CA2036220C - Process for the preparation of 1,1,1,3,3,3-hexafluoropropane and 2-chloro-1,1,1,3,3,3-hexafluoropropane - Google Patents
Process for the preparation of 1,1,1,3,3,3-hexafluoropropane and 2-chloro-1,1,1,3,3,3-hexafluoropropaneInfo
- Publication number
- CA2036220C CA2036220C CA002036220A CA2036220A CA2036220C CA 2036220 C CA2036220 C CA 2036220C CA 002036220 A CA002036220 A CA 002036220A CA 2036220 A CA2036220 A CA 2036220A CA 2036220 C CA2036220 C CA 2036220C
- Authority
- CA
- Canada
- Prior art keywords
- hexafluoropropane
- reaction
- catalyst
- mol
- hydrogen
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
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
- C07C17/20—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
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)
- Catalysts (AREA)
Abstract
Hexafluoropropanes of the formula CF3-CHX-CF3 where X is hydxogen or chlorine are prepared by reacting hexachloropropene with hydrogen fluoride in the gas phase in the presence of a catalyst.
Description
2036Z;~0 The hexafluoropropanes mentioned in the title have previously only been obtainable by expensive processes, using starting materials which are difficult to obtain and/or in poor yields. Thus, J. Org. Chem. 28, 112 (1963) describes that 1,1,1,3,3,3-hexafluoropropane can be obtained only in about 20 ~ yield from hexachloropropane and pentachloropropene by reaction with potassium fluor-ide in the presence of a polar solvent.
J. Org. Chem. 54, 1432 (1989) describes the preparation of 2-chloro-1,1,1,3,3,3-hexafluoropropane from 1,1,1,3,3,3-hexafluoro-2-propanol, which is first conver-ted to the corresponding nonaflate compound (i.e. a nonafluorobutanesulphonate) into which a chlorine atom is then introduced in the 2-position using lithium chloride in the presence of a crown ether.
1,1l1,3l3,3-Hexafluoropropane and 2-chloro-1,1,1,3,3,3-hexafluoropropane increasingly are gaining interest in industry - the former compound as a propellant which does not endanger the ozone layer of the atmosphere (see Bild der Wissenschaften 2, 49 (1988)) and the latter compound as a heat exchanger liquid (see EP-A 72,308).
There is therefore a need for a technically advantageous preparation process for these substances.
A process has now been found for the prep~ration of hexafluoropropanes of the fo 1~ (I) Le A 27 473 - 1 -20~6;;~20 CF3-CHX-CF3 (I) in which X represents hydrogen or chlorine, which process is characterised in that hexachloropropene is reacted with hydrogen fluoride in the gas phase in the presence of a catalyst.
The fitarting material hexachloropropene is available at low cost, since it is obtainable from simple base chemi-cals (for example from chloroform and tetrachloroethane).
A suitable fonm of hydrogen fluoride i8 commercially available hydrogen fluoride. It can be used as such but also in dilute form, for example mixed with nitrogen.
According to the invention, both reactants are reacted in the gas phase. Suitable reaction temperatures are, for example, those in the range from 250 to 600~C. Prefer-ably, the reaction is carried out in the range from 300 to 550~C, in particular in the range from 350 to 500~C.
The process according to the invention can be carried out at any desired pressures in the reaction zone, as long as the reactants r i n in the gas phase at the pressure chosen in each case. Preferably, the pressure used is 1 to 3 bar, in particular atmospheric pressure or super-atmospheric pressure corresponding to the flow resistance of the apparatus used.
Le A 27 473 - 2 -X03~i~220 The relative amounts of hexachloropropene and hydrogen fluoride used can be varied wilthin wide limits. It is advantageous to use the hydrogen fluoride in excess, for example 5 to 100 mol of hydrogen fluoride per 1 mol of hexachloropropene. It is particularly preferred to use 10 to 50 mol of hydrogen fluoride per 1 mol of hexa-chloropropene.
