(12) United States Patent
`
`
`Mukhopadhyay et al.
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`
`
`(10) Patent No.:
`
`
`(45) Date of Patent:
`
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`
`US 7,396,965 B2
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`Jul. 8, 2008
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`US007396965B2
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`
`
`............. .. 570/151
`10/1992 Sieveit et al.
`
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`
`
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`11/1992 Krespan ......... ..
`570/126
`
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`7/1993 Ohnishi et al.
`............ .. 570/172
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`7/1994 Aoyama et al.
`........... .. 570/172
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`5/1995 Krespan et al.
`570/151
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`7/1999 Krespan et al.
`570/153
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`2/2001 Belen’Kill et al.
`........ .. 570/172
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`(54) METHOD FOR PRODUCING FLUORINATED
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`ORGANIC COMPOUNDS
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`(75)
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`Inventors; Sudip Mukhopadhyay; Buffalo; NY
`
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`(US); Hsuehsung Tung; Getzville; NY
`
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`(US); Haridasan Nair; Williamsville;
`
`
`
`
`NY (US); Jingji Ma; West Seneca; NY
`
`
`
`
`
`
`(US)
`
`
`5,157,171 A
`
`5,162,594 A
`
`5,227,547 A
`
`5,326,913 A
`
`5,416,246 A
`
`5,929,293 A
`
`6,184,426 B1
`
`
`
`
`
`
`
`(73) Assignee: Honeywell International Inc.,
`Momstowm NJ (US)
`
`
`Subject to any disclaimer, the term of this
`
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`patent is extended or adjusted under 35
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`
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`( * ) Notice:
`
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`
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`
`
`wo
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`
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`W0
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`
`
`
`
`FOREIGN PATENT DOCUMENTS
`wo 97/02227
`1/1997
`
`
`
`W0 98/42645
`
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`10/1998
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`
`
`(21) Appl. No.: 11/127,892
`
`
`
`
`
`(22)
`
`
`
`Filed:
`
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`May 12, 2005
`
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`
`
`(65)
`
`
`
`Prior Publication Data
`
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`
`
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`
`
`N0V~ 16, 2006
`
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`
`
`
`Us 2006/0258891 A1
`Int. Cl.
`
`
`
`
`
`C07C 21/18
`(2006.01)
`(52) U.S. Cl.
`...................... .. 570/172; 570/155; 570/156
`
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`
`
`
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`
`
`(58) Field of Classification Search ..............5..7.0/52(5)/117526,
`
`fil f
`’
`h h,
`S
`1,
`,
`1
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`
`
`
`
`
`
`ee app lcanon
`e or Comp ete Seam lstory‘
`
`
`References Cited
`U.S. PATENT DOCUMENTS
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`
`
`2/1949 Joyce, Jr.
`.................. .. 260/653
`
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`
`51
`
`(
`
`)
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`
`(56)
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`2,462,402 A
`
`
`R. Eric Banks, Michael G. Barlow, Mahm00dNickkh0-Amiry, Jour-
`
`
`
`
`
`
`
`nal 0fFlu0rine Chemistry 82 (1997) 171-174.
`
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`
`
`alkylation of
`Belen’Kii GG et
`“Electrophilic,
`catalytic
`al:
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`
`
`
`
`
`
`polyfluoroolefins by some fluoroalkanes” V01. 108, N0. 1, Mar. 1,
`
`
`
`
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`
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`2001 p. 15-20 XP004231215.
`
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`
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`
`
`Primary Examiner—ElVis 0 Price
`
`
`
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`(74) Attorney, Agent, or Firm—Colleen D. Szuch
`
`
`(57)
`ABSTRACT
`
`
`
`A method for preparing fluorinated Organic Compounds
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`wherein at least one fluorinated olefin is reacted with methyl
`fluoride in the gas-phase and in the presence of a Lewis Acid
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`catalyst to form at least one product having at least 3 carbon
`atoms.
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`4 Claims, No Drawings
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`Page 1 of 5
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`Arkema Exhibit 1032
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`Arkema Exhibit 1032
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`Page 1 of 5
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`US 7,396,965 B2
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`2
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`luoroproanes. It was generally believed that these solvation
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`agents, which could bring the reactants into physical contact,
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`were necessary in order to facilitate a synthesis reaction. The
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`use of solvating agents required that these reactions be con-
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`ducted in the liquid phase. Applicants have discovered, how-
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`ever, that a synthesis reaction can also occur in the absence of
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`solvation agents and therefore can be conducted in the gas
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`phase. In addition, Applicants have also discovered that such
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`a gas phase process produces not only a hydrofluoroproane
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`product, but also a hydrofluoropropene coproduct.
