GB1585938A - Process for the production of 1,1,1-trifluoro-2-chlorethane - Google Patents
Process for the production of 1,1,1-trifluoro-2-chlorethane Download PDFInfo
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- GB1585938A GB1585938A GB16720/78A GB1672078A GB1585938A GB 1585938 A GB1585938 A GB 1585938A GB 16720/78 A GB16720/78 A GB 16720/78A GB 1672078 A GB1672078 A GB 1672078A GB 1585938 A GB1585938 A GB 1585938A
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- United Kingdom
- Prior art keywords
- trifluoro
- chloroethane
- difluoro
- dichloroethane
- mole
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 48
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 53
- 239000003054 catalyst Substances 0.000 claims description 37
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 34
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 34
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 24
- 238000003682 fluorination reaction Methods 0.000 claims description 24
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052787 antimony Inorganic materials 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229960003750 ethyl chloride Drugs 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 13
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 150000003623 transition metal compounds Chemical class 0.000 claims description 12
- 150000001495 arsenic compounds Chemical class 0.000 claims description 10
- 229940093920 gynecological arsenic compound Drugs 0.000 claims description 10
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 claims description 9
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims description 9
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229940065285 cadmium compound Drugs 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229940100892 mercury compound Drugs 0.000 claims description 3
- 150000002731 mercury compounds Chemical class 0.000 claims description 3
- 150000001463 antimony compounds Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- -1 antimony halides Chemical class 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical class F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- UDKYUQZDRMRDOR-UHFFFAOYSA-N tungsten Chemical compound [W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W] UDKYUQZDRMRDOR-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
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
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(54) A PROCESS FOR THE PRODUCTION OF 1,1,1 TRIFLUORO-2-CHLORETHANE (71) We BAYER AKTIENGESELLSCHAFT, a body corporate organised under the Laws of Germany of 509 Leverkusen, Germany do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a process for the production of l,l,l-trifluoro-2chloroethane.
More particularly, the invention relates to a process for the production of 1,1,1 -trifluoro-2-chloroethane, optionally in admixture with 1,1,1-difluoro-1,2- dichloroethane, by reacting trichloroethylene with anhydrous hydrogen fluoride in the liquid phase optionally under pressure in the presence of small quantities of a fluorination catalyst in accordance with the following general empirical reaction formulae:
cat.
CHCl = CCI2 + 3 HF ç CF3-CH2Cl+2HCl cat.
CHCl = CCI2 + 2 HF < CF2Cl-CH2Cl+HCl By virtue of its properties (for example non-inflammability, low boiling point), I, I, I -trifluoro-2-chloroethane is an extremely versatile product. Thus, it has already been used as a constituent of aerosol packs (cf. for example US Patents
Nos. 3,583,921 and 3,655,865; German Auslegeschrift No. 1,542,076), as an additive to gaseous pain killers (cf for example US Patent No. 3,325,352) even as a constituent of shampoos (cf for example French Patent No. 2,152,371).
In addition, I, I, I -trifluoro-2-chloroethane (R 133 a) is of particular interest as a possible replacement for perhalogenated fluorochloro alkanes because, unlike perhalogenated fluorochloro alkanes, it is degradable in the atmosphere (cf: for example "Spraydose verboten" Symposium, 17-18.2.77, Gottlieb Duttweiler institut, Ruschlikon Zurich 1977, page 209), and according to all previous investigations is toxicologically acceptable.
Although various processes have already been proposed for the production of I, I, l -trifluoro-2-chloroethane, they are still attended by considerable disadvantages. For example, it is formed alongside a number of other products in the chlorination of 1,1,1-trifluoroethane, in the reaction of antimony fluorides with
CF2CICH2CI at 140 to 1500C/45 bars, in the reaction of 1,1,1,2-tetrachloroethane with HF and HgO at 85 to 950C (in addition to CF2Cl-CH2Cl), in the reaction of
HF with CF2=CHCI in the presence of BF3 at 250C and, finally, in the reaction of trichlorethylene with HF in the presence of antimony catalysts at 170 to 1900C (cf Beilsteins Handbuch der Organ.Chemie, System No. 8, pages 139-140 E III 1).
Unfortunately, none of these processes is suitable for working on a commercial scale because either the processes are too complicated or the starting substances are not available in sufficient quantities.
It has also been proposed to react sym. tetrachloroethane with HF. According to W. B. Walley, J.Soc.Chem. ind. 66, 430 (1947), however, the liquid phase fluorination with HF in the presence of large quantities of SbCl5 at 120 to 1259C only leads to the corresponding monofluorinated and difluorinated compounds.
