""
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`PATENT APPLICATION TRANSMITTAL LETTER
`(Large Entity)
`
`Docket No-
`H0003789US
`
`TO THE COMMISSIONER FOR PATENTS
`
`Transmitted herewith for filing under 35 U.S.C. 111 and 37 C.F.R. 1.53 is the patent application of:
`
`Daniel C. Merkel, Rajiv R. Singh, Hsueh Sung Tung
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`For: PROCESS FOR PRODUCING FLUOROPROPENES
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`Enclosed are:
`
`EDCDCIDCIIZ
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`Certificate of Mailing with Express Mail Mailing Label No.
`sheets of drawings.
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`EL262354613US
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`A certified copy of a
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`application.
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`Declaration
`Power of Attorney
`Information Disclosure Statement
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`Cl Signed.
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`Preliminary Amendment
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`Cl Unsigned.
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`Other: Application Data Sheet, Two Acknowledgement Postcards
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`CLAIMS AS FILED
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`_
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`II1
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`Multiple Dependent Claims (check if applicable) D
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`|
`I
`BASIC FEEI
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`I A
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`to cover the filing fee is enclosed.
`$1,760.00
`check in the amount of
`IZI The Director is hereby authorized to charge and credit Deposit Account No.
`as described below.
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`19-5425
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`Cl Charge the amount of
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`as filing fee.
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`Credit any overpayment.
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`IX] Charge any additional filing fees required under 37 C.F.R. 1.16 and 1.17.
`E] Charge the issue fee set in 37 C.F.R. 1.18 at the mailing of the Notice of Allowance,
`pursuant to 37 C.F.R. 1.31 1 (b).
`
`Dated: October27,2003
`
`’ RMSignature
`
`Peter J. Butch III, Reg. No. 32,203
`Honeywell International, Inc.
`101 Columbia Road, Building Meyer 5
`Morristown, NJ 07962-2245
`Telephone: 973-455-2587
`
`P01LARGEIREV06
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`Arkema Exhibit 1037
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`Page 1 of 40
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`Arkema Exhibit 1037
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`Page 1 of 40
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`

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`CERTIFICATE OF MAILING BY EXPRESS MAIL UNDER 37 CFR 1.10
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`EV262354613US
`Express Mail Label Number
`
`Attorney Docket No. H0O03789US
`S&L Docket No. P26,267 USA
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`I hereby certify that the attached Patent Application Transmittal Letter for
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`Large Entity Concerning Filing Under 35 U.S.C. 111 and 37 C.F.R. 1.53, including a
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`duplicate copy of the Transmittal Letter, Patent Application specification, an
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`Abstract, an Application Data Sheet, Declaration and Power of Attorney, two
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`acknowledgment postcards and a check in the amount of $1 ,760.00 are being
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`deposited with the United States Postal Service "Express Mail Post Office to
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`Addressee" under 37 C.F.R. § 1.10 in an envelope addressed to the Mail Stop
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`Patent Application, Commissioner for Patents, P. O. Box 1450, Alexandria, VA
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`22313-1450 on October 27, 2003.
`
`
`
` Christophe
`
`.
`Synnestvedt & Lechner LLP
`2600 Aramark Tower
`1101 Market Street
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`Philadelphia, PA 19107-2950
`Telephone: (215) 923-4466
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`EXPRESS MAIL LABEL NO. EV262354613US
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`Dock t No. H0003789US
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`PROCESS FOR PRODUCING FLUOROPROPENES
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`Invented by:
`
`DANIEL C. MERKEL
`
`64 Glenmar Drive
`
`West Seneca, NY 14224
`Citizen of USA
`
`RAJIV R. SINGH
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`18 Foxfire Drive
`
`Getzville, NY 14068
`Citizen of USA
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`HSUEH SUNG TUNG
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`16 Vassar Drive
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`Getzville, NY 14068
`Citizen of U.S.A.
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`Patent Docket No. HO003789US
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`Express Mail Label No. EV262354613US
`S&L File No. P26,267 USA
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`PROCESS FOR PRODUCING FLUOROPROPENES
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`Background of the Invention
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`The present invention relates to a process for producing fluoropropenes in good yield on an industrial
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`scale using commercially and readily available starting materials. More particularly, the present
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`invention relates to a process for producing fluoropropenes by the dehydrohalogenation of halo-
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`propanes, either by reaction with an essentially miscible alkali or alkaline earth metal hydroxide
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`solution in a non-alcohol solvent, or by thermal decomposition.