Examples of suitable catalysts for the process according to the invention are halides and oxides of metals and transition metals. In particular, chlorides, fluorides and/or oxides of copper, chromium, iron, bismuth, zinc, lanthanum, cerium, zirconium, vanadium, molybdenum, tungsten and/or platinum which may have been mixed are suitable. Preference is given to chromium(III~ salts alone or in a mixture with the metal chlorides, fluorides and/or oxides mentioned. The catalysts can be used as such, for example in pallet form, but can also be depo-sited on a support, for example on alumina, magnesium oxide, magnesium fluoride, calcium fluoride, zinc chlor-ide and/or activated carbon.
Particular preference is given to chromium(III) salts, inparticular chromium(III) fluorides, chromium(III) chlor-ides and chromium(III) oxides on one of the support materials mentioned.
The flow rate of the reaction mixture and the catalyst amount can be chosen such, for example, that catalyst charges of 50 to 1000 g/l x h, preferably 150 to Le A 27 473 - 3 -~3~i2;~0 500 g/l x h, are obtained.
Suitable materials for the reaction and secondary appara-tuses are material~ which are resistant to the attack of hydrogen fluoride and hydrogen chloride even at high temperature~, for example nickel, chromium and/or molyb-denum steels, and pure nickel.
The reaction according to the invention can be carried out, for example, by heating the starting materials combined or separately to the reaction temperature, then passing them through a reaction zone (for example a heatable tube containing the catalyst), if desired washing the g~fi mixture leaving the reaction zone and cooling it, so that at least the organic components are condensed and, if desired, separating them further by distillation and purifying them.
After carrying out the process according to the inven-tion, mixtures of fluorine- and/or chlorine-containing propanes and propenes are in ~eneral obtained. The propenes can be recycled into the reaction according to the invention.
The composition of the mixture leaving the reaction zone can be influenced by the reaction temperature. Particu-larly high proportions of 1,1,1,3,3,3-hexafluoropropane (formula (I), X = hydrogen) are obtAine~ by carrying out the reaction at relatively high temperatures, for example at 435 to 525~C, in particular at 450 to 500~C.
Le A 27 473 - 4 -X03~0 Particularly high proportions of 2-chloro-1,1,1,3,3,3~
hexafluoropropane are obtained by carryinq out the reaction at relatively low temperatures, for example at 325 to 415~C, in particular at 350 to 400~C.
~he process according to the invention enables the preparation of hexafluoropropanes of the formula (I) in a simple and low-cost manner. If the halogenated propenes present in the reaction mixture are recycled, hexafluoro-propanes of the formula (I) can in general be obtained in yields of more than 80 ~, relative to the hexachloro-propene used. If desired, CF3-CCl2-CF3 and/or CF3-CHCl-CF3 can be separated off from the reaction mixture and hydrogenated catalytically either separately or in a mixture with 1,1,1,3,3,3-hexafluoropropane to give 1,1,1,3,3,3-hexafluoropropane.
This catalytic hydrogenation can be carried out in a manner known per se, for example by passing a mixture of hydrogen and CF3-CCl2-CF3 and/or CF3 CHCl-CF3 over a fixed bed of hydrogenation catalyst. The molar ratio of hydro-genatable compounds to hydrogen can be, for example, 1:3to 1:50. Preferably it is 1:4 to 1:20.
The hydrogenation can be carried out, for example, at atmospheric pressure or at superatmospheric pressures, for example in the range from atmospheric pressure to 20 bar. Preferably, it is carried out at atmospheric pressure.
Le A 27 473 - 5 -~(~3~i221~
Suitable hydrogena~ion catalysts are in particular those containing transition metals on support materials. Of the transition metals, palladium and platinum are preferred, in particular palladium. Examples of support materials are activated carbons, aluminas, silicas, barium sul-phate, spinels, silicates and titanium dioxide. Activated carbons and lithium/aluminium spinels are preferred. The catalysts can contain, for example, 0.5 to 30 g of transition metal per litre of support material. Prefera-bly, this content is in the range 2 to 20 g/l.