More highly fluorinated compounds are not observed.
The fluorination of trichloroethylene, a widely used commercial product, has always been of considerable interest. Two methods have been described for this purpose, namely fluorination in the gas phase and fluorination in the liquid phase.
Where fluorination is carried out in the gas phase, trichlorethylene and HF are passed together over catalysts, for example of chromium or aluminium or compounds of these metals. Although good yields can be obtained from gas phase fluorination reactions of this type, there are in general no suitable installations in which to carry them out. In addition, these processes are attended by the disadvantage that, because of the high temperatures involved, decomposition can occur both in the starting materials and also in the end products. At the same time, the catalysts are also deactivated by deposits.
Gas phase fluorination processes are described for example in DT-OS No.
1,442,835 and in DT-OS No. 2,032,098.
Where fluorination is carried out in the liquid phase (cf. for example DT-AS No. 1,020,968; DT-AS No. 1,104,496 or DT-AS No. 1,246,703), it has hitherto only been possible to obtain satisfactory yields with very large quantities of catalyst (for example antimony halides). In addition, it is necessary according to DT-AS No. 1,020,968 to use what is basically an unusual autoclave material, namely aluminum in order to obtain good yields. In spite of this considerable outlay, however, long reaction times are still necessary. For these reasons, the processes in question appear never to have been adopted for working on a commercial scale.
Although, by virtue of its properties, 1,1,1-trifluoro-2-chloroethane (R 133 a) would be eminently suitable for example for replacing the perhalogenated fluorochloro alkanes, such as CCI3F, CCI2F2, CClF2-CClF2 as a propel ant for aerosols, its poor availability is an obstacle to this commercial application.
Accordingly, there is a considerable need to find an economic and commercially workable process for the production of 1,1,1-trifluoro-2-chloroethane.
The present invention provides a process for the production of 1,1,1 -trifluoro- 2-chloroethane, optionally in admixture with 1,1 -difluoro-l 2-dichloroethane, which comprises reacting trichloroethylene with substantially anhydrous hydrogen fluoride in the liquid phase in the presence of a fluorination catalyst, comprising a combination of one or more antimony and/or arsenic compounds and one or more transition metal compounds. Preferably the trichloroethylene used is free from stabilizers.
We have surprisingly found that both the product yield and also the volumetime yield of conventional processes can be significantly improved by the process according to the invention. The reaction is so surprising because, hitherto, there have only been a few compounds, particularly antimony halides, which catalyze the Cl-F-exchange in the liquid phase chlorination of aliphatic chlorinated hydrocarbons (cf. A. K. Barbour et al., in "Advances in Fluorine Chemistry", Vol.
3, 1963, Butterworths London, page 181 and M. Hudlicky, "Chemistry of Organic
Fluorine Compounds", Ellis Harwood, 1976, page 95).
It is not known what is responsible for the intensification of the fluorinating effect of conventional catalysts for liquid-phase fluorination reactions.
It has now surprisingly been found that it is possible to fluorinate trichlorethylene with HF in the presence of optionally stabilizer-free trichlorethylene in high yields and in short reaction times, even in the presence of only very small quantities i.e. catalytic quantities of the fluorination catalysts. The particular advantage of this procedure is that it is not necessary to use large quantities of catalyst so that there is no danger of any undesirable secondary reactions such as otherwise occur with halogen derivatives of the C2 series (cf. for example Houben-Weyl, Methoden der organ. Chemie, 1964, Vol. 5/3, pages 107 and 135).
In addition to the catalysts known per se based on antimony or arsenic compounds, transition metal compounds from Secondary Groups lb to 7b or from the Eighth Main Group (cf. Periodic Table of the Elements, E. H. Sargent & Co., 1964, or Sanderson, Chemical Periodicity, Reinhold Publishing Corp, New York 1962) are in -combination with the antimony and/or arsenic compounds as the fluorination catalysts in the process according to the invention.
Transition metals may primarily be regarded as the elements belonging to the
Secondary Groups of the Periodic System, namely copper to nickel, silver to palladium and gold to platinum. The following elements are mentioned as preferred examples: nickel, cobalt, rare earth metals, iron, copper, palladium, platinum, manganese, vanadium, molybdenum, zirconium, chromium, zinc, mercury, cadmium, silver. Chromium, nickel, cobalt and iron, and especially zinc, cadmium and mercury, are particularly suitable.
These elements are preferably used in the form of their chlorides or fluoride, although they may also be used in the form of the metals or in the form of other compounds, for example sulphates or complex compounds. Mixtures of the metal compounds are of course also suitable.
