is a process for the synthesis of fluorinated olefins, and in particularly preferred embodiments tetrafluorinated olefins having F on an unsaturated, non-terminal carbon, such as 2,3,3,3-tetrafluoropropene. The preferred processes of the present invention in accordance with one embodiment generally comprise: 
     (a) reacting a compound of formula (I) 
       X 1 X 2    (I)
 
     with a compound of formula (II) 
       CX 1 X 2 X 3 CX 1 ═CX 1 X 2    (II)
 
     to produce a reaction product comprising a compound of formula (III) 
       CF 3 CHX 1 CH 2 X 2    (III),
 
       and 
     (b) exposing said compound of formula (III) to reaction conditions effective to convert said compound of formula (III) to a compound of formula (IV) 
       CF 3 CZ═CH 2    (IV)
 
     wherein X 1 , X 2 , and X 3  are each independently selected from the group consisting of hydrogen, chlorine, bromine, fluorine and iodine, provided that X 1  and X 2  in formula (I) are not both hydrogen and Z is Cl, I, Br, or F.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a division of U.S. application Ser. No. 12/249,958, filed Oct. 12, 2008, (now U.S. Pat. No. 9,079,818, issued Jul. 14, 2015), which application claims the priority benefit of U.S. Provisional Application No. 60/068,509, filed Oct. 15, 2007, which are incorporated herein by reference. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention relates to methods for the preparation of fluorinated olefins, and in particular tetrafluorinated propenes. In specific embodiments, the invention concerns processes for the preparation of 2,3,3,3-tetrafluoropropene, CF 3 CF═CH 2  (HFO-1234yf). 
       BACKGROUND 
       [0003]    Hydrofluorocarbons (HFC&#39;s), in particular hydrofluoroalkenes (i.e. hydrofluoroolefins (HFOs)) such as tetrafluoropropenes (including 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf)) have been disclosed to be effective refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids for buffing abrasive agents, displacement drying agents and power cycle working fluids. Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), both of which potentially damage the Earth&#39;s ozone layer, HFCs do not contain chlorine and, thus, pose no threat to the ozone layer. However, compared to HFCs, HFOs are generally even more ecologically friendly because they generally have a lower Global Warming Potential (GPW). 
         [0004]    Several methods for preparing hydrofluoroalkanes are known. For example, U.S. Pat. No. 4,900,874 describes a method of making fluorine containing olefins by contacting hydrogen gas with fluorinated alcohols. U.S. Pat. No. 2,931,840 describes a method of making fluorine containing olefins by pyrolysis of methyl chloride and tetrafluoroethylene or chlorodifluoromethane. The preparation of HFO-1234yf from trifluoroacetylacetone and sulfur tetrafluoride has been described. See Banks, et al., Journal of Fluorine Chemistry, Vol. 82, Iss. 2, p. 171-174 (1997). Also, U.S. Pat. No. 5,162,594 discloses a process wherein tetrafluoroethylene is reacted with another fluorinated ethylene in the liquid phase to produce a polyfluoroolefin product. 
         [0005]    U.S. Pat. No. 6,548,719 describes generally the production of a wide range of fluoroolefins by dehydrohalogenating, in the presence of a phase transfer catalyst, a compound of formula CF 3 C(R 1   a R 2   b )C(R 3   c R 4   d ) with at least one alkali metal hydroxide, where the R substituents are as defined in the patent, provided that there is at least one hydrogen and one halogen on adjacent carbon atoms. 
         [0006]    The preparation of 1,3,3,3-tetrafluoropropene is disclosed in U.S. Pat. No. 5,986,151 and U.S. Pat. No. 6,124,510. These patents disclose processes that comprise catalytic dehydrofluorination of CF 3 CH 2 CF 2 H in the gas phase to afford CF 3 CH═CHF. However, each of these methods has the disadvantage of being limited by the requirement of isolating 1,1,1,3,3-pentafluoropropane (“245fa”) as a starting reactant, which may be undesirable for reasons including cost and material availability. 
       SUMMARY OF THE INVENTION 
       [0007]    Applicants have discovered a process for the synthesis of fluorinated olefins, and in particularly preferred embodiments, tetrafluorinated olefins having F on an unsaturated, non-terminal carbon, such as 2,3,3,3-tetrafluoropropene. 
         [0008]    The preferred processes of the present invention in accordance with one embodiment generally comprise: 
         [0009]    (a) reacting a compound of formula (I) 
         [0000]      X 1 X 2    (I)
 