The flow rate of the hydrogenation mixture and the amountof catalyst can be chosen, for example, such that cata-lyst charges of 10 to 1000 g/l x h, preferably those of 50 to 500 g/l x h, are obtained. The reaction tempera-tures are in general above 20~C, preferably in the range100 to 250~C.
The mixture formed in the hydrogenation can be worked up, for example, by washing it with water or dilute base to remove the hydrogen chloride formed and condensing the gaseous products, if desired after drying.
Examples Examples 1 to 4 40 g of hexachloropropene, 80 g of hydrogen fluoride and 1 1 of nitrogen per hour were passed through a nickel tube containing 750 ml of a catalyst prepared according to Example 8 at the temperature given in each case. The Le A 27 473 - 6 -;~03~Z~
gas mixture leaving th~ reaction zone was washed with water, dried, and the condensable portions were condensed at -78~C.
The content of organic components in the condensate was determined by gas chromatography and by nuclear magnetic resonance spectroscopy. The following results were obtained:
Le A 27 473 - 7 -~)3~
c D c~
o ~
o ~ In r~
to a u o o ~;
U D
o oo cn ~ a~ ~) ~ .4 O
Z .,~
¢ ~Q
,_ 0 J U a) O
U~ O ~ ~ U~
~ J
~ O O ~D ~ ~ I ~n ,4-- I ~ ~ 0 ~a .
O
", ~" U ~ 14 14 U ~, U ~U U U C) U ~ H
Le A 27473 - 8 -: 03~
Examples 5 to 7 An upright electrically heatable tubular quartz reactor (length 310 mm, diameter 36 mm) was charged with 200 ml of a supported catalyst containing 18 g of palladium per litre of a globular lithium/al~minium spinel ~globule diameter 3 to 5 mm).
The catalyst was conditioned at 250~C for 6 hours while passing 20 to 25 ml of hydrogen per hour through it.
After that, the hydrogenations described below were carried out in each case. The gases leaving the quartz tube were condensed at -78~C and analysed by means of l9F-NMR spectroscopy.
Example 5 Amounts used: 0.16 mol/h of CF3-CHCl-CF3 and 2.5 mol/h of hydrogen Reaction conditions: 200~C, atmospheric pressure Catalyst charge: 150 g/l x h CF3-CH2-CF3 was obtained at a conversion of 95 ~ and a selectivity of 94 ~.
Example 6 Amounts used: 0.2 mol/h of CF3-CHcl-cF3 and 0.8 mol/h of hydrogen Reaction conditions: 200~C, atmospheric pressure Catalyst charge: 180 g/l x h Le A 27 473 - 9 -~0;3~;2~
CF3-CH2-CF3 was obtained at a conversion of 92 ~ and a selectivity of 85 ~.
Example 7 ~ mounts used: 0.21 mol/h of CF3-CC12-CF3 and 1.1 mol/h of hydrogen Reaction conditions: 200~C, atmospheric pressure Catalyst charge: 200 g/l x h CF3-CH2-CF3 was obtained at a conversion of 89 % and a selectivity of 87 ~.
Example 8 300 g of CrCl3 x 6 HzO and 30 g of MgF2 were heated to 90~C in lO l of water. After 1 hour, 1300 g of an 11 %
strength aqueous ammonia solution were metered in. The mixture was then stirred for 1 hour, allowed to cool, and the precipitated solid was filtered off through a nutsche filter. The solid was washed twice with water, dried, powdered and mixed homogeneously with 2 % by weight of graphite. This mixture was compacted to give tablets of 4 mm in size.
Le A 27 473 - 10 -
J. Org. Chem. 54, 1432 (1989) describes the preparation of 2-chloro-1,1,1,3,3,3-hexafluoropropane from 1,1,1,3,3,3-hexafluoro-2-propanol, which is first conver-ted to the corresponding nonaflate compound (i.e. a nonafluorobutanesulphonate) into which a chlorine atom is then introduced in the 2-position using lithium chloride in the presence of a crown ether.