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`The production of fluoropropenes such as CF3CH=CH2 by catalytic vapor phase fluorination of various
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`saturated and unsaturated halogen—containing C3 compounds is described in U.S. Patent Nos.
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`2,889,379; 4,798,818 and 4,465,786. U.S. Patent No. 5,532,419 discloses a vapor phase catalytic
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`process for the preparation of fluoroalkene using a ch|oro- or bromo-halofluorocarbon and HF. EP
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`974,571 discloses the preparation of 1,1,1,3—tetrafluoropropene by contacting 1,1,1,3,3-
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`pentafluoropropane (HFC-245fa) in the vapor phase with a chromium—based catalyst at elevated
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`temperature, or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg(OH)2_
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`A fluoropropene of particular interest is 1,3,3,3-tetrafluoropropene (HFC-1234ze), which has potential
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`use as a low global warming potential refrigerant. However. this material is presently not available in
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`commercial quantity. The existing technology to make HFC—1234ze is a fluorination process using
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`1,1,1,3,3—pentachloropropane (HCC-240fa) and HF in the presence of a vapor phase catalyst. HFC-
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`1234ze is a by-product of the reaction that is made in relatively small quantity, i.e., less than about 8
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`area % in a gas chromatograph (GC) of the organic reaction product.
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`Patent Docket No. HO0O3789US
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`Express Mail Label No. EV262354613US
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`The process is very expensive because of the low selectivity for the desired product, HFC-1234ze.
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`The reaction is actually intended for the manufacture of HFC-245fa, in which small quantities of HFC-
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`1234ze is produced as a by-product. Complicating matters, the process involves handling large
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`quantities of hazardous materials such as HF and HCI.
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`Henne et al., J.Am. Chem. Soc. 68 496-497 (1946) described the synthesis of various
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`fluoropropenes from CF3CH2CF3 using, e.g., alcoholic KOH, with varying degrees of success. For
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`example, it is stated that in some instances dehydrohalogenation was unsuccessful.
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`In another
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`instance, a protracted reaction time (3 days) was required, or relatively low product yield (40%, 65%)
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`10
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`was obtained.
`
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`Tarrant, et al., J. Am. Chem. Soc. 77 2783-2786 (1955) described the synthesis of CF3CH=CF2
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`starting with: (1) 3-bromo-1,1,3,3-pentafluoropropane and reacting it with a hot solution of KOH in
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`water; and (2) 3-bromo-1,1,3,3—tetraf|uoropropene, reacting it with HF at 150EC and neutralizing the
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`reaction products with a KOH solution.
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`Kimura, et al., J. Org. Chem. 48, 195-198 (1983) described multi-phase dehydrohalogenation of
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`brominated compounds using aqueous KOH and a phase transfer catalyst based on polyethylene
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`glycols and polyethylene glycol-grafted copolymers. The preparation of fluoropropenes by the
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`dehydrohalogenation of fluoropropane using aqueous KOH and a phase transfer catalyst, but with
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`improved yields and selectivity is disclosed by U.S. Patent No. 6,548,719.
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`There is a continuing need for means by which fluoropropenes can be produced commercially with
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`high yield and selectivity, either catalytically or non-catalytically.
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`Patent Docket No. H0003789US
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`Express Mail Label No. EV262354613US
`S&L File No. P26,267 USA
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`Summary of the Invention
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`The present invention provides two new dehydrohalogenation methods by which fluoropropenes may
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`be commercially produced with high yield and selectivity. According to one aspect of the present
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`invention, a dehydrohalogenation process is provided for the preparation of fluoropropenes of the
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`formula CF3CY=CXNHp wherein X and Y are independently hydrogen or a halogen selected from the
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`fluorine, chlorine, bromine and iodine, and N and P are independently integers equal to 0, 1 or 2,
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`provided that (N+P)=2, in which there is reacted, without a catalyst, a halopropane of the formula:
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`CF3C(YR1)C(XNHpR2)
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`wherein R, [R2, X and Yare independently hydrogen or a halogen selected from fluorine, chlorine,
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`bromine and iodine, provided that at least one of R1, R2, X and Y is a halogen and there is at least one
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`hydrogen and one halogen on adjacent carbon atoms; with a solution of at least one alkali or alkaline
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`earth metal hydroxide in a non-aqueous, non—alcoho| solvent therefor that is at least essentially
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`miscible with the halopropane, wherein the reaction is performed at a temperature at which
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`dehydrohalogenation will occur.
