WO1994003418A1 - Process for the preparation of 1,1,1-trichloro-2,2,2-trifluoroethane - Google Patents
Process for the preparation of 1,1,1-trichloro-2,2,2-trifluoroethane Download PDFInfo
- Publication number
- WO1994003418A1 WO1994003418A1 PCT/GB1993/001583 GB9301583W WO9403418A1 WO 1994003418 A1 WO1994003418 A1 WO 1994003418A1 GB 9301583 W GB9301583 W GB 9301583W WO 9403418 A1 WO9403418 A1 WO 9403418A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- trifluoroethane
- range
- process according
- chloro
- chlorine
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- This invention relates to a chlorination process for the preparation of 1,1,1-trichlorotrifluoroethane.
- 1,1,1-Trichlorotrifluoroethane is a valuable chemical intermediate which is used, inter alia, in the preparation of precursors of pyrethroid insecticides, such as cyhalothrin anf tefluthrin. Hitherto it has been obtained by various processes including by rearrangement of the isomeric product 1,1,2-trichlorotrifluoroethane in the presence of aluminium halides, and by gas-phase photochemically-initiated chlorination of non-perhalogenated precursors such as 1,1,1-trifluoroethane. However the use of these processes is considered unsatisfactory because of low conversion rates, difficulty in separating the product from the starting material, and/or the formation of undesirable by-products.
- the present invention provides a process for the preparation of 1,1,1-trichlorotrifluoroethane in which l-chloro-2,2,2-trifluoroethane is subjected to chlorination by bringing the l-chloro-2,2,2-trifluoroethane into contact with chlorine within a reaction vessel characterised in that the process is conducted in the liquid phase in the presence of a chemical free radical initiator under a pressure of from 1 to 20 bar and at a temperature within the range 50 to 120°C, and the product is separated from the reaction mixture by fractional distillation.
- the reactants are continuously fed into the reaction vessel at a rate consistent with the steady state production of 1,1,1-trichlorotrifluoroethane and within a preferred molar ratio of chlorine to l-chloro-2,2,2-trifluoroethane within the range 1.0 to 2.5.
- the molar ratio of chlorine to total chlorinatable hydrogen atoms is also preferably within the range 0.5 to 1.0.
- the process is conducted within a closed system with arrangements to admit the reactants and remove the product.
- the conditions of the process may be controlled by regulation of the rate of addition of the reactants, the reaction temperature and the pressure under which the reaction is conducted.
- the rates of the potentially competing reactions may be influenced by the choice of temperature and pressure.
- Pressure is partially dependent on the relative vapour pressure contributions of all the components in the gaseous phase which is in equilibrium with the liquid phase in which the reaction occurs, and may be augmented by introducing pressurised inert gas, for example nitrogen.
- the pressure is preferably maintained within the range 5 to 15 bar and more preferably within the range 7 to 13 bar.
- the temperature at which the process is conducted is also an important determinant of optimum conversion and is preferably within the range 80 to 110°C.
- the process is conducted in the presence of a chemical free-radical initiator intended to catalyse the production of chlorine radicals to promote the chlorination reaction.
- Suitable free-radical initiators include for example aroyl peroxides such as dibenzoyl peroxide, and azo compounds such as azobisisobutyronitrile, which is particularly preferred. It is preferred that the initiator be present at a constant amount during the process and therfore where continuous operation is used the initiator may be fed continuously at a constant rate in proportion to the continuous addition of the reactants. It is also prefered that the initiator be present in a dissolved form to maximise its effect and to avoid the complications arising from a the presence of a solid phase in the reaction vessel.
- a particularly preferred combination of conditions for conducting the reaction in a continuous manner comprises carrying out the process at a pressure within the range 7 to 13 bar and a temperature within the range 80 to 120 C in the presence of azobisisobutyronitrile whilst continuously feeding the reactants at a molar ratio of chlorine to l-chloro-2,2,2-trifluoroethane within the range 1.2 to 1.4.