1,1l1,3l3,3-Hexafluoropropane and 2-chloro-1,1,1,3,3,3-hexafluoropropane increasingly are gaining interest in industry - the former compound as a propellant which does not endanger the ozone layer of the atmosphere (see Bild der Wissenschaften 2, 49 (1988)) and the latter compound as a heat exchanger liquid (see EP-A 72,308).
There is therefore a need for a technically advantageous preparation process for these substances.
A process has now been found for the prep~ration of hexafluoropropanes of the fo 1~ (I) Le A 27 473 - 1 -20~6;;~20 CF3-CHX-CF3 (I) in which X represents hydrogen or chlorine, which process is characterised in that hexachloropropene is reacted with hydrogen fluoride in the gas phase in the presence of a catalyst.
The fitarting material hexachloropropene is available at low cost, since it is obtainable from simple base chemi-cals (for example from chloroform and tetrachloroethane).
A suitable fonm of hydrogen fluoride i8 commercially available hydrogen fluoride. It can be used as such but also in dilute form, for example mixed with nitrogen.
According to the invention, both reactants are reacted in the gas phase. Suitable reaction temperatures are, for example, those in the range from 250 to 600~C. Prefer-ably, the reaction is carried out in the range from 300 to 550~C, in particular in the range from 350 to 500~C.
The process according to the invention can be carried out at any desired pressures in the reaction zone, as long as the reactants r i n in the gas phase at the pressure chosen in each case. Preferably, the pressure used is 1 to 3 bar, in particular atmospheric pressure or super-atmospheric pressure corresponding to the flow resistance of the apparatus used.
Le A 27 473 - 2 -X03~i~220 The relative amounts of hexachloropropene and hydrogen fluoride used can be varied wilthin wide limits. It is advantageous to use the hydrogen fluoride in excess, for example 5 to 100 mol of hydrogen fluoride per 1 mol of hexachloropropene. It is particularly preferred to use 10 to 50 mol of hydrogen fluoride per 1 mol of hexa-chloropropene.
Examples of suitable catalysts for the process according to the invention are halides and oxides of metals and transition metals. In particular, chlorides, fluorides and/or oxides of copper, chromium, iron, bismuth, zinc, lanthanum, cerium, zirconium, vanadium, molybdenum, tungsten and/or platinum which may have been mixed are suitable. Preference is given to chromium(III~ salts alone or in a mixture with the metal chlorides, fluorides and/or oxides mentioned. The catalysts can be used as such, for example in pallet form, but can also be depo-sited on a support, for example on alumina, magnesium oxide, magnesium fluoride, calcium fluoride, zinc chlor-ide and/or activated carbon.
Particular preference is given to chromium(III) salts, inparticular chromium(III) fluorides, chromium(III) chlor-ides and chromium(III) oxides on one of the support materials mentioned.
The flow rate of the reaction mixture and the catalyst amount can be chosen such, for example, that catalyst charges of 50 to 1000 g/l x h, preferably 150 to Le A 27 473 - 3 -~3~i2;~0 500 g/l x h, are obtained.
Suitable materials for the reaction and secondary appara-tuses are material~ which are resistant to the attack of hydrogen fluoride and hydrogen chloride even at high temperature~, for example nickel, chromium and/or molyb-denum steels, and pure nickel.
The reaction according to the invention can be carried out, for example, by heating the starting materials combined or separately to the reaction temperature, then passing them through a reaction zone (for example a heatable tube containing the catalyst), if desired washing the g~fi mixture leaving the reaction zone and cooling it, so that at least the organic components are condensed and, if desired, separating them further by distillation and purifying them.
After carrying out the process according to the inven-tion, mixtures of fluorine- and/or chlorine-containing propanes and propenes are in ~eneral obtained. The propenes can be recycled into the reaction according to the invention.
The composition of the mixture leaving the reaction zone can be influenced by the reaction temperature. Particu-larly high proportions of 1,1,1,3,3,3-hexafluoropropane (formula (I), X = hydrogen) are obtAine~ by carrying out the reaction at relatively high temperatures, for example at 435 to 525~C, in particular at 450 to 500~C.