         [0000]    with a compound of formula (II) 
         [0000]      CX 1 X 2 X 3 CX 1 ═CX 1 X 2    (II)
 
         [0000]    to produce a reaction product comprising a compound of formula (III) 
         [0000]      CF 3 CHX 1 CH 2 X 2    (III),
 
         [0000]      and 
         [0010]    (b) exposing said compound of formula (III) to reaction conditions effective to convert said compound of formula (III) to a compound of formula (IV) 
         [0000]      CF 3 CZ═CH 2    (IV)
 
         [0000]    wherein X 1 , X 2 , and X 3  are each independently selected from the group consisting of hydrogen, chlorine, bromine, fluorine and iodine, provided that X 1  and X 2  in formula (I) are not both hydrogen and that Z is Cl, I, Br, or F. 
         [0011]    In specifically preferred embodiments directed to the formation of 1,3,3,3-tetrafluoropropene (HFO-1234yf), the processes comprise: 
         [0012]    (a) reacting a compound of formula (IA) 
         [0000]      X 1 X 2    (IA)
 
         [0000]    with a compound of formula (IIA) 
         [0000]      CH 2 X 2 CX 2 ═CX 2 X 2    (IIA)
 
         [0000]    to produce a reaction product comprising a compound of formula (IIIA) 
         [0000]      CF 3 CHFCH 2 Cl   (IIIA),
 
         [0000]      and 
         [0013]    (b) exposing said compound of formula (IIIA) to reaction conditions effective to convert said compound of formula (IIIA) to a compound of formula (IVA) 
         [0000]      CF 3 CF═CH 2    (IVA)
 
         [0000]    wherein X 1  is selected from the group consisting of hydrogen, chlorine, bromine, fluorine and iodine, and each X 2  is each independently selected from the group consisting of chlorine, bromine, fluorine and iodine. 
         [0014]    In certain highly preferred embodiments, the compound of formula (I) comprises HF, the compound of formula (II) comprises CCl 2 ═CClCH 2 Cl (HFCO-1230), and the compound of formula (III) comprises CF 3 CHFCH 2 F (HFC-245eb). 
         [0015]    The present invention is, thus, directed to processes which involve, in one embodiment, the production of CF 3 CF═CH 2  and which are amenable to scale up from readily available and relatively inexpensive starting materials. 
     