Fluorination catalyst known per se, such as are described in Houben-Weyl, loc. cit., pages 124 et seq, may be used as one catalyst component of the catalyst combination used.
SbCl5 mixtures of SbCI3 and chlorine, mixtures of SbCl3 and SbCl5 or reaction
Droducts or the above-mentioned compounds with HF which correspond to the general formula SbXnYs-n (X = Cl, Y = F), are particularly suitable for the process according to the invention. It is preferred to use SbCl5. According to a particular embodiment of the present invention, the catalyst is a combination of SbCl5 and a zinc, cadmium and/or mercury compound. The catalyst is used in a quantity of from about 0.005 to 0.2 mole per mole of trichlorethylene and preferably in a quantity of about 0.008 to 0.1 mole. The Sb-compounds may be replaced by the corresponding arsenic compounds.
The additional catalysts are used in similar quantities (molar quantities) to the antimony and/or arsenic components of the fluorination catalyst according to the invention. In general, quantities of as small as about 0.001 mole (based on trichloroethylene) are sufficient. It is not necessary to use more than about 0.4 mole. In general, it is preferred to use quantities of about 0.008 to 0.1 mole.
The Sb or As component is best present in excess in the catalyst mixture, although the other component may also be present in excess. It is possible for example to use from about 10 to 400 mole % of the transition metal catalyst, based on the quantity of the Sb or As compound.
Compounds possibly existing within these composition ranges (such as for example the complex compunds Ni(SbFs)2 aq known in the aquo system or the corresponding Cu or Mn compounds) are equally suitable.
The small quantities of fluorination catalyst used in accordance with the invention are sufficient, above all when the trichlorethylene used does not contain any of the usual stabilizers. It is known that stabilizers such as, for example, amines, epoxides or other organic substances can be added to trichloroethylene (cf. for example Ullmann, Enzyklopadie der Techn. Chemie, 1975, Vol. 9, page 458). These stabilizers can obviously inhibit the catalysts and, for this reason, should be removed. If stabilized trichlorethylene is used with antimony halides, the reaction mixture turns black in color and after a while tar-like products are deposited.
Although it is not completely clear whether these tar-like products adversely affect the process according to the invention, deposits of the type in question must impair the process to a considerable extent, particularly where it is carried out continuously. According to the invention, therefore, it is preferred to use nonstabilized trichlorethylene. The non-stabilized trichlorethylene is obtained for example in known manner (cf. Ullmann, I.c. Vol. 9, page 455) by the dehydrohalogenation of sym. tetrachloroethane and is directly reacted in accordance with the invention. It is also possible to use trichlorethylene containing inactivated stabilizer. This may be done for example by contacting the trichlorethylene with HF or other suitable substances before the actual reaction and in the absence of the catalyst.
The hydrogen fluoride is used in standard commercial, substantially anhydrous form. Its water content does not exceed about 01% by weight.
In one general embodiment, the process according to the invention is carried out by thoroughly mixing the reaction components, catalysts, HF and trichlorethylene in a pressure vessel. Thereafter the pressure vessel is brought to an initial pressure of from about 5 to 20 bars, preferably from about 10 to 15 bars, optionally by the introduction of an inert gas such as N2 or HCI.
With further heating to around 10e-145"C, preferably 1 1O--1350C, the pressure continues to rise (to around 3040 bars, depending on the setting of the pressure stabilizing valve) and is then kept constant. After about 0.5 to 3 hours, the pressure vessel is cooled and the gaseous products escaping are condensed after the usual purifying and drying operations. It is of course also possible to apply higher pressures, although this should be avoided for economic reasons.
It is particularly important that the readily volatile hydrogen fluoride remains in intimate contact with the substance to be fluorinated, even during the heating phase.
The reaction may be carried out both in batches and also continuously, providing the reaction apparatus is set up accordingly.
The process according to the invention, in which it is preferred to use a fairly large excess of HF (2 to 10 times and preferably 4 to 8 times the molar amount of the trichlorethylene), may be carried out in conventional pressure vessels of, for example, steel, nickel, monel. The nature and constituent material of the apparatus used do not have to meet any particular requirements. The process according to the invention is carried out in apparatus known per se, of the type described for example in Houben-Weyl, loc. cit., page 97.
In addition to 1,1,1 -trifluoro-2-chloroethane, 1,1 -difluoro- 1 ,2-dichloroethane may also be formed during the fluorination reaction, particularly in cases where fairly small quantities of hydrogen fluoride are used. This product is also extremely valuable because it can also be reacted by further fluorination to form 1,1,1trifluoro-2-chloroethane. However, l,l-difluoro-l,2-dichloroethane may also be used in its own right, for example as a solvent, cleaning agent or as an intermediate product for numerous other reactions (for example to form CF2 = CHCI). If it is desired to obtain a larger proportion of I, I -difluoro- 1,2-dichloroethane, it is merely necessary to use a smaller excess of HF.