Le A 27 473 - 4 -X03~0 Particularly high proportions of 2-chloro-1,1,1,3,3,3~
hexafluoropropane are obtained by carryinq out the reaction at relatively low temperatures, for example at 325 to 415~C, in particular at 350 to 400~C.
~he process according to the invention enables the preparation of hexafluoropropanes of the formula (I) in a simple and low-cost manner. If the halogenated propenes present in the reaction mixture are recycled, hexafluoro-propanes of the formula (I) can in general be obtained in yields of more than 80 ~, relative to the hexachloro-propene used. If desired, CF3-CCl2-CF3 and/or CF3-CHCl-CF3 can be separated off from the reaction mixture and hydrogenated catalytically either separately or in a mixture with 1,1,1,3,3,3-hexafluoropropane to give 1,1,1,3,3,3-hexafluoropropane.
This catalytic hydrogenation can be carried out in a manner known per se, for example by passing a mixture of hydrogen and CF3-CCl2-CF3 and/or CF3 CHCl-CF3 over a fixed bed of hydrogenation catalyst. The molar ratio of hydro-genatable compounds to hydrogen can be, for example, 1:3to 1:50. Preferably it is 1:4 to 1:20.
The hydrogenation can be carried out, for example, at atmospheric pressure or at superatmospheric pressures, for example in the range from atmospheric pressure to 20 bar. Preferably, it is carried out at atmospheric pressure.
Le A 27 473 - 5 -~(~3~i221~
Suitable hydrogena~ion catalysts are in particular those containing transition metals on support materials. Of the transition metals, palladium and platinum are preferred, in particular palladium. Examples of support materials are activated carbons, aluminas, silicas, barium sul-phate, spinels, silicates and titanium dioxide. Activated carbons and lithium/aluminium spinels are preferred. The catalysts can contain, for example, 0.5 to 30 g of transition metal per litre of support material. Prefera-bly, this content is in the range 2 to 20 g/l.
The flow rate of the hydrogenation mixture and the amountof catalyst can be chosen, for example, such that cata-lyst charges of 10 to 1000 g/l x h, preferably those of 50 to 500 g/l x h, are obtained. The reaction tempera-tures are in general above 20~C, preferably in the range100 to 250~C.
The mixture formed in the hydrogenation can be worked up, for example, by washing it with water or dilute base to remove the hydrogen chloride formed and condensing the gaseous products, if desired after drying.
Examples Examples 1 to 4 40 g of hexachloropropene, 80 g of hydrogen fluoride and 1 1 of nitrogen per hour were passed through a nickel tube containing 750 ml of a catalyst prepared according to Example 8 at the temperature given in each case. The Le A 27 473 - 6 -;~03~Z~
gas mixture leaving th~ reaction zone was washed with water, dried, and the condensable portions were condensed at -78~C.
The content of organic components in the condensate was determined by gas chromatography and by nuclear magnetic resonance spectroscopy. The following results were obtained:
Le A 27 473 - 7 -~)3~
c D c~
o ~
o ~ In r~
to a u o o ~;
U D
o oo cn ~ a~ ~) ~ .4 O
Z .,~
¢ ~Q
,_ 0 J U a) O
U~ O ~ ~ U~
~ J
~ O O ~D ~ ~ I ~n ,4-- I ~ ~ 0 ~a .
O
", ~" U ~ 14 14 U ~, U ~U U U C) U ~ H
Le A 27473 - 8 -: 03~
Examples 5 to 7 An upright electrically heatable tubular quartz reactor (length 310 mm, diameter 36 mm) was charged with 200 ml of a supported catalyst containing 18 g of palladium per litre of a globular lithium/al~minium spinel ~globule diameter 3 to 5 mm).
The catalyst was conditioned at 250~C for 6 hours while passing 20 to 25 ml of hydrogen per hour through it.