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
       [0016]    The present invention is directed, in preferred embodiments, to methods for the production of 2,3,3,3-tetrafluoropropene, CF 3 CF═CH 2  (“HFO-1234yr”). 
         [0017]    The step of reacting a compound of formula (I), including compounds of formula (IA) (preferably HF), with a compound of formula (II), including compounds of formula (IIA) (preferably HFCO-1230), is amenable to a large number of specific processing condition and steps in accordance with the teachings contained herein, and all such variations are within the broad scope of the present invention. For example, the reaction step (a) may comprise a liquid-phase or a gas-phase addition reaction, either catalyzed or uncatalyzed, although catalyzed liquid-phase reactions are generally preferred. 
         [0018]    For embodiments in which the compound of formula (I) comprises HF and the compound of formula (II) comprises a compound of formula (IIA), and more preferably HFCO-1230, it is preferred that the reaction step comprises exposing the reactants, preferably at a temperature of from about 0° C. to about 250° C., and even more preferably at a temperature of from about 150° C. to about 250° C., in the presence of a catalyst, preferably a halide of a metal selected from period 5, groups 10 through 15. Highly preferred catalyst comprises, and preferably comprises in major proportion, one or more halides of antimony, preferably SbCl 5 . 
         [0019]    It is contemplated that numerous and varied other reaction conditions may be used for the reaction step (a). For example, the reaction pressure may vary widely, but in preferred embodiments the reaction occurs under pressure, preferably pressure of at least about 500 psig of pressure, more preferably at pressures of from about 500 to about 1000 psig, and even more preferably at pressures of from about 700 to about 1000 psig. Furthermore, for batch reaction conditions in particular, it is contemplated that the reaction time is from about 5 hours to about 24 hours, more preferably from about 5 hours to about 15 hours. 
         [0020]    Preferably, the reaction step (a) produces a reaction product comprising a compound of formula (III), more preferably formula (IIIA), and even more preferably HFCO-1230. In preferred embodiments, the conversion of the compound of formula II in the reaction is from about 70% to about 100% and the selectivity of the reaction to formula (III) compounds, more preferably formula (IIIA) compounds, and even more preferably HFC-245eb, is from about 40% to about 70%. In certain preferred embodiments the reaction product also contains, in addition to the preferred HFC-245eb, CF 3 CHFCH 2 Cl (HCFC-244), CF 3 CHClCH 2 Cl (HCFC-243), CF 3 CHClCH 2 F (HCFC-244), CF 3 CCl═CH 2 , (HFCO-1233), CF 3 CFClCH 3  (HCFC-244), and tar. 
         [0021]    Optionally, but preferably, the reaction product from the reaction step (a) is subjected to one or more separation steps, including preferably distillation, to produce a product having a relatively higher concentration of compounds of formula (III), and even more preferably compounds of formula (IIIA), for use as a feed material to the exposing step (b). In certain preferred embodiments, the concentration of formula (III) compounds (exclusive of carrier fluid or other inert components) is at least about 90%, and even more preferably at least about 95%, by weight. 
         [0022]    After the reaction step (a), the reaction product, or at least a portion thereof, with or without fractionation, is preferably exposed to reaction conditions effective to produce a reaction product comprising at least one compound of formula (IV), more preferably formula (IVA), and even more preferably 2,3,3,3-tetrafluoropropene (HFO-1234yf). In preferred embodiments, the exposing step comprises dehydrohalogenating the compound of formula (III), in the gas and/or liquid phase. Although it is contemplated that numerous dehydrohalogenation steps can be utilized with good effect in accordance with the teachings contained herein, it is preferred in certain embodiments that the dehydrohalogenation step comprises contacting the compound of formula (III), in the liquid phase with a potassium hydroxide solution, in the presence, or not, of Crown ether, or in the gas phase with a catalyst, at a relatively elevated temperature for a time sufficient to convert the compound to 2,3,3,3-tetrafluoropropene. 
         [0023]    For embodiments involving the preferred liquid phase dehyrdofluorination, it is generally preferred that the compound of formula (III) is reacted in aqueous KOH in a concentration of from about 10% to about 35%, preferably from about 20% to about 25%, at temperatures of from about 25° C. to about 90° C., and more preferably from about 45° C. to about 80° C. 
         [0024]    It is contemplated that numerous and varied other reaction conditions may be used for the liquid phase dehydrohalogenation. For example, the reaction pressure may vary widely, but in preferred embodiments the reaction occurs, at least in part, under pressure, preferably a pressure of at least about 100 psig, more preferably a pressure from about 150 psig to about 200 psig, and even more preferably a pressure of from about 150 to about 180 psig. Furthermore, particularly for batch reaction conditions, it is contemplated that the reaction time is from about 5 hours to about 24 hours, more preferably from about 15 hours to about 25 hours. 
         [0025]    Preferred gas phase dehydrohalogenation reactions comprise introducing a stream containing the compound of formula (III) into a reactor which preferably contains a catalyst, preferably a bed of metal-based catalyst, more preferably Pd or Ni on carbon, maintained at temperature of from about 200° C. to about 500° C., and even more preferably at temperatures of from about 250° C. to about 500° C. 
         [0026]    It may be possible in certain embodiments to utilize an exposing step conducted in accordance with the teachings of U.S. Pat. No. 6,548,719, which is assigned to the assignee of the present invention and which is incorporated herein by reference. Gas phase dehydrofluorination with an appropriate catalyst and at elevated temperature may also be performed in certain embodiments in accordance with the procedures as described in U.S. Pat. No. 5,986,151, which is also incorporated herein by reference. 
         [0027]    The exposing step preferably produces a reaction product stream which comprises tetrafluoropropene, and in particular 2,3,3,3-tetrafluoropropene (HFO-1234yf). In preferred embodiments, the conversion of the compound of formula III in the dehydrohalogenation reaction is from about 70% to about 100% and the selectivity of the reaction for formula (IV), and for HFO-1234yf in particular, is from about 70 to about 95%, more preferably from about 80 to 95%. 
         [0028]    Optionally, but preferably, the reaction product from the exposing step (b) is subjected to one or more separation steps, including preferably distillation, to produce a product having a relatively higher concentration of compounds of formula (IV), more preferably compounds of formula (IV), and even more preferably HFO-1234yf. In certain preferred embodiments, the concentration of formula (IV) compounds (exclusive of carrier fluid or other inert components) is at least about 90%, and even more preferably at least about 95%, by weight. 
       EXAMPLES 
     Example 1 
     Synthesis of CF 3 CHFCH 2 F (245eb) by Liquid-Phase Catalytic Reaction of CCl 2 ═CClCH 2 Cl with HF 
       [0029]    350 grams HF and 50 grams CCl 2 ═CClCH 2 Cl were charged into a 1-L Teflon-lined, Monel autoclave. The reaction mixture was stirred at 100° C. and when the temperature reaches to 100° C., 75 grams SbCl 5  was added into the reaction mixture. The mixture was stirred for 12 hours under 625 psig of pressure. After the reaction, the reactor was cooled to room temperature and 300 ml water was then added slowly into the autoclave over a period of 45 min. After complete addition of water under stirring, the reactor was cooled to room temperature and then the overhead gases were transferred to another collecting cylinder. The yield of CF 3 CHFCH 2 F was 53% at a CCl 2 ═CClCH 2 Cl conversion level of about 100%. The other major by-products were CF 3 CHFCH 2 Cl, CF 3 CHClCH 2 F, CF 3 CHClCH 2 Cl, CF 3 CCl═CH 2 , CF 3 CFClCH 3 , and an unidentified isomer. The desired product, CF 3 CHFCH 2 F was isolated by distillation with 99% purity. 
       Example 2 
     Synthesis of CF 3 CHFCH 2 F (245eb) by Liquid-Phase Catalytic Reaction of CCl 2 ═CClCH 2 Cl with HF 
       [0030]    350 grams HF, 50 grams CCl 2 ═CClCH 2 Cl and 75 grams SbCl 5  were charged into a 1-L Teflon-lined, Monel autoclave. The reaction mixture was stirred at 125° C. for 12 h under 743 psig of pressure. After the reaction, the reactor was cooled to room temperature and 300 ml water was then added slowly into the autoclave over a period of 45 min. After complete addition of water under stirring, the reactor was cooled to room temperature and then the overhead gases were transferred to another collecting cylinder. The yield of CF 3 CHFCH 2 F was 57% at a CCl 2 ═CClCH 2 Cl conversion level of about 100%. The other major by-products were CF 3 CHFCH 2 Cl, CF 3 CHClCH 2 Cl, CF 3 CHClCH 2 F, CF 3 CCl═CH 2 , CF 3 CFClCH 3 , and tar. The desired product, CF 3 CHFCH 2 F was isolated by distillation with 99% purity. 
       Example 3 
     Synthesis of CF 3 CHFCH 2 F (245eb) by Liquid-Phase Catalytic Reaction of CCl 2 ═CClCH 2 Cl with HF 
       [0031]    350 g HF, 50 g CCl 2 ═CClCH 2 Cl, and 75 g SbCl 5  were charged into a 1-L autoclave. The reaction mixture was stirred at 150° C. for 8 h under 910 psig of pressure. After the reaction, the reactor was cooled to room temperature and 300 ml water was then added slowly into the autoclave over a period of 45 min. After complete addition of water under stirring, the reactor was cooled to room temperature and then the overhead gases were transferred to another collecting cylinder. The yield of CF 3 CHFCH 2 F was 59% at a CCl 2 ═CClCH 2 Cl conversion level of about 100%. The other major by-products were mostly polymers and tars. 
       Example 4 
     Synthesis of CF 3 CF═CH 2  (HFO-1234yf) by Gas-Phase Reaction of CF 3 CHFCH 2 F 
       [0032]    1.32 Kg (9.85 mol) CF 3 CHFCH 2 F (99% pure) is stirred with 2.5 L (10.1 mol) of 25% KOH solution in the presence or absence of 18-Crown ether at 50° C. Without being bound to theory, the reaction is believed proceed as indicated below: 
         [0000]      CF 3 CHFCH 2 F+KOH→CF 3 CF═CH 2 +KF+H 2 O
 