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`Thus, according to certain preferred embodiments of the
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`present invention, processes are provided for preparing flu-
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`orinated organic compounds by reacting, in the gas-phase and
`in the presence of a Lewis Acid catalyst, methyl fluoride with
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`at least one fluorinated olefin having the structure:
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`1
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`METHOD FOR PRODUCING FLUORINATED
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`ORGANIC COMPOUNDS
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`
`BACKGROUND OF INVENTION
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`(1) Field of Invention:
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`This invention relates to novel methods for preparing flu-
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`orinated organic compounds via a gas-phase reaction. In par-
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`ticular, the present invention relates to methods of producing
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`fluorinated alkanes, fluorinated alkenes, and fluorocarbon
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`polymers via a gas-phase reaction.
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`(2) Description of Related Art:
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`Hydrofluorocarbons (HFC’s), in particular hydrofluoro-
`alkenes such as 2,3,3,3-tetrafluoro-1-propene (R-1234yf) and
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`hydrofluoroalkanes
`such as 1,1,1,2,2-pentafluoropropane
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`(R-245cb), are known to be effective refrigerants, fire extin-
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`guishants, heat transfer media, propellants, foaming agents,
`blowing agents, gaseous dielectrics, sterilant carriers, poly-
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`merization media, particulate removal fluids, carrier fluids,
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`bufling abrasive agents, displacement drying agents and
`power cycle working fluids. Unlike chlorofluorocarbons
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`(CFCs) and hydrochlorofluorocarbons (HCFCs), both of
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`which potentially damage the Earth’s ozone layer, HFCs do
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`not contain chlorine and thus pose no threat to the ozone layer.
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`Several methods of preparing hydrofluoroalkanes are
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`known. For example, U.S. Pat. No. 6,184,426 (Belen’Kill)
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`describes a method of making R-245cb via the liquid phase
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`reaction of tetrafluoroethylene (TFE) and methyl fluoride in
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`the presence of antimony pentafluoride catalyst. Other pro-
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`cesses
`for producing hydrofluoroalkanes
`include those
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`described in WO 97/02227 (DuPont) wherein carbon tet-
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`rafluoride or chloro-trifluoromethane are reacted with a flu-
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`orinated ethylene compound in the liquid phase to produce a
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`fluorinated propane or a chlorofluorinated propane.
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`Methods of prepareing hydrofluoroalkenes are likewise
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`known. For example, the preparation of R-1234yf from trif-
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`luoroacetylacetone
`and sulfur
`tetrafluoride has been
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`described. See Banks, et al., Journal ofFluorine Chemistry,
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`Vol. 82, Iss. 2, p. 171-174 (1997).Also, U.S. Pat. No. 5,162,
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`594 (Krespan) discloses a process wherein tetrafluoroethyl-
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`ene is reacted with another fluorinated ethylene in the liquid
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`phase to produce a polyfluoroolefin product.
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`However, the above-mentioned processes have a serious
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`disadvantage in that they are solvation reactions; that is, a
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`solvent is necessary to facilitate the reaction. Solvation reac-
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`tions have a number of disadvantages. For example, certain
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`solvents pose health risks and the risk of environmental con-
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`tamination. Also, their use can dramatically increase the costs
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`associated with synthesizing hydrofluorocarbons due to the
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`cost of the solvent itself as well as the added expense of
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`recovering the solvent. An additional disadvantage is the fact
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`that the product is produced in the liquid phase instead of the
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`gas phase. Liquid phase separation processes are substan-
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`tially more diflicult and costly compared to gas phase sepa-
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`rations.
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`Therefore, there remains a need for methods of efficiently
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`preparing certain hydrofluorocarbons, such as R-1234yf and
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`R-245cb, via a gas-phase reaction. These and other needs are
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`satisfied by the present invention.
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`SUMMARY OF THE INVENTION
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`Applicants have discovered an economical method for pro-
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`ducing fluorinated organic compounds, including hydrofluo-
`roproanes and hydrofluoropropenes, involving the reaction of
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`a fluorinated olefin with methyl fluoride in the gas phase.