After that, the hydrogenations described below were carried out in each case. The gases leaving the quartz tube were condensed at -78~C and analysed by means of l9F-NMR spectroscopy.
Example 5 Amounts used: 0.16 mol/h of CF3-CHCl-CF3 and 2.5 mol/h of hydrogen Reaction conditions: 200~C, atmospheric pressure Catalyst charge: 150 g/l x h CF3-CH2-CF3 was obtained at a conversion of 95 ~ and a selectivity of 94 ~.
Example 6 Amounts used: 0.2 mol/h of CF3-CHcl-cF3 and 0.8 mol/h of hydrogen Reaction conditions: 200~C, atmospheric pressure Catalyst charge: 180 g/l x h Le A 27 473 - 9 -~0;3~;2~
CF3-CH2-CF3 was obtained at a conversion of 92 ~ and a selectivity of 85 ~.
Example 7 ~ mounts used: 0.21 mol/h of CF3-CC12-CF3 and 1.1 mol/h of hydrogen Reaction conditions: 200~C, atmospheric pressure Catalyst charge: 200 g/l x h CF3-CH2-CF3 was obtained at a conversion of 89 % and a selectivity of 87 ~.
Example 8 300 g of CrCl3 x 6 HzO and 30 g of MgF2 were heated to 90~C in lO l of water. After 1 hour, 1300 g of an 11 %
strength aqueous ammonia solution were metered in. The mixture was then stirred for 1 hour, allowed to cool, and the precipitated solid was filtered off through a nutsche filter. The solid was washed twice with water, dried, powdered and mixed homogeneously with 2 % by weight of graphite. This mixture was compacted to give tablets of 4 mm in size.
Le A 27 473 - 10 -
Claims (9)
1. A process for the preparation of hexafluoropropanes of the formula (I) CF3-CHX-CF3 (I) in which X represents hydrogen or chlorine,, in which process hexachloropropene is reacted with hydrogen fluoride in the gas phase in the presence of a catalyst.
2. The process of Claim 1, in which the reaction is carried out at 250 to 600°C.
3. The process of Claim 1, in which 5 to 100 mol of hydrogen fluoride are used per 1 mol of hexachloropropene.
4. The process of Claim 1, in which halides and/or oxides of metals and/or transition metals are used as catalyst.
5. The process of Claim 1, in which a catalyst containing a chromium(III) salt is used.
6. The process of Claim 1, in which 1,1,1,3,3,3-hexafluoropropene is prepared by carrying out the reaction at 435 to 525°C.
7. The process of Claim 1, in which 2-chloro-1,1,1,3,3,3-hexafluoropropane is prepared by carrying out the process at 325 to 415°C.
8. The process of Claim 1, in which CF3-CCl2-CF3 and/or CF3-CHCl-CF3 separated off from the reaction mixture is hydrogenated catalytically to give 1,1,1,3,3,3-hexafluoropropane.