The products obtained in accordance with the invention are extremely simple to work up. Following the removal of HCI and excess HF, the reaction product is distilled. since the boiling points of the two compounds are far apart from one another and since no tetrafluorinated- compound is formed, l,l,l-trifluoro-2- chloroethane immediately accumulates in highly pure form (purity 99.9% and more), which is of considerable importance in one field of application, namely aerosols, while l,1-difluoro-2-chloroethane initially remains in the distillation sump and may then be separately distilled.
The process according to the invention is illustrated in the following Examples:
Example 1.
6.25 g (0.0234 mole of anhydrous mercury-ll-chloride, 13.98 g (0.0467 mole) of antimony pentachloride and 400 g (20 moles) of anhydrous hydrogen fluoride were thoroughly mixed in a 2-liter autoclave equipped with a pressure condenser and stirrer. Following the addition -of 328.5 g (2.5 moles) of trichlorethylene, which had been extracted by shaking with hydrogen fluoride to remove the stabilizers present, the apparatus was placed under a pressure of about 15 bars with dry nitrogen. On heating to around 1300C, the pressure increased rapidly, being maintained at 36 bars by means of a pressure stabilizing valve. After about 1.5 hours, the autoclave was cooled to 3040 C and vented. After passing through a water-filled washing vessel followed by a calcium chloride drying tube, the volatile products escaping were condensed in traps cooled to around -50"C, giving 282 g of condensate wich, after distillation, produced 272 g (92% of the theoretical) of 1,1,1- trifluoro-2-chloroethane (b.p. 6.90C) and 10 g of 1,l-difluoro-1,2-dichloroethane (b.p. 47"C).
l,1-Difluoro-l,2-dichloroethane may be re-reacted to form l,l,l-trifluoro- 2-chloroethane.
Products of relatively low fluorine content remaining behind in the autoclave and products dissolved in the washing liquid were not taken into consideration.
Example 2.
In the evacuated and nitrogen-fil'ed apparatus of Example 1, 400 g (20 moles) of hydrogen fluoride and 328.5 g (2.5 moles) of trichlorethylene were again reacted, re-using the catalyst of Example I for 1.25 hours at 135"C/36--40 bars to form 263 g (89 of the theoretical) of I, I, I -trifluoro-2-chloroethane and 11 g of l,l-difluoro-2- chloroethane.
Example 3.
In the apparatus of Example 1, 1.6 g (0.0155 mole) of anhydrous zinc fluoride, 9.32 g (0.031 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) of trichlorethylene over a period of 1.5 hours at 1250C/30 bars to form 225 g (76% of the theoretical) of 1,1,1 -trifluoro-2-chloroethane and 32 g of l,l-difluoro-1,2- dichloroethane.
Example 4.
In the apparatus of Example 1, 3.14 g (0.0234 mole) of anhydrous copper-ll- chloride, 13.98 g (0.0467 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) of trichlorethylene over a period of 1.75 hours at 1320C/36 bars to form 231 g (81.5% of the theoretical) of l,l,1-trifluoro-2-chloroethane and 18 g of l,l-difluoro-1,2- dichloroethane.
Example 5.
In the apparatus of Example 1, 1.03 g (0.0234 mole) of anydrous nickel chloride, 13.98 g (0.0467 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) ot trichlorethylene over a period of 1.5 hours at 1320C/34 bars to form 248 g (83% of the theoretical) of 1,1,1 -trifluoro-2-chloroethane and 24 g of 1,1 -difluoro- 1,2- dichloroethane.
Example 6.
In the apparatus of Example 1, 4 g (0.031 mole of anhydrous cobalt chloride,
18.64 g (0.062 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) of trichlorethylene over a period of 1.25 hours at 1300C/32 bars to form 251 g (85% of the theoretical) of l,1,l-trifluoro-2-chloroethane and 12 g of 1,1-difluoro-1,2- dichloroethane.
Example 7.
In the apparatus of Example 1, 2.53 g (0.0156 mole) of anhydrous iron(III)chloride, 13.98 g (0.0467 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5
moles) of trichlorethylene over a period of 1.5 hours at 1 320C/36 bars to form 216 g (73% of the theoretical) of 1,1,1-trifluoro-2-chloroethane and 35 g ot I,l-dlfluoro 1 ,2-dichloroethane.
