WO1992006942A1 - Procede de production de polyfluorolefines - Google Patents

Procede de production de polyfluorolefines Download PDF

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Publication number
WO1992006942A1
WO1992006942A1 PCT/US1991/007242 US9107242W WO9206942A1 WO 1992006942 A1 WO1992006942 A1 WO 1992006942A1 US 9107242 W US9107242 W US 9107242W WO 9206942 A1 WO9206942 A1 WO 9206942A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
reaction
reactants
tfe
hfp
Prior art date
Application number
PCT/US1991/007242
Other languages
English (en)
Inventor
Carl George Krespan
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to AU90281/91A priority Critical patent/AU9028191A/en
Priority to EP91920551A priority patent/EP0552303B1/fr
Priority to DE69110475T priority patent/DE69110475T2/de
Priority to KR1019930701092A priority patent/KR100219099B1/ko
Priority to SU915011268A priority patent/RU2093502C1/ru
Priority to JP51853991A priority patent/JP3162380B2/ja
Publication of WO1992006942A1 publication Critical patent/WO1992006942A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02—Monocyclic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02—Monocyclic halogenated hydrocarbons
    • C07C23/08—Monocyclic halogenated hydrocarbons with a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • This invention concerns a process for the production of polyfluoroolefins by the catalytic addition of polyfluoroallylic fluorides to fluoroethylenes.
  • 1:1 and 1:2 Adducts such as F-pentene-2 and F-heptene-3 can be formed selectively and reduced further to dihydro- or trihydropolyfluoroalkanes, which are useful as HFC cleaning agents.
  • Higher boiling products e.g., boiling points above 100°C are useful as solvents and stable liquids, particularly after the double bond has been saturated by hydrogenation, fluorination, or
  • the present invention provides a process for the manufacture of polyfluoroolefins having at least 5 carbon atoms comprising reacting a first polyfluoroolefin of the structure
  • R 1 is F, Cl, H or R f ;
  • R 2 is F, Cl, H or R f ;
  • R 3 is F, Cl, or H
  • R f is a C 2 to C 12 perfluoroalkyl, optionally containing 1 H or 1 Cl;
  • R 4 is F or R f or where R 4 together with R 2 is -(CF 2 )n-; wherein n is 1, 2 or 3;
  • R 5 is F, H, or Cl
  • the invention also concerns olefins of the
  • the invention also concerns olefins of the structures :
  • n 1, 2 or 3.
  • the allylic fluoride may either have the structure shown or be capable of rearranging to that structure by fluorine atom migration in the presence of a catalyst.
  • the product may also either have the structure shown or a structure resulting from fluorine atom migration.
  • isomefic products such as
  • the catalyst used is of the structure AIX 3 , where X is one or more of F, Cl or Br, with a proviso that X cannot be entirely F.
  • Active catalyst can be preformed, as in most examples, or can be formed in situ by partial halogen-F exchange with allylic fluoride, as in Examples 9 and 20.
  • Preferred catalysts are AlF x Cl y (mixed aluminum halide), where the total number of atoms of halide, x plus y equals 3, where x ranges from 0 to about 2.95 and y ranges from 3 to about .05.
  • Temperatures range from -20°C to 150°C, depending on the reactivity of the reagents but are preferably in the range of 20oC to 85°C. Pressures may vary from less than 1 atm to over 50 atm, but a preferred range is from 1 atm to 20 atm. Times for batch reactions may vary from about 5 min. to about 2 days depending on batch size. Times for a continuous reaction may vary from about 1/2 to 120 min. Times for the reaction vary depending upon the identity of the reactants, the temperature, pressure and amount of catalyst.
  • the reaction is best conducted in a liquid phase and can be carried out in several modes; batchwise with addition of reactants and catalyst to a reactor cold and warming to reaction temperature; semibatch by injection of one or both reactants optionally containing catalyst into a vessel containing catalyst and or the other reagent at reaction temperature; or continuous by passing the reactants (preferably at least partly liquified, optionally with catalyst) through a reaction zone, which also optionally contains catalyst.
  • the catalyst must be present in the reactant mixture or the reaction zone but may be present in both places.
  • Reactant mole ratios of allylic fluoride (e.g., HFP) to fluoroolefin (e.g., TFE) can vary from 5:1 to 1:50.
  • Ratios in the 5:1 to 1:1 range are generally used when high yields of one to one adducts are desired. Ratios from 1:1 to 1:50 are used when multiple additions of fluoroethylene are desired to form one-to-two and higher adducts, especially when the fluoroolefin is
  • TFE tetrafluoroethylene
  • Solvents are generally not essential, but a liquid phase is useful to facilitate reaction of low-boiling materials that are not condensed under reaction
  • Solvents are also useful for controlling any initial exotherm when a catalyst, such as aluminum chloride, is used in a large scale reaction.
  • Relatively inert materials which may be used as solvents include hexafluorobenzene, E-n-hexane, CICF 2 CF 2 CI, SO 2 CIF,
  • CF 3 CF 2 CHCI 2 CICF 2 CF 2 CHFCI, CF 3 CHFCHFCF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 3 , CICF 2 CFCI 2 , CF 3 CCI 3 , CF 3 CCl 2 CF 3 , CF 3 CHCI 2 , F-1,2-dimethylcyclobutane,
  • CCI 2 CCI 2
  • CCI 2 CHCI, CF 3 CF 2 CF 2 O[CF(CF 3 )CF 2 O] n CHFCF 3
  • (CF 3 ) 2 CFCF CFCF 2 , F-pentene-2,
  • Highly fluorinated olefins are preferred solvents and perfluoroolefins, C n F 2n , wherein n is 5 or greater are most preferred.
  • TFE tetrafluoroethylene
  • HFP hexafluoropropene
  • the sealed r.b. flask was transferred to a dry box and unloaded into a Teflon ® FEP bottle; 340 g of rather finely divided yellow-green solid. Portions of the catalyst were weighed out in the dry box as needed and taken out in plastic bottles with pressure-seal caps.
  • AICI 3 (AICI 3 + CFCI 3 ), 100 g (0.5 mol) of 1,1,2-trichloro-3,3,3-trifluoropropene, and 50 g
  • perfluorooctene also detected. Fractionation afforded 21.9 g (32%) of perfluoropentene-2, bp 24-26oC, followed by 34.1 g (39%) of perfluoroheptenes, bp 69.5-71oC.
  • perfluorononenes 22.2 g (15%) of perfluoroundecenes, and 2.0 g (1%) of perfluorotridecenes, with 0.5-1% of perfluoroolefins having even numbers of carbon atoms C 6 F 12 , C 8 F 16 and C 10 F 20 also detected.
  • Distillation afforded a series of fractions, bp 66°C (1 atm) to 66°C (18 mm), which were characterized by GC, IR and NMR analysis.
  • Tetrachloroethylene is a preferred solvent because of its availability, relative inertness under reaction conditions, and ease of separation from low boiling 1:1 and 1:2 adducts.
  • Tetrafluoroethylene (47.3 g, 0.47 mol) was pressured in and the vessel was heated slowly with stirring to 80°C, where reaction rate was appreciable. Tetrafluoroethylene was added in portions at 80°C until a total of
  • CF 3 CF 2 CF 2 CF CHCH (CF 2 CF 3 ) CF 2 CF 2 CF 2 CF 3 by IR and NMR analysis.