9. The process of Claim 8, in which transition metals on support materials are used as hydrogenation catalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4004495.5 | 1990-02-14 | ||
| DE4004495A DE4004495A1 (en) | 1990-02-14 | 1990-02-14 | METHOD FOR PRODUCING 1,1,1,3,3,3-HEXAFLUORPROPANE AND 2-CHLORINE-1,1,1,3,3,3-HEXAFLUORPROPANE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2036220A1 CA2036220A1 (en) | 1991-08-15 |
| CA2036220C true CA2036220C (en) | 1999-08-03 |
Family
ID=6400099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002036220A Expired - Fee Related CA2036220C (en) | 1990-02-14 | 1991-02-12 | Process for the preparation of 1,1,1,3,3,3-hexafluoropropane and 2-chloro-1,1,1,3,3,3-hexafluoropropane |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0442075B1 (en) |
| JP (1) | JP2672191B2 (en) |
| CA (1) | CA2036220C (en) |
| DE (2) | DE4004495A1 (en) |
| ES (1) | ES2044382T3 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4213975A1 (en) * | 1992-04-29 | 1993-11-04 | Bayer Ag | METHOD FOR PRODUCING HEXAFLUORBUTANE AND ACCESSIBLE INTERMEDIATE PRODUCTS THEREOF |
| DE4305164A1 (en) * | 1993-02-19 | 1994-08-25 | Bayer Ag | Process for the preparation of 1,1,1,3,3-pentafluoropropane |
| US5516598A (en) * | 1994-07-28 | 1996-05-14 | Polyplus Battery Company, Inc. | Secondary cell using organosulfur/metal charge transfer materials as positive electrode |
| US5481051A (en) * | 1994-12-08 | 1996-01-02 | E. I. Du Pont De Nemours And Company | 2,2-dichlorohexafluoropropane hydrogenolysis |
| US6291729B1 (en) | 1994-12-08 | 2001-09-18 | E. I. Du Pont De Nemours And Company | Halofluorocarbon hydrogenolysis |
| US5616819A (en) * | 1995-08-28 | 1997-04-01 | Laroche Industries Inc. | Process for preparing fluorinated aliphatic compounds |
| US6376727B1 (en) | 1997-06-16 | 2002-04-23 | E. I. Du Pont De Nemours And Company | Processes for the manufacture of 1,1,1,3,3-pentafluoropropene, 2-chloro-pentafluoropropene and compositions comprising saturated derivatives thereof |
| DE69842237D1 (en) * | 1997-02-19 | 2011-06-01 | Du Pont | Azeotropic compositions containing 1,1,1,2,3,3,3-heptafluoropropane and methods using these compositions |
| EP1428811B1 (en) * | 1997-02-19 | 2011-04-20 | E.I. Du Pont De Nemours And Company | Azeotropic compositions comprising 1,1,1,2,3,3,3-heptafluoropropane and processes using said compositions |
| GB9802487D0 (en) * | 1998-02-06 | 1998-04-01 | Ici Plc | Production of heptafluoropane |
| US7329786B2 (en) | 2001-09-28 | 2008-02-12 | Great Lakes Chemical Corporation | Processes for producing CF3CFHCF3 |
| US7223351B2 (en) | 2003-04-17 | 2007-05-29 | Great Lakes Chemical Corporation | Fire extinguishing mixtures, methods and systems |
| US7214839B2 (en) * | 2003-05-23 | 2007-05-08 | Honeywell International Inc. | Method of making hydrofluorocarbons |
| KR101125467B1 (en) * | 2003-10-14 | 2012-03-27 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Process for the preparation of 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3,3-hexafluoropropane |
| US8071825B2 (en) * | 2006-01-03 | 2011-12-06 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB901297A (en) * | 1960-04-12 | 1962-07-18 | Union Carbide Corp | Process for the production of pentafluoroethane |
| NL274475A (en) * | 1962-02-07 | |||
| US4873381A (en) * | 1988-05-20 | 1989-10-10 | E. I. Du Pont De Nemours And Company | Hydrodehalogenation of CF3 CHClF in the presence of supported Pd |
-
1990
- 1990-02-14 DE DE4004495A patent/DE4004495A1/en not_active Withdrawn
- 1990-12-11 EP EP90123784A patent/EP0442075B1/en not_active Expired - Lifetime
- 1990-12-11 ES ES90123784T patent/ES2044382T3/en not_active Expired - Lifetime
- 1990-12-11 DE DE9090123784T patent/DE59002322D1/en not_active Expired - Fee Related
-
1991
- 1991-02-12 CA CA002036220A patent/CA2036220C/en not_active Expired - Fee Related
- 1991-02-12 JP JP3038920A patent/JP2672191B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4004495A1 (en) | 1991-08-22 |
| EP0442075B1 (en) | 1993-08-11 |
| ES2044382T3 (en) | 1994-01-01 |
| JPH04211027A (en) | 1992-08-03 |
| JP2672191B2 (en) | 1997-11-05 |
| DE59002322D1 (en) | 1993-09-16 |
| EP0442075A1 (en) | 1991-08-21 |
| CA2036220A1 (en) | 1991-08-15 |
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