Example 8.
In the apparatus of Example 1, 2.55 g (0.0234 mole) of anhydrous chromium(lll)fluoride, 13.98 g (0.0467 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5
moles) of trichlorethylene over a period of 2 hours at 1300C/34 bars to form 247 g (84% of the theoretical) of 1,1,1-trifluoro-2-chloroethane and 26 g of l,l-difluoro- 1,2-dichloroethane.
Example 9.
In the apparatus of Example 1, 1.3 g (0.0073 mole) of anhydrous palladium chloride, 13.27 g (0.0441 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles of trichloroethylene over a period of 1.75 hours at 1280C/30 bars to form 177 g (60% of the theoretical) of 1,1,1-trifluoro-2-chloroethane and 83 g of I,l-difluoro-1,2-dichloroethane.
Example 10.
In the apparatus of Example 1, 8 g (0.0235 mole) of anhydrous platinum(lV)chloride, 13.98 g (0.047 mole of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 a (2.5 moles of trichlorethylene over a period of 1.25 hours at 128"C/30 bars to form 173 g (58% of the theoretical) of 1,1,1 -trifluoro-2-chloroethane and 70 g of I,l-difluoro- 1 ,2-dichloroethane.
Example 11.
In the apparatus of Example 1, 4 g (0.01 mole) of anhydrous tungsten(Vl)chloride, 9.09 g (0.03 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) of trichlorethylene over a period of 1.25 hours at 1 280C/30 bars to form 167 g (56.5% oT the theoretical) of 1,1,1-trifluoro-2-chloroethane and 109 g of 1,1 difluoro- 1 ,2-dichloroethane.
Example 12.
In the apparatus of Example 1, 5.1 g (0.021 mole) of anhydrous lanthanum chloride, 18.64 g (0.062 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) of trichlorethylene over a period of 1.25 hours at 1280C/30 bars to form 234 g (79% of the theoretical) of 1,1,1 -trifluoro-2-chloroethane and 26 g of 1,1 -difluoro- 1,2- dichloroethane.
Example 13.
In the apparatus of Example 1, 2.6 g (0.0155 mole) of anhydrous zirconium fluoride, 18.64 g (0.062 mole of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) of trichlorethylene over a period of 1.25 hours at 1280C/30 bars to form 237 g (80% of the theoretical) of 1,1,1 -trifluoro-2-chloroethane and 26 g of 1,1 -difluoro- 1,2- dichloroethane.
Example 14.
In the evacuated and nitrogen-filled apparatus of Example 13, 220 g (11 moles) of hydrogen fluoride and 657 g (5 moles of trichlorethylene were similarly reacted, re-using the catalyst of Example 13, over a period of 1.5 hours at 1300C/30 bars to form 581 g (88% of the theoretical) of 1,l-difluoro-1,2-dichloroethane and 5 g of 1,1,1 -trifluoro-2-chloroethane.
Example 15.
In the apparatus of Example 1, 5.7 g (0.0312 mole) of anhydrous cadmium chloride, 18.64 g (0.062 mole) of antimony pentachloride and 200 g (10 moles) of hydrogen fluoride were stirred together and reacted with 336 g (2.5 moles) of 1,1 difluoro-l,2-dichloroethane over a period of 2 hours at 1320C/38 bars to form 278 g (94% of - the theoretical) of 1,1,1 -trifluoro-2-chloroethane.
Example 16.
In the apparatus of Example 1, 2.14 g (0.023 mole) of manganese (lI)fluoride, 13.98 g (0.047 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) of trichlorethylene to form 171 g (58% of the theoretical) of l,l,l-trifluoro-2- chloroethane and 93 g of l,1-difluoro-I,2-dichloroethane.
Example 17.
In the apparatus of Example 1, 1.31 g (0.0156 mole of anhydrous aluminum fluoride, 13.98 g (0.047 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) of trichlorethylene over a period of 1.75 hours at 1280C/30 bars to form 233 g (79% of the theoretical) of l,l,1-trifluoro-2-chloroethane and 34 g of l,l-difluoro-1,2- dichloroethane.
Example 18.
In the apparatus of Example 1, 2.32 g (0.0244 mole) of anhydrous magnesium chloride, 13.98 g (0.047 mole) of antimony pentachloride and 400 g (20 moles) of hydrogen fluoride were stirred together and reacted with 328.5 g (2.5 moles) of trichlorethylene over a period of 1 hour at 1340C/38 bars to form 151 g (51% of the theoretical) of 1,1,1 -trifluoro-2-chloroethane and 83 g of 1,1 -difluoro- 1,2- dichloroethane.