- the product which is present as a substantial component of the reaction mixture is separated from the other components by a process of fractional distillation.
- the other components of the reaction mixture are unreacted chlorine, unreacted l-chloro-2,2,2-trifluoroethane and some 2,2-dichloro-3,3,3-trifluoroethane. After separation these other components can be recycled into the reaction vessel in order to maximise the conversion to the desired product.
- Fractional distillation provides a simple method of separating the components of the reaction mixture because of the differences in boiling points which are 7 C for l-chloro-3,3,3-trifluoroethane, 26 C for l,l-dichloro-2,2,2-trifluoroethane and 46 C for 1,1,1-trichlorotrifluoroethane.
- the process is operated by passing a premixed stream of the reactants into the reactor, which may be for example a bubble column chlorinator, into which a solution of the initiator is also being introduced, the rates of addition being controlled so as to allow the contents of the reactor to reach a steady state composition in which product predominates, and to continuously remove the contents, as the product stream, at a rate consistent with the rate of addition of the reactants.
- the product stream is passed into a still and fractionated to obtain the 1,1,1-trichlorotrifluoroethane free from the other components of the stream which are recycled back into the reactant stream.
- the steady state composition (excluding chlorine) may contain from 452 to 852 by weight of the desired 1,1,1-trichlorotrifluoroethane and less than about 352 by weight of l,l-dichloro-3,3,3-trifluoroethane, the remainder being unreacted l-chloro-3,3,3-trifluoroethane. It is an advantage of the process that there is little or no formation of unwanted dimeric or polymeric by-products, and consequently a very high yield with respect to the desired product when recycling is taken into account.
- the invention process is illustrated by the following Examples in which the process was conducted in a bubble column chlorinator with a capacity of 950 ml, the center section of which was fitted with a jacket heater and the upper portion, above the liquid level when filled, surrounded by a cooling jacket cooled by circulating butanol at -25 C.
- the column was connected to a supply of nitrogen under pressure.
- the components were fed into the bottom of the column at predetermined rates and ratios and the reaction allowed to proceed until a steady state, as shown by sampling the reaction mixture until an unchanging composition (as determined by gas chromatography) was reached.
- the reactants and products are designated as follows:
- Chlorine - Cl l-chloro-3,3,3-trifluoroethane - CTFE; l,l-dichloro-3,3,3-trifluoroethane - DCTFE;
- the reactor was filled to the liquid level with a 25/75 by volume mixture of CTFE/TCTFE and pressured up to 120 psig with nitrogen.
- Example 2 The process was conducted as in Example 1. During the addition the temperature was maintained within the range 90 to 100 C and the pressure was within the range 115 to 125 psig. A steady state composition (excluding chlorine) was obtained after about 150 minutes, as follows:
- a steady state composition (excluding chlorine) was obtained after about 220 minutes, as follows:
- Example 2 The process was conducted in a similar manner to that described in Example 1 except that a reactor of capacity 300 ml was used and the AIBN was added in the form of a 0.22 solution in a 1:1 (by volume) mixture of DCTFE and TCTFE. The temperature was maintained at 100 C and the pressure at 127 psig and the feed rates were as follows:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP50508394A JP3335174B2 (en) | 1992-08-03 | 1993-07-27 | Method for producing 1,1,1-trichloro-2,2,2-trifluoroethane |
UA95028107A UA35596C2 (en) | 1992-08-03 | 1993-07-27 | process for preparation of 1,1,1- trichlorotrifluoroethane |
BR9306819A BR9306819A (en) | 1992-08-03 | 1993-07-27 | Process for the preparation of 1 ,,, - trichloro-trifluoro-ethane |
DE69332408T DE69332408T2 (en) | 1992-08-03 | 1993-07-27 | METHOD FOR PRODUCING 1,1,1-TRICHLOR-2,2,2-TRIFLUOR |
KR1019950700308A KR100239231B1 (en) | 1992-08-03 | 1993-07-27 | Process for the preparation of 1,1,1-trichloro-2,2,2-trifluoroethane |
EP93917923A EP0652858B1 (en) | 1992-08-03 | 1993-07-27 | Process for the preparation of 1,1,1-trichloro-2,2,2-trifluoroethane |
CA002140443A CA2140443C (en) | 1992-08-03 | 1993-07-27 | Process for the preparation of 1,1,1-trichloro-2,2,2-trifluoroethane |
AT93917923T ATE226186T1 (en) | 1992-08-03 | 1993-07-27 | METHOD FOR PRODUCING 1,1,1-TRICHLORINE-2,2, 2-TRIFLUORINE |
AU47169/93A AU677594B2 (en) | 1992-08-03 | 1993-07-27 | Process for the preparation of 1,1,1-trichloro-2,2,2-trifluorothane |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB929216442A GB9216442D0 (en) | 1992-08-03 | 1992-08-03 | Chlorination process |
GB9216442.5 | 1992-08-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994003418A1 true WO1994003418A1 (en) | 1994-02-17 |
Family
ID=10719731
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1993/001583 WO1994003418A1 (en) | 1992-08-03 | 1993-07-27 | Process for the preparation of 1,1,1-trichloro-2,2,2-trifluoroethane |
Country Status (19)
Country | Link |
---|---|
US (1) | US5414164A (en) |
EP (1) | EP0652858B1 (en) |
JP (1) | JP3335174B2 (en) |
KR (1) | KR100239231B1 (en) |
CN (1) | CN1037961C (en) |
AT (1) | ATE226186T1 (en) |
AU (1) | AU677594B2 (en) |
BR (1) | BR9306819A (en) |
CA (1) | CA2140443C (en) |
CZ (1) | CZ284731B6 (en) |
DE (1) | DE69332408T2 (en) |
GB (1) | GB9216442D0 (en) |
HU (1) | HU215162B (en) |
IL (1) | IL106504A (en) |
IN (1) | IN183284B (en) |
RU (1) | RU2118308C1 (en) |
UA (1) | UA35596C2 (en) |
WO (1) | WO1994003418A1 (en) |
ZA (1) | ZA935410B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9315450D0 (en) * | 1993-07-26 | 1993-09-08 | Zeneca Ltd | Chlorination process |
ITMI20010287A1 (en) | 2001-02-13 | 2002-08-13 | Ausimont Spa | PROCEDURE FOR OBTAINING CFC 113A FROM CFC 113 |
CN104402665B (en) * | 2014-09-30 | 2015-07-15 | 应璐 | Preparation method of trichlorotrifluoroethane |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4060469A (en) * | 1976-12-21 | 1977-11-29 | Allied Chemical Corporation | Preparation of 1,1,1-trifluoro-2,2-dichloroethane |
EP0407990A1 (en) * | 1989-07-14 | 1991-01-16 | Hoechst Aktiengesellschaft | Method for the production of 1,1,1-trifluoro-2,2-dichloroethane under high pressure |
US5120883A (en) * | 1991-08-26 | 1992-06-09 | E. I. Du Pont De Nemours And Company | Catalytic process for producing CCl3 CF3 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2469290A (en) * | 1946-03-19 | 1949-05-03 | Allied Chem & Dye Corp | Process for making tetrachlorodifluoroethane |