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`Conventionally, solvation agents are used to produce hydrof-
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`10
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`15
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`20
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`25
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`55
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`60
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`65
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`Page 2 of 5
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`wherein R is F, C1, C1 -C2 fluorinated alkyl, or a two-carbon
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`fluorinated alkenyl
`to produce at least one product having at least 3-carbons.
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`Preferably, this reaction is conducted essentially free of sol-
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`vation agents.
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`Without being bound to any particular theory, it is believed
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`that according to certain preferred embodiments, the methyl
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`fluoride interacts with the catalyst to form a carbonium ion.
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`This carbonium ion, in turn, reacts with the fluorinated olefin
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`to form a halogenated alkane. Additionally, a portion of the
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`halogenated alkane can continue to react with the catalyst to
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`form a halogenated alkene. Thus, synthesis methods accord-
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`ing to the present invention have the distinctive advantage of
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`not requiring a solvation agent and, because the product is
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`synthesized in the gas-phase, product separation and purifi-
`cation is economical.
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`In particularly preferred embodiments, methyl fluoride is
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`reacted with tetrafluoroethylene, chlorotrifluoroethylene, or
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`some mixture thereof in the presence of activated carbon
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`catalyst impregnated with an antimony pentafluoride to pro-
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`duce R-1234yf, R-245cb, or some combination thereof.
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`DETAILED DESCRIPTION OF THE PREFERRED
`
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`EMBODIMENTS
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`The present invention provides a gas-phase, catalytic addi-
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`tion reaction wherein at least one fluorinated olefin is com-
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`bined with methyl fluoride to produce a product having at
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`least 3 carbon atoms. According to certain preferred embodi-
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`ments, the reaction can be represented as:
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`R
`/
`\
`C=c
`
`F
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`F
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`F
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`Lewis Acid
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`catalyst
`
`+ H3C—F R CxHyFz
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`(g)
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`wherein R is F, C1, C1 -C2 fluorinated alkyl, or a two-carbon
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`fluorinated alkenyl,
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`x is an integer from 3 to 5,
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`y is an integer from 2 to 3, and
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`z is an integer from 4 to 9.
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`As used herein, the term “fluorinated” refers to an organic
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`compound having at least one fluorine atom. Thus, fluori-
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`Page 2 of 5
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`

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`US 7,396,965 B2
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`3
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`nated compounds include hydrofluorocarbons, fluorocar-
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`bons, chlorofluorocarbons, and the like.
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`Preferred fluorinated olefin reactants include CClF:CF2,
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`and
`CF3CF:CF2,
`CF3CF2CF:CF2,
`CF2:CF2,
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`CF2:CF—CF:CF2, with tetrafluroethylene (TFE) and
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`chlorotrifluoroethylene (CTFE) being particularly preferred.
`Each of these compounds are readily available from a variety
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`ofcommercial sources. In certain preferred embodiments, the
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`fluorinated olefin reactant will comprise a combination of at
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`least two of the above-mentioned fluorinated olefins.
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`A Lewis Acid catalyst according to the present invention is
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`a metallic or metalloid halide that is capable of accepting a
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`pair of electrons from a coordinate covalent bond. Such cata-
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`lysts include, but are not limited to, compounds containing at
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`least one atom selected from the group consisting of Sb and
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`Al, and at least one atom selected from the group consisting of
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`F, Cl, Br, and I. Examples ofchloride catalysts suitable foruse
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`in the present invention include, but are not limited to, SbCl5
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`and AlCl3, and partially fluorinated compounds of such chlo-
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`rides. Examples of fluoride catalysts suitable for use in the
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`present invention include, but are not limited to, SbF5, SbF3,
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`and partially chlorinated compounds of such fluorides. Pre-
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`ferred Lewis Acid catalysts include SbF5, SbF3, and SbCl5,
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`with SbF5 being particularly preferred. In certain preferred
`embodiments, combination of at least two of the above-men-
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`tioned catalysts may be used together.
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`In certain preferred embodiments, the Lewis Acid catalysts
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`are impregnated onto an activated carbon substrate. Impreg-
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`nated activated carbons according to the present invention are
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`carbonaceous materials which have catalytic compounds
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`finely distributed on their internal surface. Activated carbon
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`materials generally have a porous structure and a large inter-
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`nal surface area. The volume ofpores ofthe activated carbons
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`is generally greater than 0.2 ml/g and the internal surface area
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`is generally greater than 400 m2/g. The width of the pores
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`ranges from 0.3 nm to several thousand nm.