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`Reactions performed without a catalyst produce cleaner reaction products, thereby simplifying product
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`work-up and isolation. The halopropane can be CF3CH2CF2H (a commercially available compound
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`also known as HFC-245fa) or CF3CH2CHC|F (HCFC-244fa) a by-product of the manufacture of HFC-
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`245fa. Both halopropanes will dehydrohalogenate to form HFC-1234ze.
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`According to another aspect of the present invention, a dehydrohalogenation process is provided for
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`the preparation of fluoropropenes of the formula CF3CY=CXNHp, wherein X and Y are independently
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`hydrogen or a halogen selected from fluorine, chlorine, bromine and iodine, and N and P are
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`Pat nt Docket No. H0003789US
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`independently integers equal to 0, 1 or 2 provided that (N+P)=2, comprising heating to a temperature
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`at which dehydrohalogenation by thermal decomposition occurs a halopropane of the formula:
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`CF3C(YR1)C(XNHPR2)
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`wherein R1, R2, X and Y are independently hydrogen or a halogen selected from fluorine, chlorine,
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`bromine and iodine, provided that at least one of R1, R2, X and Y is a halogen and there is at least
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`one hydrogen and one halogen on adjacent carbon atoms. The thermal decomposition reaction can
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`be performed either with or without a catalyst for hydrogen halide removal, such as transition metal
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`halides and oxides and combination thereof, preferably iron halides, nickel halides, cobalt halides and
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`combinations thereof. HFC-245fa and CF3CH2CHC|F (HCFC-244fa) can also be reacted by the
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`thermal decomposition reaction of the present invention to form HFC-1234ze.
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`Patent Docket No. H0003789US
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`Express Mail Label No. EV262354613US
`S&L File No. P26,267 USA
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`Detailed Description of the Invention
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`The present invention can be generally described as a process for the preparation of fluoropropenes
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`of the formula CF3CY=CXNHp wherein X and Y are independently a hydrogen or a halogen selected
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`from fluorine, chlorine, bromine and iodine; and N and P are integers independently equal to O, 1 or 2,
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`provided that (N+P)=2.
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`Two dehydrohalogenation methods by which the fluoropropenes may be prepared are disclosed.
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`Both methods dehydrohalogenate a halopropane having the formula:
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`CF3C(YR1)C(XNHpR2)
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`wherein R1, R2, X and Y are independently hydrogen or a halogen selected from fluorine, chlorine,
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`bromine and iodine, provided that at least one of R1, R2, X and Y is a halogen and there is at least
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`one hydrogen and one halogen on adjacent carbon atoms.
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`Included among the halopropanes that can be included in the present invention is 1,1,1,3,3-
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`pentafluoropropane or HFC-245fa and 1-chloro-1,3,3,3-tetrafluoropropane or HCFC-244fa. Various
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`methods for producing these materials are described in U.S. Patent Nos. 5,710,352; 5,969,198;
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`5,728,904; and 6,023,004. Another method described in U.S. Patent No. 5,574,192 is said to be
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`economical, amenable to large-scale application and uses readily available raw materials. The
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`process of that patent uses two steps as follows: (1) formation of CCl3CH2CHC|2 by the reaction of
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`CCI4 with vinyl chloride; and (2) conversion of CCl3CH2CHC|2 to CF3CH2CHF2 and CF3CH2CHFC| by
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`reaction with HF in the presence of a fluorination catalyst selected from antimony halides, niobium
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`halides, arsenic halides, tantalum halides; tin halides; titanium halides; antimony mixed halides;
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`niobium mixed halides, arsenic mixed halides, tantalum mixed halides, mixed tin halides; mixed
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`titanium halides and mixtures thereof. Under-fluorinated materials, such as CF3CH2CHC|2, may be
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`Patent Docket No. H0003789US
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`recycled in subsequent runs. The under—f|uorinated material CF3CH2CHC|F, or HFC-244fa, can also
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`be used as a starting material in the present invention for producing a fluoropropene. Thus, the
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`above—described process can be utilized to obtain two different starting materials for the process of
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`the present invention.