US3047642A (en) * | 1960-02-17 | 1962-07-31 | Du Pont | Halogenation intiator |
US5171899A (en) * | 1988-05-17 | 1992-12-15 | Daikin Industries Ltd. | Process for production of 1,1,1-trifluoro-2,2-dichloroethane |
US5254771A (en) * | 1989-07-14 | 1993-10-19 | Hoechst Aktiengesellschaft | Process for the preparation of 1,1,1-trifluoro-2-2-dichloroethane under elevated pressure |
GB9315450D0 (en) * | 1993-07-26 | 1993-09-08 | Zeneca Ltd | Chlorination process |
-
1992
- 1992-08-03 GB GB929216442A patent/GB9216442D0/en active Pending
-
1993
- 1993-07-27 KR KR1019950700308A patent/KR100239231B1/en not_active IP Right Cessation
- 1993-07-27 BR BR9306819A patent/BR9306819A/en not_active IP Right Cessation
- 1993-07-27 WO PCT/GB1993/001583 patent/WO1994003418A1/en active IP Right Grant
- 1993-07-27 EP EP93917923A patent/EP0652858B1/en not_active Expired - Lifetime
- 1993-07-27 JP JP50508394A patent/JP3335174B2/en not_active Expired - Fee Related
- 1993-07-27 RU RU95106465A patent/RU2118308C1/en active
- 1993-07-27 UA UA95028107A patent/UA35596C2/en unknown
- 1993-07-27 DE DE69332408T patent/DE69332408T2/en not_active Expired - Lifetime
- 1993-07-27 AT AT93917923T patent/ATE226186T1/en not_active IP Right Cessation
- 1993-07-27 CA CA002140443A patent/CA2140443C/en not_active Expired - Fee Related
- 1993-07-27 AU AU47169/93A patent/AU677594B2/en not_active Ceased
- 1993-07-27 ZA ZA935410A patent/ZA935410B/en unknown
- 1993-07-27 CZ CZ95250A patent/CZ284731B6/en not_active IP Right Cessation
- 1993-07-27 HU HU9500261A patent/HU215162B/en not_active IP Right Cessation
- 1993-07-28 IL IL106504A patent/IL106504A/en not_active IP Right Cessation
- 1993-07-30 IN IN803DE1993 patent/IN183284B/en unknown
- 1993-08-02 US US08/101,127 patent/US5414164A/en not_active Expired - Lifetime
- 1993-08-03 CN CN93117650A patent/CN1037961C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4060469A (en) * | 1976-12-21 | 1977-11-29 | Allied Chemical Corporation | Preparation of 1,1,1-trifluoro-2,2-dichloroethane |
EP0407990A1 (en) * | 1989-07-14 | 1991-01-16 | Hoechst Aktiengesellschaft | Method for the production of 1,1,1-trifluoro-2,2-dichloroethane under high pressure |
US5120883A (en) * | 1991-08-26 | 1992-06-09 | E. I. Du Pont De Nemours And Company | Catalytic process for producing CCl3 CF3 |
Also Published As
Publication number | Publication date |
---|---|
EP0652858A1 (en) | 1995-05-17 |
EP0652858B1 (en) | 2002-10-16 |
HUT69326A (en) | 1995-09-28 |
CZ25095A3 (en) | 1995-10-18 |
US5414164A (en) | 1995-05-09 |
HU9500261D0 (en) | 1995-03-28 |
AU4716993A (en) | 1994-03-03 |
KR100239231B1 (en) | 2000-01-15 |
CN1094704A (en) | 1994-11-09 |
AU677594B2 (en) | 1997-05-01 |
ZA935410B (en) | 1994-02-03 |
GB9216442D0 (en) | 1992-09-16 |
IL106504A0 (en) | 1993-11-15 |
CN1037961C (en) | 1998-04-08 |
IL106504A (en) | 1998-02-08 |
HU215162B (en) | 1998-10-28 |
CA2140443A1 (en) | 1994-02-17 |
UA35596C2 (en) | 2001-04-16 |
JP3335174B2 (en) | 2002-10-15 |
ATE226186T1 (en) | 2002-11-15 |
BR9306819A (en) | 1998-12-08 |
DE69332408D1 (en) | 2002-11-21 |
JPH08504750A (en) | 1996-05-21 |
DE69332408T2 (en) | 2003-06-26 |
CA2140443C (en) | 2003-11-25 |
IN183284B (en) | 1999-11-06 |
RU95106465A (en) | 1996-12-20 |
CZ284731B6 (en) | 1999-02-17 |
RU2118308C1 (en) | 1998-08-27 |
KR950702516A (en) | 1995-07-29 |
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