Abstract

L'invention se rapporte à un procédé de production de polyfluoroléfines par addition catalytique de fluorures polyfluorallyliques sur des fluoréthylènes. Des additifs 1:1 et 1:2 tels que F-pentène-2 et F-heptène-3 peuvent être sélectivement produits et réduits en dihydro- ou trihydropolyfluoralcanes, qui sont utiles comme agents nettoyants à base d'HFC.
PCT/US1991/007242 1990-10-11 1991-10-10 Procede de production de polyfluorolefines WO1992006942A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU90281/91A AU9028191A (en) 1990-10-11 1991-10-10 Process for production of polyfluoroolefins
EP91920551A EP0552303B1 (fr) 1990-10-11 1991-10-10 Procede de production de polyfluorolefines
DE69110475T DE69110475T2 (de) 1990-10-11 1991-10-10 Verfahren zur herstellung von perfluorolefinen.
KR1019930701092A KR100219099B1 (ko) 1990-10-11 1991-10-10 폴리플루오로올레핀의 제조 방법
SU915011268A RU2093502C1 (ru) 1990-10-11 1991-10-10 Способ получения полифторолефинов, фтор-1-этилциклопентен и перфтор-2,3-дихлогекс-2-ен или перфтор-4,5-дихлорокт-4-ен
JP51853991A JP3162380B2 (ja) 1990-10-11 1991-10-10 ポリフルオロオレフィンを製造するための方法