Example 19.
In the apparatus of Example 1, 3.5 g (0.0235 mole) of anhydrous manganese(ll)sulphate, 13.98 g (0.047 mole) of antimony pentachloride and 400g
(20 moles) of hydrogen chloride were stirred together and reacted with 328.5 g (2.5
moles) of trichlorethylene over a period of 1.5 hours at 1 200C/30 bars to form 181 g (61% of the theoretical) of 1,1,1-trifluoro-2-chloroethane and 86 g of l,l-difluoro- 1 2-dichloroethane.
Example 20.
In the apparatus of Example 1, 15 g of nickel powder which had been treated with moist hydrogen fluoride were stirred with 28 g (0.0935 mole) of antimony pentachloride and 640 g (32 moles) of hydrogen fluoride and reacted with 526 g (4 moles) of trichlorethylene over a period of 2 hours at 1200C/20 bars to form 386 g (81% of the theoretical) of 1,1,1-trifluoro-2-chloroethane and 61 -g of l,l-difluoro- 1 ,2-dichloroethane.
WHAT WE CLAIM IS: 1. A process for the production of l,1,1-trifluoro-2-chloroethane, optionally adniixture with l,1-difluoro-1,2-dichloroethane, which comprises reacting trichloroethylene with substantially anhydrous hydrogen fluoride in the liquid phase in the presence of a fluorination catalyst comprising a combination of one or more antimony and/or arsenic compounds and one or more transition metal compounds.
2. A process as claimed in claim 1, wherein the trichloroethylene is free from stabilisers.
3. A process for the production of 1,1,1-trifluoro-2-chloroethane, optionally in admixture with 1,1 -difluoro- I ,2-dichloroethane, which comprises reacting trichloroethylene which is substantially free from stabilisers with substantially anhydrous hydrogen fluoride in the liquid phase in the presence of a fluorination catalyst, comprising a combination of one or more antimony or arsenic compounds and one or more transition metal compounds.
4. A process for the production of l,1,1-trifluoro-2-chloroethane, optionally in admixture with 1,1 -difluoro- 1 2-dichloroethane, which comprises reacting trichloroethylene which is substantially free from stabilisers with substantially anhydrous hydrogen fluoride in the liquid phase and in the presence of a catalytic quantity of a fluorination catalyst comprising a combination of arsenic or antimony compounds and one or more transition metal compounds.
5. A process as claimed in claim 4, characterised in that the trichloroethylene is produced from sym.tetrachloroethane and directly reacted.
6. A process as claimed in claim 4, characterised in that the trichloroethylene is brought into contact with HF before addition of the catalyst.
7. A process as claimed in any of claims 1 to 6, wherein the transition metal compound comprises one or more of zinc, cadmium, mercury, nickel, cobalt and iron.
8. A process as claimed in any of claims 1 to 7, wherein the catalyst is a combination of SbCI5 and a zinc, cadmium and/or mercury compound.
9. A process as claimed in any of claims I to 8, wherein the antimony a
Claims (14)
- **WARNING** start of CLMS field may overlap end of DESC **.Example 20.In the apparatus of Example 1, 15 g of nickel powder which had been treated with moist hydrogen fluoride were stirred with 28 g (0.0935 mole) of antimony pentachloride and 640 g (32 moles) of hydrogen fluoride and reacted with 526 g (4 moles) of trichlorethylene over a period of 2 hours at 1200C/20 bars to form 386 g (81% of the theoretical) of 1,1,1-trifluoro-2-chloroethane and 61 -g of l,l-difluoro- 1 ,2-dichloroethane.WHAT WE CLAIM IS: 1. A process for the production of l,1,1-trifluoro-2-chloroethane, optionally adniixture with l,1-difluoro-1,2-dichloroethane, which comprises reacting trichloroethylene with substantially anhydrous hydrogen fluoride in the liquid phase in the presence of a fluorination catalyst comprising a combination of one or more antimony and/or arsenic compounds and one or more transition metal compounds.
- 2. A process as claimed in claim 1, wherein the trichloroethylene is free from stabilisers.
- 3. A process for the production of 1,1,1-trifluoro-2-chloroethane, optionally in admixture with 1,1 -difluoro- I ,2-dichloroethane, which comprises reacting trichloroethylene which is substantially free from stabilisers with substantially anhydrous hydrogen fluoride in the liquid phase in the presence of a fluorination catalyst, comprising a combination of one or more antimony or arsenic compounds and one or more transition metal compounds.