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`Furthermore, commercial quantities of CF3CH2CF2H are available from Honeywell International, |nc.,
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`Morristown, New Jersey, for use as the starting material of the present process for direct conversion
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`to the fluoroalkene CF3CH=CFH by dehydrofluorination according to either process disclosed herein.
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`Other useful starting materials for the production of fluoropropenes and/or fluorohalopropenes include
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`the following: CF3CH2CF2Br; CF3CH2CF2l; CF3CHFCF2Br; CF3CH2CH2Cl; CF3CH2CH2Br;
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`CF3CH2CH2l; CF3CHBrCF2Br; CF3CHClCF2C|; CF3CH2CFHCl; CF3CH2CFHBr; CF3CHC|CF2H;
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`CF3CH2CC|3;
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`and the
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`In another embodiment of the invention, HCFC-244fa and/or HFC-245fa can be prepared by
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`fluorinating 1,1,1 ,3,3-pentachloropropane(HCC-240fa).
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`In this embodiment, in a preliminary step, the
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`process of the invention involves the formation of HCFC-244fa and/or HFC-245fa by reacting
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`1,1,1,3,3-pentachloropropane (HCC-240fa) with hydrogen fluoride (HF) in the vapor phase, or the
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`liquid phase, preferably in the presence of a fluorination catalyst as is well known in the art.
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`The result is a reaction product of one or both of the two products, HCFC-244fa and/or HFC-245fa.
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`In
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`the preferred embodiment of the invention, the HF to HCC-240fa mole ratio preferably ranges from
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`about 2:1 to about 100:1; more preferably from about 4:1 to about 50:1 and most preferably from
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`about 5:1 to about 20:1.
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`Useful fluorination catalysts include, but are not limited to, transition metal halides, Group lVb and Vb
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`metal halides, and combinations thereof, preferably supported on activated carbon or fluorinated
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`alumina. More specifically, preferred vapor phase fluorination catalysts non-exclusively include SbCl5,
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`Patent Docket No. H0003789US
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`Express Mail Label No. EV262354613US
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`SbC|3, SbF5, TaCl5. SnCl4, NbCl5, TiCl4, MoCl5, Cr2O3,Cr2O3/AIZO3, Cr2O3/AIF3, Cr2O3/carbon,
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`CoC|2/Cr2O3/Al2O3, NiC|2/Cr2O3/AIZO3, CoCl2/AIF3, NiCl2/AlF3 and mixtures thereof. Preferred liquid
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`phase fluorination catalysts non-exclusively include SbC|5, SbC|3, SbF5, TaC|5, SnCl4, NbC|5, TiCl4, and
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`MoC|5.
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`It is understood that after pre—treatment with HF or during reaction in the presence of HF the
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`above mentioned catalyst will be partially fluorinated_ Chromium oxide/aluminum oxide catalysts are
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`described in U.S. Pat. No. 5,155,082 which is incorporated herein by reference. Chromium (Ill) oxides
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`such as crystalline chromium oxide or amorphous chromium oxide are preferred vapor phase
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`fluorination catalysts with amorphous chromium oxide being the most preferred vapor phase catalyst.
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`Chromium oxide (Cr2O3) is a commercially available material which may be purchased in a variety of
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`particle sizes. Unsupported SbCl5 and SbCl3 halides are preferred liquid phase catalysts. Both of
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`these liquid phase catalysts are commercially available and well known in the art. Fluorination
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`catalysts having a purity of at least 98% are preferred. The fluorination catalyst is present in an
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`amount sufficient to drive the reaction. The fluorination reaction may be conducted in any suitable
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`fluorination reaction vessel or reactor but it should preferably be constructed from materials which are
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`resistant to the corrosive effects of hydrogen fluoride such as nickel and its alloys, including Hastelloy,
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`lnconel, lncoloy, and Monel or vessels lined with fluoropolymers.