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US59583990A 1990-10-11 1990-10-11
US595,839 1990-10-11
USNOTFURNISHED 2010-10-29

Publications (1)

Publication Number Publication Date
WO1992006942A1 true WO1992006942A1 (fr) 1992-04-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/007242 WO1992006942A1 (fr) 1990-10-11 1991-10-10 Procede de production de polyfluorolefines

Country Status (8)

Country Link
JP (1) JP3162380B2 (fr)
KR (1) KR100219099B1 (fr)
CN (1) CN1030908C (fr)
AR (1) AR247874A1 (fr)
MX (1) MX9101544A (fr)
TW (1) TW324710B (fr)
WO (1) WO1992006942A1 (fr)
ZA (1) ZA918128B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013059544A1 (fr) * 2011-10-19 2013-04-25 E. I. Du Pont De Nemours And Company Nouveaux mélanges d'isomères 1,1,1,4,4,5,5,6,6,6-décafluorohex-2-ène et utilisations associées

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX344006B (es) * 2011-09-30 2016-12-02 Honeywell Int Inc Proceso para producir 2,3,3,3 - tetrafluoropropeno.
JP6223345B2 (ja) * 2011-10-14 2017-11-01 ハネウェル・インターナショナル・インコーポレーテッドＨｏｎｅｙｗｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｉｎｃ． ２，３，３，３−テトラフルオロプロペンの製造方法
IN2014DN02914A (fr) * 2011-10-14 2015-05-15 Honeywell Int Inc
JP7209995B2 (ja) * 2018-06-18 2023-01-23 国立研究開発法人産業技術総合研究所 フッ素化合物の製造方法
CN113906003A (zh) * 2019-04-18 2022-01-07 科慕埃弗西有限公司 路易斯酸催化的1，2-双(全氟烷基)乙烯的合成
CN112094627B (zh) * 2020-11-03 2021-03-16 北京宇极科技发展有限公司 环骨架含氟传热流体、制备方法及其应用
CN113816824B (zh) * 2021-09-07 2023-03-10 浙江巨化技术中心有限公司 一种全氟烯烃齐聚物的制备方法及应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE856145C (de) * 1943-03-12 1952-11-20 Hoechst Ag Verfahren zur Herstellung von Fluor und Chlor enthaltenden Kohlenwasserstoffen
DE2048772A1 (de) * 1969-10-07 1971-04-08 Air Products and Chemicals Ine , Philadelphia, Pa (V St A) Cyclische Perfluorolefme und Ver fahren zu ihrer Herstellung
US3662009A (en) * 1969-11-24 1972-05-09 Phillips Petroleum Co Preparation of unsaturated fluorocompounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE856145C (de) * 1943-03-12 1952-11-20 Hoechst Ag Verfahren zur Herstellung von Fluor und Chlor enthaltenden Kohlenwasserstoffen
DE2048772A1 (de) * 1969-10-07 1971-04-08 Air Products and Chemicals Ine , Philadelphia, Pa (V St A) Cyclische Perfluorolefme und Ver fahren zu ihrer Herstellung
US3662009A (en) * 1969-11-24 1972-05-09 Phillips Petroleum Co Preparation of unsaturated fluorocompounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 112, no. 21, 21 May 1990, Columbus, Ohio, US; abstract no. 197607P, page 640 ; see abstract & PL,A,145 018 (POLSKA AKADEMIA NAUK, INSTYTUT CHEMII ORGANICZNEJ) 30 July 1988 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013059544A1 (fr) * 2011-10-19 2013-04-25 E. I. Du Pont De Nemours And Company Nouveaux mélanges d'isomères 1,1,1,4,4,5,5,6,6,6-décafluorohex-2-ène et utilisations associées

Also Published As

Publication number Publication date
ZA918128B (en) 1993-04-13
JP3162380B2 (ja) 2001-04-25
CN1061399A (zh) 1992-05-27
AR247874A1 (es) 1995-04-28
MX9101544A (es) 1992-06-05
KR100219099B1 (ko) 1999-09-01
KR930702259A (ko) 1993-09-08
JPH07502254A (ja) 1995-03-09
CN1030908C (zh) 1996-02-07
TW324710B (en) 1998-01-11

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