         [0000]    A cleaned and leak tested 2 gallon autoclave was evacuated and then 2.5 L KOH water solution as indicated above was charged into it. The KOH solution was cooled down to 0° C. by chiller. The autoclave was evacuated again and using vacuum, 1.32 Kg CF 3 CFHCFH 2  was then charged into it. The sealed reactor was gradually heated with stirring to 55° C. and then was heated by setting temperature at 55° C. After a reaction time of about 45 min., the temperature increased to 70° C. by exothermic reaction (pressure was 165 psig). A 0° C. cooling liquid was applied to bring the temperature down to 57° C. Then the reaction was continued at 55° C. for 20 h. 
         [0033]    The reaction mixture was cooled down to 30° C. and the gas product was transferred into a cylinder at dry ice-acetone temperature. 1.1 Kg CF 3 CF═CH 2  with GC purity 98.6% was collected. 
       Example 5 
     Synthesis of CF 3 CF═CH 2  (HFO-1234yf) by Gas-Phase Reaction of CF 3 CHFCH 2 F, CF 3 CHFCH 2 Cl, and CF3CHClCH 2 F 
       [0034]    In a gas phase dehydrohalogenation reaction, 50 sccm CF 3 CHFCH 2 F was passed over a 100 cc catalyst bed comprised of Cr 2 O 3  or Ni-mesh or activated carbon or Pd/C or Ni/C kept inside a monel reactor in the presence of 20 sccm of HF at 250-400° C. to synthesize CF 3 CF═CH 2  which was finally trapped in a dry ice tap. The results using different catalysts are shown in Table 1. 
         [0035]    In a typical reaction, a 22-inch long monel reactor with ½-inch inner diameter was charged with 100 cc catalyst. A flow of 20 sccm of N 2  was always kept during the reaction. The reactor temperature was then raised gradually to the desired reaction temperature. HFC-245eb was passed through gas-flow controllers into a preheater. The preheater temperature was kept at 300° C. The gas stream coming out of the preheater was passed through the catalyst bed at the desired temperature over a specified period of time. An on-line GC and a GCMS were used to analyze samples taken at the reactor exit line at regular time intervals. Finally, the reactor exit stream was run into a 20% KOH scrubber solution at room temperature to eliminate any acid HF formed in-situ during the reaction. The exit gas mixture coming out of the scrubber solution was then condensed in a dry-ice trap to collect the products. The desired product CF 3 CF═CH 2  (1234yf) was then isolated from the mixture by distillation. Results are shown in Table 1 
         [0000]    
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Dehydrofluorination of 245eb different heterogeneous catalysts 
               
             
          
           
               
                   
                   
                 245eb flow 
                   
                 Conversion of  
                 Selectivity for 
               
               
                 # 
                 Catalyst 
                 rate, g/h 
                 T° C. 
                 245eb 
                 1234yf 
               
               
                   
               
             
          
           
               
                 1A 
                 Ni-mesh 
                 10 
                 495 
                 36 
                 100 
               
               
                 1B 
                 Ni-mesh 
                 10 
                 525 
                 67 
                 100 
               
               
                 1C 
                 Ni-mesh 
                 10 
                 565 
                 89 
                 78 
               
               
                 2A 
                 2-wt % Ni/C 
                 10 
                 495 
                 63 
                 94 
               
               
                 2B 
                 2-wt % Ni/C 
                 10 
                 525 
                 79 
                 84 
               
               
                 2C 
                 2-wt % Ni/C 
                 8 
                 565 
                 100 
                 69 
               
               
                 3A 
                 Cr-Oxyfluoride 
                 11 
                 420 
                 69 
                 47 
               
               
                 3B 
                 Cr-Oxyfluoride 
                 10 
                 440 
                 78 
                 43 
               
               
                 4A 
                 Carbon 
                 10 
                 500 
                 32 
                 96 
               
               
                 4B 
                 Carbon 
                 11 
                 550 
                 69 
                 86 
               
               
                 4C 
                 Carbon 
                 12 
                 600 
                 85 
                 76 
               
               
                 5A 
                 1.5-wt %-Pd/C 
                 5 
                 450 
                 56 
                 58 
               
               
                 5B 
                 1.5-wt %-Pd/C 
                 7 
                 475 
                 68 
                 53 
               
               
                 6A 
                 4-6-wt %-FeCl 3 /C 
                 8 
                 250 
                 42 
                 49 
               
               
                 6B 
                 4-6-wt %-FeCl 3 /C 
                 8 
                 300 
                 59 
                 37