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`Impregnation utilizes the physical properties of activated
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`carbon to increase the activity of the catalyst. For example,
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`the activated carbon, in part, is used as an inert porous carrier
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`material for distributing catalysts on the material’s large
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`internal surface, thus making them more accessible to the
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`reactants.
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`In certain preferred embodiments, the impregnation occurs
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`by depositing the catalyst on dried activated carbon under a
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`nitrogen blanket at 0-5° C.
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`Hydrofluorocarbon products of the present invention pref-
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`erably are of the formula:
`
`
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`c,Hy1=Z
`
`4
`
`
`In a highly preferred embodiment of the present invention,
`
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`methyl fluoride is reacted with chlorotrifluoroethylene in the
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`gas-phase and in the presence of catalyst comprising acti-
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`vated carbon impregnated with antimony pentafluoride. One
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`would expect that the major product of such a reaction to be
`
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`l-chloro-2,2,3,3-tetrafluoropropane. Surprisingly, Appli-
`cants have found that the actual product of this reaction is
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`primarily a mixture of 2,3,3,3-tetrafluoro-l-propene and 1,1,
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`1,2,2-pentafluoropropane. Although not being bound by any
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`particular theory, Applicants believe that this embodiment
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`proceeds according to the reaction scheme:
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`CC1F:CF2+CH3F+SbF5—>CClF:CF2+CH3*SbF5’
`—>CH3CF2CClF2+SbF5—>CH3CF2CF3+
`SbClF4—>CH2:CFCF3+SbF5+HCl
`
`The reactions of the present invention are conducted in the
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`gas-phase, preferably at a temperature offrom about 40° C. to
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`about 150° C. and at a pressure offrom about 0.5 psig to about
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`150 psig. More preferably, reactions are conducted at from
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`about 50° C. to about 70° C. and at a pressure from about 10
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`psig to about 20 psig.
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`The optimal temperature and pressure for a particular reac-
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`tion will depend,
`in part, on the final product desired.
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`Although, the conversion of the reactants generally increases
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`with an increase in temperature and pressure, the relatively
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`high vapor pressure of SbF5 moderates the reaction tempera-
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`ture and pressure. One skilled in the art would, based on the
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`present disclosure, be able to readily determine the optimum
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`temperature and pres sure for a given reaction without having
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`to conduct undue experimentation.
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`The present invention can be conducted via a batch or,
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`more preferably, a continuous process. In certain preferred
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`embodiments utilizing a continuous process, the reactants are
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`mixed together, heated, then passed through a catalyst bed to
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`produce a product stream. Preferably, the desired product
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`yields are obtained with a single pass of the reactant mixture
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`through the catalyst bed. However, the present invention is
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`not limited to such operations but may include operations
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`having multiple passes. In certain preferred embodiments,
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`acids in the product stream are neutralized by a scrubber. The
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`product stream can be fractionated (for example, by distilla-
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`tion) to isolate the individual products.
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`10
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`25
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`30
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`35
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`45
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`EXAMPLES
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`50
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`Additional features ofthe present invention are provided in
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`the following examples, which should not be construed as
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`limiting the claims in any way.
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`wherein x is an integer from 3 to 5,
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`y is an integer from 2 to 3, and
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`z is an integer from 4 to 9.
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`Preferred hydrofluorocarbon products produced by the
`present invention include fluorinated alkanes and fluorinated
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`alkenes. Where the present invention is practiced as a con-
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`tinuous process, the product stream will include either or both
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`of these products. Preferred fluorocarbon products will have
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`at least 3 carbon atoms and may, for embodiments in which R
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`is a fluorinated alkenyl, be a polymer. Examples of preferred
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`hydrofluorocarbon products include, but are not limited to,
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`CH3CF2CF3,
`CH3CF2CF2CF3,
`CH3CF2CF3,
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`CH3CF2CF2CF2CF3, CH2:CFCF3, CH2:CFCF2CF3, and
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`CH2:CFCF2CF2CF3. Highly preferred hydrofluorocarbon
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`products include tetrafluoropropenes, particularly 2,3,3,3-
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`tetrafluoro-l -propene, and pentafluoropropanes, particularly
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`l,1,l,2,2-pentafluoropropane.
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`
`55
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`Examples 1-5
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`These examples show the activity of different catalysts.