- 4. A process for the production of l,1,1-trifluoro-2-chloroethane, optionally in admixture with 1,1 -difluoro- 1 2-dichloroethane, which comprises reacting trichloroethylene which is substantially free from stabilisers with substantially anhydrous hydrogen fluoride in the liquid phase and in the presence of a catalytic quantity of a fluorination catalyst comprising a combination of arsenic or antimony compounds and one or more transition metal compounds.
- 5. A process as claimed in claim 4, characterised in that the trichloroethylene is produced from sym.tetrachloroethane and directly reacted.
- 6. A process as claimed in claim 4, characterised in that the trichloroethylene is brought into contact with HF before addition of the catalyst.
- 7. A process as claimed in any of claims 1 to 6, wherein the transition metal compound comprises one or more of zinc, cadmium, mercury, nickel, cobalt and iron.
- 8. A process as claimed in any of claims 1 to 7, wherein the catalyst is a combination of SbCI5 and a zinc, cadmium and/or mercury compound.
- 9. A process as claimed in any of claims I to 8, wherein the antimony and/or arsenic compound is used in a quantity of from 0.008 to 0.1 mole per mole of trichloroethylene.
- 10. A process as claimed in any of claims 1 to 9, wherein the transition metal compound is used in a quantity of from 0.008 to 0.1 mole per mole of trichloroethylene.
- 11. A process as claimed in any of claims 1 to 10, wherein the catalyst comprises from 10 to 400 mole % of the transition metal compound based on the antimony or arsenic compound.
- 12. A process as claimed in any of claims 1 to 11, wherein the reaction is carried out under pressure.
- 13. A process for the production of 1,1,1-trifluoro-2-chloroethane optionally in admixture with 1,1 -difluoro- I ,2-dichloroethane substantially as herein described with reference to any of the specific Examples.
- 14. 1,1,1 -trifluoro-2-chloroethane optionally in admixture with 1,1 -difluoro- 1,2-dichloroethane when produced by a process as claimed in any of claims 1 to 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772719021 DE2719021A1 (en) | 1977-04-28 | 1977-04-28 | 1,1,1-Tri:fluoro-2-chloro-ethane prodn. - from tri:chloro-ethylene and hydrogen fluoride using arsenic or antimony cpd. catalyst |
| DE19772737950 DE2737950A1 (en) | 1977-08-23 | 1977-08-23 | 1,1,1-Tri:fluoro-2-chloroethane prepn. - from stabiliser-free tri:chloroethylene by liq. phase fluorination with anhydrous hydrogen fluoride using catalyst mixt. (J5 28.11.78) |
| DE19772739621 DE2739621C2 (en) | 1977-09-02 | 1977-09-02 | Process for the preparation of 1,1,1-trifluoro-2-chloroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1585938A true GB1585938A (en) | 1981-03-11 |
Family
ID=27187183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB16720/78A Expired GB1585938A (en) | 1977-04-28 | 1978-04-27 | Process for the production of 1,1,1-trifluoro-2-chlorethane |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS53135909A (en) |
| ES (1) | ES469216A1 (en) |
| FR (1) | FR2388785A1 (en) |
| GB (1) | GB1585938A (en) |
| IT (1) | IT7849068A0 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851595A (en) * | 1987-07-07 | 1989-07-25 | E. I. Du Pont De Nemours And Company | Liquid phase halogen exchange process for the manufacture of 1,1,1,2-tetrafluoroethane |
| US5324873A (en) * | 1991-04-15 | 1994-06-28 | Daikin Industries Limited | Azeotropic mixture of hydrogen fluoride and 1,1,1-trifluoro-2-chloroethane and process for purification of 1,1,1-trifluoro-2-chloroethane |
| US5401430A (en) * | 1991-04-15 | 1995-03-28 | Daikin Industries, Ltd. | Azeotropic mixture of hydrogen fluoride and 1,1,1-trifluoro-2-chloroethane |
| US5449842A (en) * | 1989-04-05 | 1995-09-12 | Atochem North America, Inc. | Gas phase process for the production of 1,1-dichloro-1-fluoroethane and/or 1-chloro-1,1-difluoroethane from vinylidene chloride |
| US5545773A (en) * | 1991-12-17 | 1996-08-13 | Elf Atochem S.A. | Liquid phase fluorination process and fluorinated organic products resulting therefrom |