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`Any water in the hydrogen fluoride (HF) will react with and deactivate the fluorination catalyst.
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`Therefore substantially anhydrous hydrogen fluoride is preferred. By "substantially anhydrous" it is
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`meant that the HF contains less than about 0.05 weight % water and preferably contains less than
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`about 0.02 weight % water. However, one of ordinary skill in the art will appreciate that the presence
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`of water in the HF can be compensated for by increasing the amount of catalyst used.
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`The liquid phase fluorination of HCC—240fa is preferably conducted at a temperature of from about
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`50°C to about and 450°C, more preferably from about 60°C to about 180°C and most preferably from
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`about 65°C and 150°C. Fluorination is preferably conducted at a pressure of from about 50 psig to
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`about 400 psig. The reactor is preferably preheated to the desired fluorination reaction temperature
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`Patent Docket No. HO003789US
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`while anhydrous HF is fed to the reactor. The HCC-240fa and HF may be fed to the reactor at the
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`desired temperatures and pressures that are described herein.
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`In a preferred embodiment of the
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`invention, either or both of the HCC-240fa and HF are pre-vaporized or preheated prior to entering the
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`reactor.
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`When HCC-240fa and HF are reacted in a vapor phase with the fluorination catalyst the HCC-240fa
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`and HF may be fed to the reactor at the desired temperatures and pressures that are described
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`herein. The reactor is preheated to the fluorination reaction temperature while anhydrous HF is fed to
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`the reactor. The HCC-240fa and HF may be fed to the reactor at any convenient temperature and
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`pressure. In a preferred embodiment either or both of the HCC-240fa and HF are pre-vaporized or
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`preheated to a temperature of from about 30 °C to about 000 °C prior to entering the reactor. in
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`another embodiment, the HCC-240fa and HF are vaporized in the reactor.
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`The HF and HCC-240fa feeds are then adjusted to the desired mole ratio. The HF to HCC-240fa mole
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`ratio preferably ranges from about 2:1 to about 100:1; more preferably from about 4:1 to about 50:1
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`and most preferably from about 5:1 to about 20:1.
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`The fluorination reaction is conducted at a preferred temperature ranging from about 80 °C to about
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`400 °C; more preferably from about 100 °C to about 350 °C and most preferably from about 200 °C to
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`about 330°C. Reactor pressure is not critical and can be superatmospheric, atmospheric or under
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`vacuum. The vacuum pressure can be from about 5 torr to about 760 torr. The reactant vapor is
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`allowed to contact the fluorination catalyst for from about 0.01 to about 240 seconds, more preferably
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`from about 0.1 to about 60 seconds and most preferably from about 0.5 to about 20 seconds.
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`Usually the process flow of the HCC-240fa and HF is in the down direction through a bed of the
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`catalyst. Before each use, the catalyst is preferably dried, pre-treated and activated.
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`It may also be
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`advantageous to periodically regenerate the catalyst after prolonged use while in place in the reactor.
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`Patent Docket No. H0003789US
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`Express Mail Label No. EV262354613US
`S&L File N . P26,267 USA
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`For Cr2O3', Cr-203/AIZO3, Cr2O3/AIF3, Cr2O3/carbon, CoC|2/Cr2O3/Al2O3, NiCl2/Cr2O3/Al2O3, CoC|2/AIF3,
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`NiC|2/AIF3 catalysts, pre-treatment can be done by heating the catalyst to about 250 °C to about 430
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`°C in a stream of nitrogen or other inert gas. The catalyst may then be activated by treating it with a
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`stream of HF diluted with a large excess of nitrogen gas in order to obtain high catalyst activity.
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`Regeneration of the catalyst may be accomplished by any means known in the art such as, for
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`example, by passing air or air diluted with nitrogen over the catalyst at temperatures of from about
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`100°C to about 400°C, preferably from about 200°C to about 375°C, for from about 1 hour to about 3
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`days, depending on the size of the reactor. For SbC|5, SbCl3, TaC|5, SnC|.,, NbCl5, TICI4, MoC|5
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`catalysts, supported on an solid support such as activated carbon, pre-treatment or activation can be
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`done by first heating the catalyst to about 30°C to 250°C in a stream of nitrogen or other inert gas.
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`it is
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`then treated with a stream of HF in the absence or presence of an oxidizing agent such as chlorine gas in
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`order to obtain high catalyst activity.
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`In addition, the catalyst may optionally be kept active by co-
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`feeding chlorine to the reactor during reaction.
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`HCFC-244fa and HFC-245fa may be recovered from the fluorination reaction product mixture
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`comprised of unreacted starting materials and by—products, including HCI, by any means known in the
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`art, such as by scrubbing, extraction, and preferably distillation. For example, the distillation may be
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`preferably conducted in a standard distillation column at a pressure, which is less than about 300
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`psig, preferably less than about 150 psig and most preferably less than 100 psig. The pressure of the
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`distillation column inherently determines the distillation operating temperature. HCI may be recovered
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`by operating the distillation column at from about -40 °C to about 25 °C, preferably from about -40 °C
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`to about —20°C. Single or multiple distillation columns may be used. The distillate portion includes
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`substantially all the HCFC-244fa, HFC-245fa, unreacted HF and HCI produced in the reaction as well
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`as any other impurities.
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`In the preferred embodiment, HCFC-244fa and the HFC-245fa are separated
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`from all other reaction by-products and unreacted HF for further reaction in step (b) described herein.
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`In the preferred embodiment, any HF present may also be recovered and recycled back for
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`subsequent fluorination reactions.
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`Patent Docket No. H0003789US
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`Express Mail Label No. EV262354613US
`S&L File No. P26,267 USA
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`1234ze is formed by the dehydrochlorination of 1—chloro-1,3,3,3-tetrafluoropropane (HCFC-244fa) or
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`the dehydrofluorination of 1,1,1,3,3-pentafluoropropane (HFC-245fa).
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`According to one method of the present invention, the halopropane is dehydrohalogenated with an
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`alkali metal or alkaline earth metal hydroxide in a non-aqueous, non-alcohol solvent for the alkali
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`metal or alkaline earth metal hydroxide that is at least partially miscible with the halopropane. Alkali
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`metal and alkaline earth metal hydroxides suitable for use in the present invention include, but are not
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`limited to LiOH, KOH, NaOH, CaO, Ca(OH)2, CaCO3, and/or lime stone, and the like. By either
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`method, the dehydrochlorination of HCFC—244fa proceeds as follows:
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`The dehydrohalogenation is performed within a temperature range at which the halopropane will
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`dehydrohalogenate. According to one aspect of this method, alkali metal or alkalin eearth metal
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`hydroxide pellets are dissolved in the solvent with agitation under otherwise ambient conditions. The
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`halopropane is then bubbled through the alkali metal or alkaline earth metal hydroxide solution as the
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`temperature of the solution is gradually increased by heating. Gradual heating is continued until
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`initiation of dehydrohalogenation is observed, after which the temperature at which
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`dehydrohalogenation initiation occurred is maintained until completion of the process.
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`In carrying out the process, the molar ratio of alkali metal or alkaline earth metal hydroxide relative to
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`the amount of halopropane is from about 1:1 to about 20;1, preferably from about 1:1 to about 15:1;
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`and more preferably from about 1:1 to about 12:1; for example, from 1:1 to about 10:1. In the
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`preferred embodiment of the invention, the caustic strength of the caustic solution is from about 2 wt
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`% to about 100 wt %, more preferably from about 5 wt % to about 90 wt % and most preferably from
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`about 10 wt °/o to about 80 wt%. The reaction is preferably conducted at a temperature of from about
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`20°C to about 150°C, more preferably from about 30°C to about 110°C and most preferably from
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`about 40°C to about 90°C. The reaction pressure is not critical. The reaction can be conducted at
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`Patent Docket No. H0O03789US
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`Express Mail Label No. EV262354613US
`S&L File No. P26,267 USA
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`atmospheric pressure, super-atmospheric pressure or under vacuum. The vacuum pressure can be
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`from about 5 torr to about 760 torr. Preferably, the reaction is conducted at atmospheric or super-
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`atmospheric pressure.
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`The dehydrohalogenation reaction can be accomplished using a solution of at least one alkali metal or
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`alkaline earth metal hydroxide in a non, aqueous, non—alcohol solvent for the alkali metal or alkaline
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`earth metal hydroxide that is essentially miscible with the halopropane. For purposes of the present
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`invention, “essentially miscible” means that an agitated mixture containing 50 wt. % halpropane and
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`50 wt. % solvent does not separate to form more than one liquid phase over the temperature range at
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`which the dehydrohalogenation will occur, or, if such separation does occur, one of the liquid phases
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`is very small, less than 10 wt. % of the total weight of the blend.
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`Examples of non—alcohol solvents suitable for use with the present invention include, but not limited
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`to, nitriles such as acetonitrile, ethers such as diethyl ether, tetrahydrofuran and perfluoro—
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`tetrahydrofuran, esters such as methyl acetate and ethyl acetate, amides, ketones, sulfoxides,
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`phosphates, carboxylates, and the like.
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`The alkali metal or alkaline earth metal hydroxide need not be highly soluble in the solvent. An
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`amount of water, alcohol, or mixture thereof may be added to the solvent for the alkali metal or
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`alkaline earth metal hydroxide in quantities that improve the solubility of the alkali metal or alkaline
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`earth metal hydroxide therein. Embodiments according to this aspect of the present invention will
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`blend a solution of the alkali metal or alkaline earth metal hydroxide in water, alcohol or a mixture of
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`water and alcohol, with the solvent. Typically, the amount of water, alcohol, or water-alcohol blend
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`will not exceed about 50 wt.% of the total quantity of solvent for the alkali metal or alkaline earth metal
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`hydroxide, and preferably will not exceed about 20 wt.%. Alcohols that may be used contain from 1 to
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`5 carbon atoms, and preferably from 1 to 3 carbon atoms.
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`Patent Docket No. H0003789US
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`S&L File No. P26,267 USA
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`Solvents are selected that are at least partially miscible with the alkali metal or alkaline earth metal
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`hydroxide solution, which may be in water, alcohol or a mixture thereof. For purposes of the present
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`invention “partially miscible” means a level of miscibility that permits the solvent to dissolve in the
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`alkali metal or alkaline earth metal hydroxide solution to the extent that the dehydrohalogenation
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`reaction will occur upon contact of the halopropane therewith the blend. A high degree is miscibility is
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`not required in order for the reaction to proceed at the interface of the solvent and alkali metal or
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`alkaline earth metal hydroxide solution. More caustic will dissolve as the amount in solution is
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`depleted by the dehydrohalogenation reaction. The solvent need only be at least about 1%,
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`preferably at least about 5%, and more preferably at least 10% soluble, the alkali metal or alkaline
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`earth metal hydroxide solution on a weight basis.
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`In an alternate embodiment of the invention, the dehydrochlorination of HCFC-244fa and dehydro-
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`fluorination of HFC-245fa may be done by thermal decomposition in the presence or in the absence of
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`a catalyst. Suitable catalysts include transition metal halides and oxides, supported or bulk.
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`Preferred catalysts include, but not limited to, FeCl2, FeC|3, NiCl2, CoCl2, supported or in bulk. The
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`preferred temperatures for the thermal decomposition are from about 30°C to about 400°C. more
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`preferably from about 50°C to about 350°C and most preferably from about 75°C to about 300°C. As
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`above, the reaction is preferably conducted at atmospheric pressure, super—atmospheric pressure.
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`Reaction under vacuum is also acceptable. The vacuum pressure can be from about 5 torr to about
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`760 torr.
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`The reactions may be conducted in any suitable reactor. Further, the dehydrochlorination of HCFC-
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`244fa and the dehydrofluorination of HFC-245fa may either be conducted simultaneously in the same
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`reactor, or they may first be separated followed by separately dehydrochlorinating HCFC-244fa with
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`the caustic solution or by thermal decomposition and separately dehydrofluorinating HFC-245fa with the
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`caustic ‘solution or by thermal decomposition. The result of this two step process is a high yield of
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`HFC-1234ze.
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`Patent Docket No. H0003789US
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`Express Mail Lab I No. EV262354613US
`S&L File No. P26,267 USA
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`Therefore, according to preferred embodiments of the invention, the dehydrochlorination of HCFC—
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`244fa and dehydrofluorination of HFC-245fa are accomplished either by thermal decomposition or by
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`reacting these with a strong caustic solution at an elevated temperature. By either method, the
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`dehydrochlorination of HCFC-244fa proceeds as follows:
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`CF3-CH2-CHCIF —> CF3-CH=CHF + HCI
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`(HCFC-244fa)
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`(HFC—1234ze)
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`Furthermore, by either method, the dehydrofluorination of HFC-245fa proceeds as follows:
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`CF3-CH2-CHF2 -) CF3-CH=CHF + HF
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`(HFC-245fa)
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`(HFC—1234ze)
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`Both the dehydrochlorination of HCFC-244fa and dehydrofluorination of HFC-245fa are achieved
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`according to the present invention by using caustic for hydrogen halide removal or by thermal
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`decomposition in the absence of a catalyst or with a catalyst selected from transition metal halides
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`and oxides and combinations thereof, preferably iron halides, nickel halides, cobalt halides and
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`combinations thereof.
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`Both processes described herein are useful for the preparation of fluoropropenes and/or
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`fluorohalopropenes having the following formula:
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`CF3CY=CXNHp
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`wherein X and Y and independently hydrogen or a halogen selected from fluorine, chlorine, bromine
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`and iodine; and N and P are integers independently equal to O, 1 or 2, provided that (N+P)=2. Such
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`compounds include CF3CH=CF2,CF3CH=CFH, CF3CBr=CF2, CF3CH=CH2,CF3CF=CF2_ CF3CC|=CF2,
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`Patent Docket No. H0O03789US
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`Express Mail Label No. EV262354613US
`S&L File No. P26,267 USA
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`CF3CF=CC|F, CF3CC|=CHF, CF3CH=CHC|, CF3CC|=CClF, CF3CH=CC|z_ CF3CF=CCl2, and the like.
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`The fluoropropenes prepared by both methods of this invention are readily recovered by any means
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`known in the art, such as by scrubbing, extraction, and preferably disti||ation.. Depending on extent of
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`conversion of the starting material, the product can be used directly or further purified by standard
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`distillation techniques. Unreacted halopropane and certain reaction by-products can be recycled back
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`to the reaction vessel to provide a continuous process. Alternatively, fresh halopropane may be
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`supplied to the reaction mixture in order to run the process continuously.
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`The fluoropropenes obtained by the inventive processes are useful as monomers for producing
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`fluorine-containing oligomers, homopolymers and copolymers, as well as intermediates for other
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`fluorine-containing industrial chemicals.
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`The following examples are given as specific illustrations of the invention.
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`It should be understood,
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`however, that the invention is not limited to these specific details set forth in the examples. All parts
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`and percentages in the examples, as well as in the remainder of the specification, are by weight
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`unless otherwise specified.
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`Further, any range of numbers recited in this specification or paragraphs hereinafter describing or
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`claiming various aspects of the invention, such as that representing a particular set of properties, units
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`of measure, conditions, physical states or percentages, is intended to literally incorporate expressly
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`herein by reference or otherwise, any number falling within such range, including any subset of
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`numbers or ranges subsumed within any range so recited. The term “about” when used as a modifier
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`for, or in conjunction with, a variable, is intended to convey that the numbers and ranges disclosed
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`herein are flexible and that practice of the present invention by those skilled in the art using
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`temperatures, concentrations, amounts, contents, carbon numbers, and properties that are outside of
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`the range or different from a single value, will achieve the desired result, namely, processes for the
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`preparation of fluoropropenes and reactants used in such processes.
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`Patent Docket No. HO0O3789US
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`Express Mail Label No. EV262354613US
`S&L File No. P26,267 USA
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`EXAMPLES
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`EXAMPLE 1
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`To a reaction setup consisting of a 3—neck round bottom flask (5 L), mechanical agitator, reflux
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`condenser, and low temperature cold trap was added to 3000 ml acetonitrile and 9.9 moles (504 g) of
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`KOH pellets. After mixing, 5.1 moles (684 g) of HFC-245fa were added through a dip tube. The
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`reagents were heated slowly with vigorous agitat