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`60
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`65
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`Catalyst Preparation:
`Catalyst A
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`A catalyst comprising activated carbon impregnated with
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`SbF5 is prepared by first drying 100 g of activated carbon in a
`oven at 180° C. under vacuum for 72 hours. After drying, the
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`carbon is covered with aluminum foil and then cooled gradu-
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`ally to room temperature under vacuum.
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`Page 3 of 5
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`Page 3 of 5
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`

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`US 7,396,965 B2
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`5
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`A 250 ml HDPE bottle is flushed with anhydrous N2 to
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`remove ambient air. Approximately 50 g ofthe dried activated
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`carbon is then placed in the bottle inside a glove box under a
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`N2 blanket. Inside the glove box, 50 g of SbF5 is slowly added
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`(approximately 2 g/min) to the activated carbon while swirl-
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`ing the contents of the bottle. The contents of the bottle are
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`stirred with a plastic rod until all the liquid is adsorbed into the
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`pores of carbon or until fumes of SbF5 are no longer emitted.
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`Catalyst B
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`This procedure is the same as that described for catalyst A,
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`except that (1) the bottle was emerged in a 0-5° C. tempera-
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`ture bath to facilitate the adsorption of SbF5 through the pores
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`of activated carbon; and (2) the SbF5 is added to the bottle at
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`a rate of 5 g/min.
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`10
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`15
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`Catalyst C
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`This procedure is the same as that described for catalyst B,
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`except that only 20 g of SbF5 is added to the 50 g of activated
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`carbon
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`20
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`6
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`40° C. in a pre-heater that is connected to the reactor. The
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`heated reactant mixture is passed into the reactor at a flow of
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`20 SCCM. The exit line from the reactor is connected to an
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`on-line GC and GCMS for analysis. A 15% KOH scrubber
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`solution was used at 50° C. to neutralize acids coming out
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`from the reactor. The gas stream coming out of the scrubber
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`solution is then condensed in a cylinder under liquid N2 and
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`then finally fractionated (distilled) to isolate products. The
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`results for each catalyst are shown below:
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`Example
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`Catalyst
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`% Conv. of
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`
`CTFE
`
`
`% Conv. to
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`CF3CF:CH2
`
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`
`% Conv. to
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`CF3CF2CH3
`
`
`1
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`2
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`3
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`4
`
`5
`
`
`A
`
`B
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`C
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`D
`
`E
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`
`15
`22
`20
`2
`12
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`52
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`54
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`53
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`2
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`27
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`34
`37
`37
`6
`39
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`Catalyst D
`
`This procedure is the same as that described for catalyst B,
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`except that the 50 g of activated carbon is impregnated with
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`30 g of SbCl5 and is then fluorinated in a 1/2 inch Monel reactor
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`with 30 g/l1r of HF at 70° C. over a period of 20 hours under
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`50 psig pressure. After the fluorination, 50 Standard Cubic
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`Centimeters per Minute (SCCM) of N2 is passed through the
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`catalyst bed at 30° C. for 30 hours to remove free HF from the
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`bed.
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`Catalyst E
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`This procedure is the same as that described for catalyst B,
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`except that the 50 g of the dried activated carbon is impreg-
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`nated with 50 g of SbF3 and is then fluorinated in a 1/2 inch
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`monel reactor with 10 g/hr of F2 (a mixture of 50 wt % N2 and
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`50 wt % F2) at 70° C. over a period of 30 hours under 50 psig
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`pressure. After the fluorination, 50 SCCM of 100 wt % N2 is
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`passed through the bed at 30° C. for 2 hours to remove free F2
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`from the bed.
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`Catalyst Activity:
`The activity of each of the above-mentioned catalysts are
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`shown by the following procedure.
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`A 1/2-inch Monel flow reactor is charged with 50 g of a
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`freshly prepared catalyst and then uniformly heated to 50° C.
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`A gaseous mixture of CTFE and CH3F at 20 psig is heated to
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`25
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`It is observed that Catalyst B is the most active catalyst
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`under the reaction conditions shown.
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`
`Examples 6-14
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`30
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`35
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`40
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`45
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`These examples show the conversion rates of chlorotrif-
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`luoroethylene (CTFE) and tetrafluoroethylene (TFE) in the
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`presence of a Sb-based catalyst.
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`A 1/2-inch Monel flow reactor is charged with 50 g of a
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`freshly prepared catalyst B and then uniformly heated to the
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`temperature indicated in the table below. A gaseous mixture
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`of CTFE or TFE and CH3F is heated to 10° C. below the
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`reactor temperature. The heated reactant mixture is then
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`passed into the reactor at a flow of 20 SCCM at the pressure
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`indicated in the table below. The exit line from the reactor is
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`connected to an on-line GC and GCMS for analysis. A 15%
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`KOH scrubber solution was used at 50° C. to neutralize acids
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`coming out from the reactor. The gas stream coming out ofthe
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`scrubber solution is then condensed in a cylinder under liquid
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`N2 and then finally fractionated (distilled) to isolate products.
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`The results for each experimental run are shown below:
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`Experiment
`
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`T
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`(° C.)
`
`50
`50
`50
`60
`70
`50
`60
`60
`50
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`Page 4 of 5
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`Olefin
`P
`
`
`(psig) Reactant
`
`1.2 CTFE
`5
`CTFE
`
`20
`CTFE
`
`2.1 CTFE
`
`3.5 CTFE
`
`3.2 TFE
`
`3.2 TFE
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`20
`TFE
`
`100
`TFE
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`% Conv. of
`
`
`CTFE/TFE
`
`15
`17
`
`22
`
`24
`
`21
`
`35
`
`37
`
`38
`
`39
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`% Conv. to
`
`
`CF3CF:CH2
`48
`52
`
`54
`
`50
`
`42
`
`20
`
`22
`
`26
`
`18
`
`
`
`% Conv. to
`
`
`CF3CF2CH3
`
`45
`40
`
`37
`
`40
`
`42
`
`74
`
`72
`
`68
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`64
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`Page 4 of 5
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`

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`wherein R is F, Cl, C1-C2 fluorinated alkyl, or two-carbon
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`fluorinated alkenyl, to produce at least one product hav-
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`ing at least 3 carbon atoms, wherein said reaction occurs
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`in the gas-phase and in the presence of a Lewis Acid
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`catalyst, wherein said Lewis Acid catalyst is impreg-
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`nated on activated carbon.
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`4. The method of claim 3 wherein said activated carbon is
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`essentially anhydrous.
`*
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`*
`
`*
`
`*
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`*
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`
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`
`
`US 7,396,965 B2
`
`C:C
`
`
`
`wherein R is F, Cl, C1-C2 fluorinated alkyl, or two-carbon
`
`
`
`
`
`
`fluorinated alkenyl,
`to produce at least one product having at least 3 carbon
`
`
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`
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`atoms, wherein said reaction occurs in the gas-phase and
`
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`
`
`in the presence of a Lewis Acid catalyst, wherein said
`
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`
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`product includes 2,3,3,3-tetrafluoro-l -propene.
`
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`3. A method of preparing fluorinated organic compounds
`
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`comprising reacting methyl fluoride with at least one fluori-
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`nated olefin having the structure
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`C:
`
`7
`
`It is observed that the reaction is generally more selective
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`for TFE compared to CTFE, but that a CTFE feed produces a
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`higher percent conversion to CF3CF:CH2.
`
`
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`Having thus described a few particular embodiments ofthe
`
`
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`
`
`invention, various alterations, modifications, and improve-
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`
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`ments will readily occur to those skilled in the art. Such
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`alterations, modifications, and improvements, as are made
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`obvious by this disclosure, are intended to be part of this
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`description though not expressly stated herein, and are
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`intended to be within the spirit and scope of the invention.
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`Accordingly, the foregoing description is by way of example
`only, and not limiting. The invention is limited only as defined
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`
`in the following claims and equivalents thereto.
`
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`What is claimed is:
`
`
`1. A method of preparing fluorinated organic compounds
`
`
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`
`
`comprising reacting methyl fluoride with at least one fluori-
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`
`
`nated olefin having the structure:
`
`
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`
`
`
`C:C
`
`
`
`wherein R is F, Cl, C1-C2 fluorinated alkyl, or two-carbon
`
`
`
`
`
`
`
`fluorinated alkenyl,
`to produce at least one product having at least 3 carbon
`
`
`
`
`
`
`
`
`atoms, wherein said reaction occurs in the gas-phase and
`
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`
`
`
`in the presence of a Lewis Acid catalyst, wherein said
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`product includes a fluorocarbon polymer.
`
`
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`
`2. A method of preparing fluorinated organic compounds
`
`
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`
`
`
`comprising reacting methyl fluoride with at least one fluori-
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`
`
`nated olefin having the structure:
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`5
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`10
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`15
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`20
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`25
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`30
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`Page 5 of 5
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`Page 5 of 5