| US5608127A (en) * | 1990-02-09 | 1997-03-04 | E. I. Dupont De Nemours And Company | Halogen exchange process for manufacture of hydrochlorofluoropropanes |
| CN1127460C (en) * | 1999-07-28 | 2003-11-12 | 浙江省化工研究院 | Process for preparing 1,1,1-trichloro-2-chloroethone |
| CN111138292A (en) * | 2018-11-08 | 2020-05-12 | 福建永晶科技股份有限公司 | Method for producing 1,1, 1-trifluoro-2-chloroethane and/or trifluoroethylamine |
| CN112299948A (en) * | 2020-12-01 | 2021-02-02 | 山东华安新材料有限公司 | Preparation method of 1, 1, 1-trifluoro-2-chloroethane |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0366797A4 (en) * | 1988-04-28 | 1990-12-27 | Showa Denko Kabushiki Kaisha | Process for producing organofluorine compound |
| US5202509A (en) * | 1989-09-01 | 1993-04-13 | Societe Atochem | Catalysts for liquid phase fluorination |
| US5243105A (en) * | 1990-03-29 | 1993-09-07 | Imperial Chemical Industries Plc | Chemical process |
| JPH085817B2 (en) * | 1990-06-18 | 1996-01-24 | ダイキン工業株式会社 | Method for producing 1-chloro-2,2,2-trifluoroethane |
| JPH05194287A (en) * | 1992-01-13 | 1993-08-03 | Daikin Ind Ltd | Production of halogenated butene and butane |
| US5659093A (en) * | 1992-06-10 | 1997-08-19 | Daikin Industries Ltd. | Method of producing 1,1,1,3,3-pentafluoropropane, a method of producing 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane, and a method of producing 1,1,1,2,3,3-hexachloropropene |
| FR2835830A1 (en) * | 2002-02-11 | 2003-08-15 | Atofina | COMPOSITION BASED ON STABILIZED TRICHLOROETHYLENE USABLE AS RAW MATERIAL |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1020968B (en) * | 1956-02-03 | |||
| GB881003A (en) * | 1958-05-07 | 1961-11-01 | Ici Ltd | Improvements in the manufacture of organic halogen compounds |
-
1978
- 1978-04-26 IT IT7849068A patent/IT7849068A0/en unknown
- 1978-04-26 JP JP4880978A patent/JPS53135909A/en active Pending
- 1978-04-27 ES ES469216A patent/ES469216A1/en not_active Expired
- 1978-04-27 GB GB16720/78A patent/GB1585938A/en not_active Expired
- 1978-04-28 FR FR7812746A patent/FR2388785A1/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851595A (en) * | 1987-07-07 | 1989-07-25 | E. I. Du Pont De Nemours And Company | Liquid phase halogen exchange process for the manufacture of 1,1,1,2-tetrafluoroethane |
| US5449842A (en) * | 1989-04-05 | 1995-09-12 | Atochem North America, Inc. | Gas phase process for the production of 1,1-dichloro-1-fluoroethane and/or 1-chloro-1,1-difluoroethane from vinylidene chloride |
| US5608127A (en) * | 1990-02-09 | 1997-03-04 | E. I. Dupont De Nemours And Company | Halogen exchange process for manufacture of hydrochlorofluoropropanes |
| US5324873A (en) * | 1991-04-15 | 1994-06-28 | Daikin Industries Limited | Azeotropic mixture of hydrogen fluoride and 1,1,1-trifluoro-2-chloroethane and process for purification of 1,1,1-trifluoro-2-chloroethane |
| US5401430A (en) * | 1991-04-15 | 1995-03-28 | Daikin Industries, Ltd. | Azeotropic mixture of hydrogen fluoride and 1,1,1-trifluoro-2-chloroethane |
| US5545773A (en) * | 1991-12-17 | 1996-08-13 | Elf Atochem S.A. | Liquid phase fluorination process and fluorinated organic products resulting therefrom |
| CN1127460C (en) * | 1999-07-28 | 2003-11-12 | 浙江省化工研究院 | Process for preparing 1,1,1-trichloro-2-chloroethone |
| CN111138292A (en) * | 2018-11-08 | 2020-05-12 | 福建永晶科技股份有限公司 | Method for producing 1,1, 1-trifluoro-2-chloroethane and/or trifluoroethylamine |
| CN111138292B (en) * | 2018-11-08 | 2023-12-12 | 福建永晶科技股份有限公司 | Process for producing 1, 1-trifluoro-2-chloroethane and/or trifluoroethylamine |
| CN112299948A (en) * | 2020-12-01 | 2021-02-02 | 山东华安新材料有限公司 | Preparation method of 1, 1, 1-trifluoro-2-chloroethane |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2388785A1 (en) | 1978-11-24 |
| IT7849068A0 (en) | 1978-04-26 |
| JPS53135909A (en) | 1978-11-28 |
| ES469216A1 (en) | 1979-07-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |