WO1991001287A1 - Process for producing a dichloropentafluoropropane - Google Patents

Process for producing a dichloropentafluoropropane Download PDF

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Publication number
WO1991001287A1
WO1991001287A1 PCT/JP1990/000924 JP9000924W WO9101287A1 WO 1991001287 A1 WO1991001287 A1 WO 1991001287A1 JP 9000924 W JP9000924 W JP 9000924W WO 9101287 A1 WO9101287 A1 WO 9101287A1
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Prior art keywords
reaction
conducted
tetrafluoroethylene
catalyst
reactor
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PCT/JP1990/000924
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French (fr)
Inventor
Shinsuke Morikawa
Shunichi Samejima
Keiichi Ohnishi
Hidekazu Okamoto
Takashi Ohmori
Toshihiro Tanuma
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Asahi Glass Company Ltd.
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Priority claimed from JP1187523A external-priority patent/JP2738042B2/en
Priority claimed from JP21755489A external-priority patent/JP2734670B2/en
Priority claimed from JP21755589A external-priority patent/JP2734671B2/en
Priority claimed from JP21755389A external-priority patent/JP2734669B2/en
Priority claimed from JP26309889A external-priority patent/JP2849129B2/en
Application filed by Asahi Glass Company Ltd. filed Critical Asahi Glass Company Ltd.
Priority to KR1019910700305A priority Critical patent/KR920701092A/en
Publication of WO1991001287A1 publication Critical patent/WO1991001287A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
    • C07C19/12—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine having two carbon atoms

Definitions

  • the present invention relates to a process for producing a dichloropentafluoropropane (R225) such as 3,3-dichloro-l,l,l,2,2-pentafluoropropane (R225ca) or l,3-dichloro-l,l,2,2,3-pentafluoropropane (R225cb).
  • R225 dichloropentafluoropropane
  • Such a dichloropentafluoropropane is expected to be useful as a foaming agent, a cooling medium or a cleaning agent like conventional chlorofluorocarbons (CFC S ).
  • the present invention has been accomplished on the basis of this discovery.
  • trichlorofluoromethane Rll
  • tetrafluoroethylene 4F
  • trichloropentafluoropropanes such as 1,1,3- trichloro-1,2,2,3,3-pentafluoropropane (R215ca) and l,l,l-trichloro-2,2,3,3,3-pentafluoropropane (R215cb) are obtained in good yield.
  • R215ca and R215cb formed by this addition reaction vary depending upon the catalyst and reaction conditions employed.
  • the Lewis acid catalyst useful for the reaction of the present invention it is possible to employ a halide containing at least one element selected from the group consisting of B, &£ , Ga, In, Fe, Ni, Co, Sb, Nb, Sn, Ti, Zr, W, Hf and Ta, such as a chloride, e.g. BC ⁇ 3 , A£C4 3 , GaC- ⁇ ?
  • the reaction can be conducted in an inert solvent such as perfluorooctane or perfluorobutyltetrahydrofuran. However, to make the purification easy, it is usually preferred to conduct the reaction in the absence of any solvent.
  • the catalyst is used usually in an amount of from 0.01 to 50% by weight, preferably from 0.1 to 10% by weight, relative to the starting material.
  • the reaction temperature is usually within a range of from -80 to 200°C, preferably from -20 to 100°C, and the reaction pressure is usually from 0 to 20 kg/cm , preferably from 0 to 10 kg/cm 2 .
  • 4F is used usually 1.0 to 1.5 times the molar quantity of Rll.
  • the Lewis acid catalyst is usually used in an amount of from 0.1 to 50 weight%, preferably from 0.1 to 10 weight%, relative to Rll.
  • the reduction of trichloropentafluoropropane (R215) obtained by this reaction can be conducted by using various reducing methods such as a method of conducting the reduction under irradiation, a method for conducting the reduction by means of zinc, or a method for conducting the reduction by using hydrogen in the presence of a catalyst, whereby dichloropentafluoropropane (R225), such as 3,3-dichloro- 1,1,1,2,2-pentafluoropropane (R225ca) or 1,3-dichloro- 1,1,2,2,3-pentafluoropropane (R225cb) can be obtained.
  • dichloropentafluoropropane R225
  • R225ca 3,3-dichloro- 1,1,1,2,2-pentafluoropropane
  • R225cb 1,3-dichloro- 1,1,2,2,3-pentafluoropropane
  • an organic compound having a hydrogen atom bonded thereto is used as a compound used as a proton source.
  • an alcohol such as methanol, ethanol, isopropyl alcohol or sec-butyl alcohol, an alkane such as hexane or heptane, or an aromatic compound such as toluene or xylene, is preferred.
  • a secondary alcohol such as isopropyl alcohol, is particularly preferred.
  • a solvent mixture thereof may also be employed.
  • the light source to be used in the present invention is not particularly limited so long as it is capable of emitting light having a wavelength of shorter than 400 nm.
  • a high pressure mercury lamp, a moderate pressure mercury lamp or a low pressure mercury lamp may preferably be employed.
  • the reaction is conducted usually within a temperature range of from -80 to 100°C, preferably from 0 to 40°C. There is no particular restriction as to the pressure. However, the reaction is conducted usually within a pressure range of from 0 to 10 kg/cm 2 G, preferably from 0 to 2 kg/cm 2 G.
  • the solvent used for the reduction by means of zinc is not particularly limited. However, it is preferred to employ an alcohol such as methanol, ethanol or isopropyl alcohol, an organic acid such as acetic acid or formic acid, an ether such as tetrahydrofuran or water, or a mixture thereof. In particular, an alcohol such as methanol, ethanol or isopropyl alcohol is preferred.
  • Zinc may be used in any form such as a powder, granules or fragments. However, it is most preferred to employ zinc powder. It is unnecessary to apply any special pretreatment such as activating treatment before use.
  • the amount of zinc is not particularly limited. But it is usually preferred to employ it at least stoichiometric amount relative to the starting material.
  • the reaction is conducted usually within a temperature range of from room temperature to 150°C, preferably from 50 to 80°C. There is no particular restriction as to the pressure, but the reaction is conducted usually within a pressure range of from 0 to 10 kg/cm 2 G, preferably from 0 to 3 kg/cm 2 G.
  • the reaction may be carried out either in a liquid phase or a gas phase.
  • the reducing catalyst may be a noble metal catalyst such as platinum, palladium, rhodium or ruthenium, or a base metal catalyst such as nickel. However, it is particularly preferred to use a noble metal catalyst.
  • As the carrier for the reducing catalyst alumina or active carbon is, for example, suitable.
  • the conventional method for preparation of a noble metal catalyst can be applied as a method for supporting the catalyst on the carrier. To use the catalyst, it is preferred to preliminarily apply reduction treatment to the catalyst to obtain the constant performance. However, such a pretreatment is not necessarily required. At least a part of such a metal compound is reduced.
  • the ratio of hydrogen to the starting material may be varied to a large extent.
  • the halogen atom is removed by using hydrogen in a stoichiometrical amount.
  • the molar ratio of the hydrogen to the starting meterial may be larger than one to one, for example, four to one or higher.
  • the reaction temperature is usually from 100 to 350°C, preferably from 100 to 200°C.
  • the contact time is usually from 0.1 to 300 seconds, preferably from 2 to 60 seconds.
  • an alcohol such as ethanol or isopropyl alcohol, acetic acid or pyridine may be used.
  • the reaction can be conducted without any solvent.
  • the reaction temperature for the liquid phase reaction is preferably from room temperature to 150°C, and the reaction pressure - 1 -
  • Lewis acid catalyst > CC ⁇ F 2 CF 2 CHC ⁇ 2
  • the fluorination of l,3,3-trichloro-l,l,2,2- tetrafluoropropane (R224ca) obtained by this reaction is conducted preferably in a gas phase in the presence of a catalyst, or in a liquid phase by using hydrogen fluoride.
  • the proportions of R225ca and R225cb formed by the fluorination vary depending upon the catalyst and reaction conditions empolyed.
  • the catalyst used in the gas phase it is possible to employ a halide or an oxide containing at least one element selected from the group consisting of K£, Cr, Mg, Ca, Ba, Sr, Fe, Ni, Co and Mn.
  • any method may be employed so long as it is a method capable of uniformly dispersing the halide or oxide containing at least one element selected from the above elements.
  • a coprecipitation method or a kneading method may be used.
  • Particularly preferred is a method of coprecipitating hydrates from an aqueous solution of salts of the above mentioned metal elements, or a method of kneading or attriting a cake of hydroxides by a ball mill or a homogenizer.
  • hydroxides those precipitated from an aqueous solution of inorganic salts such as nitrates or sulfates by means of aqueous ammonia or urea, or those prepared by the hydrolysis of organic salts, may be employed.
  • the catalyst in the form of hydrates is preferably dried at a temperature of from 120 to 150°C, followed by calcining usually at a temperature of from 300 to 600°C, preferably from 350 to 450°C.
  • the activation can be conducted in the fluorination reaction system, or by heating with a fluorinated hydrocarbon.
  • the reaction is conducted usually in a gas phase under atmospheric pressure or an elevated pressure within a temperature range of from 150 to 550°C, preferably from 250 to 450°C.
  • the ratio of hydrogen fluoride to the starting material may be varied to a large extent.
  • the chlorine atom is substituted usually by using a stoichiometrical amount of hydrogen fluoride. However, it is possible to use hydrogen fluoride in a larger amount, for example, four molar excess or higher than the stoichiometrical amount of the total molar amount of the starting material.
  • the contact time is usually from 0.1 to 300 seconds, preferably from 5 to 30 seconds.
  • a fluorination catalyst consisting of a halide of e.g. Sb, Nb, Ta or Sn, such as SbF 5 , SbC ⁇ 5 , SbC ⁇ 2 F 3 , NbC ⁇ 5 , NbF 5 , SbC ⁇ 5 , NbC ⁇ 5 , NbF 5 , TaF 5 , aC ⁇ 5 or SnC- 4 .
  • the fluorination reaction is conducted in a liquid phase under atmospheric pressure or an elevated pressure usually within a temperature range of from 0 to 200°C, preferably from room temperature to 150°C. In the present invention, the reaction is usually conducted in the absence of any solvent. However, a solvent may be employed.
  • the solvent employed in such a case is not particularly limited so long as it is capable of dissolving propanes as the starting materials, and the solvent itself is hardly fluorinated as compared with the starting material.
  • the reaction pressure is usually from 0 to 10 kg/cm 2 G, and when a solvent is used, the reaction pressure depends upon the type of the solvent.
  • Hydrogen fluoride may be charged before the reaction. However, it is more effective to feed it into the liquid phase as the reaction proceeds. As another embodiment, when carbon tetrachloride
  • R214cb obtained by the addition reaction of 4F with RIO may firstly be fluorinated in the same manner as the fluorination of R224ca, to form trichloropentafluoropropane such as R215ca or R215cb, which is then reduced in the same manner to obtain dichloropentafluoropropane such as R225cb or R225ca.
  • This powder was molded into cylinders having a diameter of 5 mm and a height of 5 mm by means of a tabletting machine.
  • the catalyst thus obtained was fluorinated in a stream of a gas mixture of hydrogen fluoride/nitrogen at a temperature of from 200 to 400°C for activation prior to the reaction.
  • Example 3
  • Example 4 Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added, and the autoclave was deaerated under reduce pressure. Then, 9 kg (75.3 mol) of R20 (CHC ⁇ 3 ) was added thereto. The autoclave was heated to 65°C, and tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 4 kg (40 mol) of tetrafluoroethylene, stirring was continued for further one hour.
  • the reaction solution was filtered, and the reaction crude solution was purified by distillation to obtain 7.5 kg of R224ca (1,3,3-trichloro-l,1,2,2-tetrafluoropropane) (yield: 85%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 m£ of a fluorination catalyst prepared as described in Preparation Example 2, was packed. The reactor was heated to 320°C, and 160 m ⁇ /min of gasified R224ca and 440 m ⁇ /min of hydrogen fluoride were supplied, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 6.9 kg of the reaction mixture was recovered and analyzed by gas chromatography and 19 F-NMR. The results are shown in Table 4. Table 4
  • the reaction mixture was purified by distillation to obtain 4.1 kg of R224ca (l,3,3-trichloro-l,l,3-trichloro- 1,1,2,2-tetrafluoropropane) (yield: 73%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 m£ of a fluorination catalyst prepared as described in Preparation Example 1, was packed. The reactor was heated to 280°C, and 160 m ⁇ /min of gasified R224ca and 440 m ⁇ /min of hydrogen fluoride were supplied thereto, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 3.7 kg of the reaction mixture was recovered and analyzed by gas chromatography and 19 F-NMR. The results are shown in Table 6.
  • Example 6 Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added and the autoclave was deaerated under reduced pressure. Then, 9 kg (58.5 mols) of RIO (CC* 4 ) was added thereto. The autoclave was heated to 65°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 3 kg (30 mols) of tetrafluoroethylene, stirring was continued for further one hour.
  • the reaction mixture was purified by distillation to obtain 4.1 kg of R224ca (l,3,3-trichloro-l,l,2,2- tetrafluoropropane) (yield: 73%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 m£ of a fluorination catalyst prepared as described in Preparation Example 2, was packed thereto. The reactor was heated to 320°C, and 160 m ⁇ /min of gasified R224ca and 440 m ⁇ /min of hydrogen fluoride were supplied thereto, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 3.8 kg of the reaction mixture was recovered and analyzed by gas chromatography and 19 F-NMR. The results are shown in Table 8. Table 8
  • the reaction mixture was purified by distillaiton to obtain 190 g of R224ca (l,3,3-trichloro-l,l,2,2- tetrafluoropropane) . Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.5 cm and a length of 100 cm as a reactor for fluorination, 200 m£ of a fluorination catalyst prepared as described in Preparation Example 1, was packed. The reactor was heated to 280°C, and 160 m ⁇ /min of R224ca and 440 m ⁇ /min of hydrogen fluoride were supplied thereto, and the reaction was conducted.
  • Example 8 Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added and the autoclave was deaerated under reduced pressure. Then, 9 kg (58.5 mols) of RIO (CC ⁇ 4 ) was added thereto. The autoclave was heated to 65°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 3 kg (30 mols) of tetrafluoroethylene, stirring was continued for further one hour.
  • the reaction mixture was purified by distillaiton to obtain 240 g of R224ca (l,3,3-trichloro-l,l,2,2- tetrafluoropropane) (yield: 70%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 £ of a fluorination catalyst prepared as described in Preparation Example 1 was packed thereto. The reactor was heated to 280°C, and 160 m ⁇ / in of gasified R224ca and 440 m- ⁇ /min of hydrogen fluoride were supplied thereto, and the reaction was conducted. The reaction was stopped when 3 kg of R224ca was supplied. The reaction crude gas was passed through an aqueous alkaline solution, and 2.7 kg of the reactoin mixture was recovered and analyzed by gas chromatography and 19 F-NMR. The results are shown in Table 12. Table 12
  • reaction mixture was filtered, and the reaction crude solution was purified by distillation to obtain 6.5 kg of R214cb (1,1,1,3- tetrachlorotetrafluoropropane) (yield: 86%).
  • R214cb (1,1,1,3- tetrachlorotetrafluoropropane)
  • Yield 86%).
  • 200 of a fluorination catalyst prepared as described in Preparation Example 1 was packed.
  • the reactor was heated to 280°C, and 240 m ⁇ /min of gasified R214cb and 360 m ⁇ /min of hydrogen fluoride were supplied thereto, and the reaction was conducted.
  • Preparation Example 2 was packed. The reactor was heated to 320°C, and 240 m ⁇ /min of gasified R214cb and 360 m ⁇ /min of hydrogen fluoride were supplied, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 5.2 kg of the reaction mixture was recovered and purified by distillation to obtain 4.9 kg of R215ca (1,1,3- trichloropentafluoropropane) (yield: 80%).
  • reaction mixture was filtered, and the products were purified by distillation to obtain 6.5 - 32 - kg of R214cb ( 1,1,1,3-tetrachlorotetrafluoropropane) ( yield: 85 % ).
  • R214cb 1,1,1,3-tetrachlorotetrafluoropropane
  • Preparation Example 1 was packed. The reactor was heated to 280° C , and 240 m ⁇ /min of gasified R214cb and 360 m ⁇ /min of hydrogen fluoride were supplied, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 6.0 kg of the reaction mixture was recovered. The products were purified by distillation to obtain 5.1 kg of R215ca ( 1,1,3-trichloropentafluoropropane) (yield: 83%). Then, into a photochemical reactor (EHB-W1F-500 Model, manufactured by Eiko Co., Ltd.), 800 m£ of isopropanol and 400 g of R215ca were charged. While cooling the reaction solution to 10°C, irradiation by a high pressure mercury lamp was conducted for 10 hours. After washing with water, the organic layer was recovered and analyzed by gas chromatography and 19 F-NMR. The results are shown in Table 15.
  • reaction mixture was purified by distillation to obtain 210 g of R225cb (3,3-dichloro-l,l,2,2,3- pentafluoropropane) (yield: 62%).
  • the ratio of R215cb to R215ca formed was 87:13. Then, into an Inconel 600 U- shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm, 100 £ of a platinum catalyst supported on active carbon (supported rate: 0.5%) was packed to obtain a reactor for reduction, and the reactor was maintained at a temperature of 150°C. To this reactor, a mixture of gasified R215cb and R215ca was supplied at a rate of 96 m ⁇ /min and hydrogen gas was supplied at a rate of 144 m ⁇ /min, and the reaction was conducted. After removing an acid content, 5.7 kg of the products were recovered in a trap cooled to -78°C, and analyzed by gas chromatography and 19 F-NMR. The results are shown in

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Abstract

A process for producing a dichloropentafluoropropane, which comprises subjecting CF2=CF2 and CCl3X (wherein X is Cl, F or H) to an addition reaction, and reducing and/or fluorinating the resulting C3Cl3F4X to obtain C3Cl2F5H.

Description

DESCRIPTION TITLE OF THE INVENTION PROCESS FOR PRODUCING A DICHLOROPENTAFLUOROPROPANE TECHNICAL FIELD
The present invention relates to a process for producing a dichloropentafluoropropane (R225) such as 3,3-dichloro-l,l,l,2,2-pentafluoropropane (R225ca) or l,3-dichloro-l,l,2,2,3-pentafluoropropane (R225cb). Such a dichloropentafluoropropane is expected to be useful as a foaming agent, a cooling medium or a cleaning agent like conventional chlorofluorocarbons (CFCS).
BACKGROUND TECHNIQUE As a method for producing the dichloropentafluoropropane (R225), it is known to synthesize it by adding dichlorofluoromethane to tetrafluoroethylene in the presence of aluminum chloride. However, this method produces, in addition to the desired products, by-products which are hardly separable by a usual method such as distillation since their boiling points are close to that of the desired products, and thus has a disadvantage that a multi-step purification process is required to obtain the products in high purity. DISCLOSURE OF THE INVENTION
The present inventors have conducted extensive studies on a process for efficiently producing the dichloropentafluoropropane (R225). As a result, they have found it possible to obtain a dichloropentafluoropropane (C3C^2F5H) in good yield by subjecting tetrafluoroethylene (CF2=CF2) and CC^3X (wherein X is W, F or H) to an addition reaction, and reducing and/or fluorinating the resulting C3C^3F4X. The present invention has been accomplished on the basis of this discovery.
Thus, the present invention provides a process for producing a dichloropentafluoropropane, which comprises subjecting CF2=CF2 and CC^3X (wherein X is W, F or H) to an addition reaction, and reducing and/or fluorinating the resulting C3C 3F4X to obtain C3C- 2F5H.
BEST MODE OF CARRYING OUT THE INVENTION Now, the present invention will be described in detail with reference to the preferred embodiments.
When trichlorofluoromethane (Rll) is reacted with tetrafluoroethylene (4F) in the presence of a Lewis acid catalyst, trichloropentafluoropropanes such as 1,1,3- trichloro-1,2,2,3,3-pentafluoropropane (R215ca) and l,l,l-trichloro-2,2,3,3,3-pentafluoropropane (R215cb) are obtained in good yield.
The proportionas of R215ca and R215cb formed by this addition reaction vary depending upon the catalyst and reaction conditions employed.
As the Lewis acid catalyst useful for the reaction of the present invention, it is possible to employ a halide containing at least one element selected from the group consisting of B, &£ , Ga, In, Fe, Ni, Co, Sb, Nb, Sn, Ti, Zr, W, Hf and Ta, such as a chloride, e.g. BC^3, A£C43 , GaC-ι?3, InC^3, FeC^3, NiC^2, CoC^2, NbC^5, SnC^2, TiC^4, ZrC^4, C^6, HfC-4 or TaC^5, a partially fluorinated compound thereof, a bromide or iodide, e.g. Gal3, HfBr4, Hfl4, InBr3, Inl3, TiBr4, TaBr5, A^Br3, &£I3 , BBr3 or BI3, a partially chlorinated or fluorinated compound thereof, or a fluoride such as BF3 or SbF5. The reaction can be conducted in an inert solvent such as perfluorooctane or perfluorobutyltetrahydrofuran. However, to make the purification easy, it is usually preferred to conduct the reaction in the absence of any solvent. The catalyst is used usually in an amount of from 0.01 to 50% by weight, preferably from 0.1 to 10% by weight, relative to the starting material. The reaction temperature is usually within a range of from -80 to 200°C, preferably from -20 to 100°C, and the reaction pressure is usually from 0 to 20 kg/cm , preferably from 0 to 10 kg/cm2. For the reaction, 4F is used usually 1.0 to 1.5 times the molar quantity of Rll. The Lewis acid catalyst is usually used in an amount of from 0.1 to 50 weight%, preferably from 0.1 to 10 weight%, relative to Rll. The reduction of trichloropentafluoropropane (R215) obtained by this reaction can be conducted by using various reducing methods such as a method of conducting the reduction under irradiation, a method for conducting the reduction by means of zinc, or a method for conducting the reduction by using hydrogen in the presence of a catalyst, whereby dichloropentafluoropropane (R225), such as 3,3-dichloro- 1,1,1,2,2-pentafluoropropane (R225ca) or 1,3-dichloro- 1,1,2,2,3-pentafluoropropane (R225cb) can be obtained. In the case of conducting the reduction under irradiation, as a compound used as a proton source, an organic compound having a hydrogen atom bonded thereto is used. For example, an alcohol such as methanol, ethanol, isopropyl alcohol or sec-butyl alcohol, an alkane such as hexane or heptane, or an aromatic compound such as toluene or xylene, is preferred. Among them, a secondary alcohol such as isopropyl alcohol, is particularly preferred. Further, a solvent mixture thereof may also be employed.
The light source to be used in the present invention is not particularly limited so long as it is capable of emitting light having a wavelength of shorter than 400 nm. For example, a high pressure mercury lamp, a moderate pressure mercury lamp or a low pressure mercury lamp, may preferably be employed. The reaction is conducted usually within a temperature range of from -80 to 100°C, preferably from 0 to 40°C. There is no particular restriction as to the pressure. However, the reaction is conducted usually within a pressure range of from 0 to 10 kg/cm2G, preferably from 0 to 2 kg/cm2G.
The solvent used for the reduction by means of zinc, is not particularly limited. However, it is preferred to employ an alcohol such as methanol, ethanol or isopropyl alcohol, an organic acid such as acetic acid or formic acid, an ether such as tetrahydrofuran or water, or a mixture thereof. In particular, an alcohol such as methanol, ethanol or isopropyl alcohol is preferred. Zinc may be used in any form such as a powder, granules or fragments. However, it is most preferred to employ zinc powder. It is unnecessary to apply any special pretreatment such as activating treatment before use. The amount of zinc is not particularly limited. But it is usually preferred to employ it at least stoichiometric amount relative to the starting material. The reaction is conducted usually within a temperature range of from room temperature to 150°C, preferably from 50 to 80°C. There is no particular restriction as to the pressure, but the reaction is conducted usually within a pressure range of from 0 to 10 kg/cm2G, preferably from 0 to 3 kg/cm2G.
In a case where the reduction is conducted by using hydrogen in the presence of a catalyst, the reaction may be carried out either in a liquid phase or a gas phase. The reducing catalyst may be a noble metal catalyst such as platinum, palladium, rhodium or ruthenium, or a base metal catalyst such as nickel. However, it is particularly preferred to use a noble metal catalyst. As the carrier for the reducing catalyst, alumina or active carbon is, for example, suitable. The conventional method for preparation of a noble metal catalyst can be applied as a method for supporting the catalyst on the carrier. To use the catalyst, it is preferred to preliminarily apply reduction treatment to the catalyst to obtain the constant performance. However, such a pretreatment is not necessarily required. At least a part of such a metal compound is reduced.
The ratio of hydrogen to the starting material may be varied to a large extent. Usually, the halogen atom is removed by using hydrogen in a stoichiometrical amount. However, in order to let the starting material react almost completely, the molar ratio of the hydrogen to the starting meterial may be larger than one to one, for example, four to one or higher.
In the gas phase reaction, the reaction temperature is usually from 100 to 350°C, preferably from 100 to 200°C. The contact time is usually from 0.1 to 300 seconds, preferably from 2 to 60 seconds. When the reaction is conducted in a liquid phase, as the solvent, an alcohol such as ethanol or isopropyl alcohol, acetic acid or pyridine may be used. However, the reaction can be conducted without any solvent. The reaction temperature for the liquid phase reaction is preferably from room temperature to 150°C, and the reaction pressure - 1 -
is preferably from atmospheric pressure to 10 kg/cm2G.
On the other hand, when chloroform (R20) is reacted with tetrafluoroethylene in the presence of a Lewis acid catalyst, 1,3,3-trichloro-l,l,2,2-tetrafluoropropane (R224ca) is obtained in good yield, as shown in the following formula: CF2=CF2 + CHC-^3
Lewis acid catalyst > CC^F2CF2CHC^2
This reaction is conducted under the same conditions as in the above mentioned addition reaction of 4F with Rll.
The fluorination of l,3,3-trichloro-l,l,2,2- tetrafluoropropane (R224ca) obtained by this reaction, is conducted preferably in a gas phase in the presence of a catalyst, or in a liquid phase by using hydrogen fluoride. The proportions of R225ca and R225cb formed by the fluorination vary depending upon the catalyst and reaction conditions empolyed. As the catalyst used in the gas phase, it is possible to employ a halide or an oxide containing at least one element selected from the group consisting of K£, Cr, Mg, Ca, Ba, Sr, Fe, Ni, Co and Mn. As a method for the preparation of the catalyst, any method may be employed so long as it is a method capable of uniformly dispersing the halide or oxide containing at least one element selected from the above elements. For example, a coprecipitation method or a kneading method may be used. Particularly preferred is a method of coprecipitating hydrates from an aqueous solution of salts of the above mentioned metal elements, or a method of kneading or attriting a cake of hydroxides by a ball mill or a homogenizer. As the hydroxides, those precipitated from an aqueous solution of inorganic salts such as nitrates or sulfates by means of aqueous ammonia or urea, or those prepared by the hydrolysis of organic salts, may be employed. The catalyst in the form of hydrates is preferably dried at a temperature of from 120 to 150°C, followed by calcining usually at a temperature of from 300 to 600°C, preferably from 350 to 450°C. In the present invention, it is preferred to conduct activation of the catalyst. This object can be accomplished usually by applying fluorinating treatment usually at a temperature of from 100 to 450°C, preferably from 200 350°C. The activation can be conducted in the fluorination reaction system, or by heating with a fluorinated hydrocarbon. The reaction is conducted usually in a gas phase under atmospheric pressure or an elevated pressure within a temperature range of from 150 to 550°C, preferably from 250 to 450°C. The ratio of hydrogen fluoride to the starting material may be varied to a large extent. The chlorine atom is substituted usually by using a stoichiometrical amount of hydrogen fluoride. However, it is possible to use hydrogen fluoride in a larger amount, for example, four molar excess or higher than the stoichiometrical amount of the total molar amount of the starting material. The contact time is usually from 0.1 to 300 seconds, preferably from 5 to 30 seconds. As the catalyst used in the liquid phase, it is possible to use a fluorination catalyst consisting of a halide of e.g. Sb, Nb, Ta or Sn, such as SbF5, SbC^5, SbC^2F3, NbC^5, NbF5, SbC^5, NbC^5, NbF5, TaF5, aC^5 or SnC- 4. The fluorination reaction is conducted in a liquid phase under atmospheric pressure or an elevated pressure usually within a temperature range of from 0 to 200°C, preferably from room temperature to 150°C. In the present invention, the reaction is usually conducted in the absence of any solvent. However, a solvent may be employed. The solvent employed in such a case is not particularly limited so long as it is capable of dissolving propanes as the starting materials, and the solvent itself is hardly fluorinated as compared with the starting material. Further, the reaction pressure is usually from 0 to 10 kg/cm2G, and when a solvent is used, the reaction pressure depends upon the type of the solvent.
Hydrogen fluoride may be charged before the reaction. However, it is more effective to feed it into the liquid phase as the reaction proceeds. As another embodiment, when carbon tetrachloride
(R10) is reacted with tetrafluoroethylene in the presence of a Lewis acid catalyst, 1,1,1,3- tetrachlorotetrafluoropropane (R214cb) obtained in good yield, as shown in the following formula: CF2=CF2 + CC 4
Lewis acid catalyst _> CC F2CF2CC 3
This reaction is conducted under the same conditions as the addition reaction of 4F with Rll mentioned above. The reduction of the resulting R214cb is conducted in the same manner as the reduction of R215cb described above, to obtain 1,3,3-trichloro-l,1,2,2-tetrafluoropropane (R224ca) .
The fluorination of the resulting R224ca is also conducted in the same manner as the above described fluorination described above to obtain dichloropentafluoropropane.
Further, R214cb obtained by the addition reaction of 4F with RIO, may firstly be fluorinated in the same manner as the fluorination of R224ca, to form trichloropentafluoropropane such as R215ca or R215cb, which is then reduced in the same manner to obtain dichloropentafluoropropane such as R225cb or R225ca.
The proportions of R215ca and R215cb formed by the fluorination vary depending upon the catalyst and reaction conditions employed. Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples. Example 1
Into a 10 e Hastelloy C autoclave, 0.5 kg (3.7 mol) of anhydrous aluminum chloride was added, and the autoclave was deaerated. Then, 5 kg (36.4 mols) of Rll was added thereto. The autoclave was cooled to 0°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature between 10 and 20°C. After adding 4 kg (40 mol) of tetrafluoroethylene, stirring was continued for further one hour. Then, the reaction mixture was filtered, and the products were purified by distillation to obtain 6.1 kg of R 215cb (yield: 71%). Then, into an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm, 100 m4 of a platinum catalyst supported on active carbon (supported rate: 0.5%) was packed to obtain a reactor for reduction, and the reactor was maintained at a temperature of 120°C. To this reactor, gasified R215cb was supplied at a rate of 96 m^/min and hydrogen gas was supplied at a rate of 144 m^/min, and the reaction was conducted. After removing an acid content, 4.5 kg of the products were recovered in a trap cooled to -78°C, and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 1. Table 1
Figure imgf000014_0001
The products were purified by distillation to obtain 3.6 kg of R225ca (yield: 68%). Example 2
Into a 10 έ Hastelloy C autoclave, 0.5 kg (3.7 mol) of aluminum chloride was added, and the autoclave was deaerated under reduced pressure. Then, 5 kg (36.4 mol) of Rll was added thereto. The autoclave was cooled to 0°C, and tetrafluoroethylene was continuously added while maintaining the reaction temperature between 10 and 20°C. After adding 4 kg (40 mol) of tetrafluoroethylene, stirring was continued for further one hour. The reaction mixture was filtered, and the products were purified by distillation to obtain 6.1 kg of R215cb (yield: 71%). Then, into a 1,000 m£ glass three-necked round bottom flask, 200 g (6 mol) of methanol and 300 of (4.6 mol) zinc powder were added, while stirring the mixture at 0°C, 1,000 g (4.2 mol) of R215cb was dropwise added thereto. After completion of the dropwise addition, stirring was continued for further 8 hours at 0°C. Then, the reaction solution was washed with a 2N hydrochloric acid aqueous solution. 900 g of the organic layer was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 2.
Table 2
Figure imgf000015_0001
The reaction mixture was purified by distillation to obtain 350 g of R225ca (yield: 41%). Preparation Example 1
1,200 g of Cr(N03)3-9H20 and 100 g of Mg(N03)2-6H20 were dissolved in 2.5 £ of water. This solution and 2,000 g of a 28% ammonium hydroxide aqueous solution were added into 4 £ of heated water under stirring to obtain precipitates of hydroxides. The precipitates were collected by filtration, washed with distilled water and dried, and then they were calcined at 450°C for 5 hours to obtain the oxide powder. This powder was molded into cylinders having a diameter of 5 mm and a height of 5 mm by means of a tabletting machine. The catalyst thus obtained was fluorinated in a stream of a gas mixture of hydrogen fluoride/nitrogen at a temperature of from 200 to 400°C for activation prior to the reaction. Preparation Example 2
1,100 g of iλ£(No3)3-9H20 as guarantied reagent, 125 g of Cr(N03)3-9H20 and 40 g of Mg(N03)2-6H20 were dissolved in 2.5 £ of water. This solution and 2,000 g of a 28% ammonium hydroxide aqueous solution were added into 4 £ of heated water under stirring to obtain precipitates of hydroxides. The precipitates were collected by filtration, washed with distilled water and dried, and then they were calcined at 450°C for 5 hours to obtain the oxide powder. This powder was molded into cylinders having a diameter of 5 mm and a height of 5 mm by means of a tabletting machine. The catalyst thus obtained was fluorinated in a stream of a gas mixture of hydrogen fluoride/nitrogen at a temperature of from 200 to 400°C for activation prior to the reaction. Example 3
Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added, and the autoclave was deaerated under reduced pressure. Then, 9 kg (75.3 mol) of R20 (CHC^3) was added thereto. The autoclave was heated to 65°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 4 kg (40 mol) of tetrafluoroethylene, stirring was continued for further one hour. Then, the reaction solution was filtered, and the reaction mixture was purified by distillation to obtain 7.5 kg of R224ca (l,3,3-trichloro-l,l,2,2- tetrafluoropropane) (yield: 85%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 m£ of a fluorination catalyst prepared as described in Preparation Example 1 was packed therein. The reactor was heated to 280°C, and 160 m^/ in of gasified R224ca and 440 m^/min of hydrogen fluoride were supplied thereto, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 6.8 kg of the reaction mixture was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 3.
Table 3
Figure imgf000017_0001
The reaction mixture was purified by distillation to obtain 4.7 kg of R225 (dichloropentafluoropropane) (yield: 68%). Example 4 Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added, and the autoclave was deaerated under reduce pressure. Then, 9 kg (75.3 mol) of R20 (CHC^3) was added thereto. The autoclave was heated to 65°C, and tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 4 kg (40 mol) of tetrafluoroethylene, stirring was continued for further one hour. The reaction solution was filtered, and the reaction crude solution was purified by distillation to obtain 7.5 kg of R224ca (1,3,3-trichloro-l,1,2,2-tetrafluoropropane) (yield: 85%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 m£ of a fluorination catalyst prepared as described in Preparation Example 2, was packed. The reactor was heated to 320°C, and 160 m^/min of gasified R224ca and 440 m^/min of hydrogen fluoride were supplied, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 6.9 kg of the reaction mixture was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 4. Table 4
Figure imgf000019_0001
The reaction mixture was purified by distillation to obtain 3.8 kg of R225 (dichloropentafluoropropane) (yield: 55%). Example 5
Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added and the autoclave was deaerated under reduced pressure. Then, 9 kg (58.5 mols) of R10 ( CC£A ) was add thereto. The autoclave was heated to 65°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 4 kg (40 mols) of tetrafluoroethylene, stirring was continued for further one hour. Then, the reaction mixture was filtered, and the products were purified by distillation to obtain 6.5 kg of R214cb (1,1,1,3-tetrachlorotetrafluoropropane) (yield: 85%). Then, into an Inconel 600 U-shaped reactor having with inner diameter of 2.54 cm and a length of 100 cm, 100m^ of a platinum catalyst supported on active carbon (supported rate: 0.5%) was packed to form a reactor for reduction, and the reactor was maintained at 120°C. To this reactor, 120 m-^/min of gasified R214cb and 180m^/min of hydrogen gas were supplied, and the reaction was conducted. An acid content was removed, and then 5.4 kg of the reaction mixture was recovered in a trap cooled to -78°C and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 5.
Table 5
Figure imgf000020_0001
The reaction mixture was purified by distillation to obtain 4.1 kg of R224ca (l,3,3-trichloro-l,l,3-trichloro- 1,1,2,2-tetrafluoropropane) (yield: 73%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 m£ of a fluorination catalyst prepared as described in Preparation Example 1, was packed. The reactor was heated to 280°C, and 160 m^/min of gasified R224ca and 440 m^/min of hydrogen fluoride were supplied thereto, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 3.7 kg of the reaction mixture was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 6.
Table 6
Figure imgf000021_0001
The reaction mixture was purified by distillation to obtain 2.5 kg of R225 (dichloropentafluoropropane) (yield: 67%). Example 6 Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added and the autoclave was deaerated under reduced pressure. Then, 9 kg (58.5 mols) of RIO (CC*4) was added thereto. The autoclave was heated to 65°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 3 kg (30 mols) of tetrafluoroethylene, stirring was continued for further one hour. Then, the reaction mixtuer was filtered, and the products were purified by distillation to obtain 6.5 kg of R214cb (1,1,1,3-tetrachlorotetrafluoropropane) (yield: 85%). Then, into an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm, 100sx£ of a platinum catalyst supported on active carbon (supporting rate: 0.5%) was packed to form a reactor for reduction, and the reactor was maintained at 120°C. To the reactor, 120 m^/min of gasified R214cb and 180 m^/min of hydrogen gas were supplied, and the reaction was conducted. An acid content was removed, and then 5.5 kg of a reaction mixture was recovered in a trap cooled to - 78°C and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 7. Table 7
Figure imgf000023_0001
The reaction mixture was purified by distillation to obtain 4.1 kg of R224ca (l,3,3-trichloro-l,l,2,2- tetrafluoropropane) (yield: 73%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 m£ of a fluorination catalyst prepared as described in Preparation Example 2, was packed thereto. The reactor was heated to 320°C, and 160 m^/min of gasified R224ca and 440 m^/min of hydrogen fluoride were supplied thereto, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 3.8 kg of the reaction mixture was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 8. Table 8
Figure imgf000024_0001
The reaction mixture was purified by distillation to obtain 2.1 kg of R225 (dichloropentafluoropropane) (yield: 57%). Example 7
Into a 10 ^ Hastelloy C autoclave, 0.5 kg (3.7 mol) of anhydrous aluminum chloride was added and the autoclave was deaerated under reduced pressure. Then, 9 kg (58.5 mol) of R10 ( CC£ ) was added thereto. The autoclave was heated to 65°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 3 kg (30 mols) of tetrafluoroethylene, stirring was continued for further one hour. Then, the reaction mixture was filtered, and the products were purified by distillation to obtain 6.5 kg of R214cb (1,1,1,3-tetrachlorotetrafluoropropane) (yield: 85%). Then, into a 1,000 £ of glass three- necked round bottom flask, 200 g (6 mols) of methanol and 300 g (4.6 mols) of zinc powder were added. While stirring the mixture at 0°C, 1,000 g (3.9 mols) of R214cb was dropwise added. After completion of the dropwise addition, stirring was continued for further 8 hours at 0°C. Then, the reaction solution was washed with a 2N hydrochloric acid aqueous solution. 900 g of the organic layer was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 9.
Table 9
Figure imgf000025_0001
- 24 -
The reaction mixture was purified by distillaiton to obtain 190 g of R224ca (l,3,3-trichloro-l,l,2,2- tetrafluoropropane) . Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.5 cm and a length of 100 cm as a reactor for fluorination, 200 m£ of a fluorination catalyst prepared as described in Preparation Example 1, was packed. The reactor was heated to 280°C, and 160 m^/min of R224ca and 440 m^/min of hydrogen fluoride were supplied thereto, and the reaction was conducted. The reaction was stopped when 1 kg of R224ca was supplied, and the reaction crude gas was passed through an aqueous alkaline solution, and 0.9 kg of a reaction mixture was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 10.
Table 10
Figure imgf000026_0001
The reaction mixture was purified by distillation to obtain 0.6 kg of R225 (dichloropentafluoropropane) (yield: 68%). Example 8 Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added and the autoclave was deaerated under reduced pressure. Then, 9 kg (58.5 mols) of RIO (CC^4) was added thereto. The autoclave was heated to 65°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 3 kg (30 mols) of tetrafluoroethylene, stirring was continued for further one hour. The reaction mixture was filtered, and the products were purified by distillation to obtain 6.5 kg of R214cb (1,1,1,3-tetrachlorotetrafluoropropane) (yield: 85%). Then, into a photochemical reactor (EHB-W1F-500 Model, manufactured by Eiko Co., LTD.), 800 m£ of isopropanol and 400 g of R214ca were charged, and the reaction solution was irradiated by a high pressure mercury lamp for 20 hours under cooling at 10°C. After washing with water, the organic layer was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 11. Table 11
Figure imgf000028_0001
The reaction mixture was purified by distillaiton to obtain 240 g of R224ca (l,3,3-trichloro-l,l,2,2- tetrafluoropropane) (yield: 70%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 £ of a fluorination catalyst prepared as described in Preparation Example 1 was packed thereto. The reactor was heated to 280°C, and 160 m^/ in of gasified R224ca and 440 m-^/min of hydrogen fluoride were supplied thereto, and the reaction was conducted. The reaction was stopped when 3 kg of R224ca was supplied. The reaction crude gas was passed through an aqueous alkaline solution, and 2.7 kg of the reactoin mixture was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 12. Table 12
Figure imgf000029_0001
The reaction mixture was purified by distillation to obtain 1.9 kg of R225 (dichloropentafluoropropane) (yield: 68%). Example 9
Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added and the autoclave was deaerated under reduced pressure. Then, 9 kg (58.5 mols) of R10 (CC^4) was added thereto. The autoclave was heated to 65°C, and then * tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 3 kg (30 mols) of tetrafluoroethylene, stirring was continued for further one hour. The reaction mixture was filtered, and the reaction crude solution was purified by distillation to obtain 6.5 kg of R214cb (1,1,1,3- tetrachlorotetrafluoropropane) (yield: 86%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200
Figure imgf000030_0001
of a fluorination catalyst prepared as described in Preparation Example 1 was packed. The reactor was heated to 280°C, and 240 m^/min of gasified R214cb and 360 m^/min of hydrogen fluoride were supplied thereto, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 6.0 kg of the reaction mixture was recovered and purified by distillation to obtain 5.1 kg of R215ca (1,1,3-trichloropentafluoropropane) (yield: 83%). Then, into an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm, 100 _xι£ of a platinum catalyst supported on active carbon (supported rate:0.5 %) was packed to form a reactor for reduction, and the reactor was maintained at 170°C. To this reactor, 96 m^/ in of gasified R215ca and 144 m^/min of hydrogen gas were supplied, and the reaction was conducted. An acid content was removed, and 4.1 kg of a reaction mixture was recovered in a trap cooled to -78°C, and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 13. Table 13
Figure imgf000031_0001
The reaction mixture was purified by distillation to obtain 3.0 kg of R225ca (3,3-dichloro-l,l,2,2,3- pentafluoropropane) (yield: 69%). Example 10
Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mols) of anhydrous aluminum chloride was added, and the autoclave was deaerated under reduced pressure. Then, 9 kg (58.5 mols) of R10 (CC^4) was added thereto. The autoclave was heated to 65°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature to a level of from 65 to 80°C. After adding 3 kg (30 mols) of tetrafluoroethylene, stirring was continued for further one hour. Then, the reaction mixture was filtered, and the products were purified by distillation to obtain 6.5 kg of R214cb (1,1,1,3-tetrachlorotetrafluoropropane) (yield: 85%) . Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.5 cm and a length of 100 cm as a reactor for fluorination, 200 £ of a fluorination catalyst prepared as described in
Preparation Example 2 was packed. The reactor was heated to 320°C, and 240 m^/min of gasified R214cb and 360 m^/min of hydrogen fluoride were supplied, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 5.2 kg of the reaction mixture was recovered and purified by distillation to obtain 4.9 kg of R215ca (1,1,3- trichloropentafluoropropane) (yield: 80%). Then, into an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm, 100 m£ of a platinum catalyst supported on active carbon (supported rate: 0.5%) was packed to form a reactor for reduction, and the reactor was maintained at 170°C. To this reactor, 96 m^/min of gasified R215ca and 144 m^/min of hydrogen gas were supplied, and the reaction was conducted. An acid content was removed, and then 3.9 kg of a reaction mixture was recovered in a trap cooled to -78°C, and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 14. Table 14
Figure imgf000033_0001
The reaction mixture was purified by distillation to obtain 2.9 kg of R225cb (3,3-dichloro-l,l,2,2,3- pentafluoropropane) (yield: 69%). Example 11
Into a 10 £ Hastelloy C autoclave, 0.5 kg (3.7 mol) of anhydrous aluminum chloride was added and the autoclave was deaerated under reduced pressure. Then, 9 kg (58.5 mols) of R10 ( CC£A ) was added thereto. The autoclave was heated to 65°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature at a level of from 65 to 80°C. After adding 3 kg (30 mols) of tetrafluoroethylene, stirring was continued for further one hour. Then, the reaction mixture was filtered, and the products were purified by distillation to obtain 6.5 - 32 - kg of R214cb (1,1,1,3-tetrachlorotetrafluoropropane) (yield: 85%). Then, using an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm as a reactor for fluorination, 200 £ of a fluorination catalyst prepared as described in
Preparation Example 1 was packed. The reactor was heated to 280°C, and 240 m^/min of gasified R214cb and 360 m^/min of hydrogen fluoride were supplied, and the reaction was conducted. The reaction crude gas was passed through an aqueous alkaline solution, and 6.0 kg of the reaction mixture was recovered. The products were purified by distillation to obtain 5.1 kg of R215ca (1,1,3-trichloropentafluoropropane) (yield: 83%). Then, into a photochemical reactor (EHB-W1F-500 Model, manufactured by Eiko Co., Ltd.), 800 m£ of isopropanol and 400 g of R215ca were charged. While cooling the reaction solution to 10°C, irradiation by a high pressure mercury lamp was conducted for 10 hours. After washing with water, the organic layer was recovered and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 15.
Table 15
Figure imgf000034_0001
The reaction mixture was purified by distillation to obtain 210 g of R225cb (3,3-dichloro-l,l,2,2,3- pentafluoropropane) (yield: 62%).
As shown by the foregoing Examples, according to the present invention, 3,3-dichloro-l,l,l,2,2- pentafluoropropane (R225ca) and 1,3-dichloro-l,1,2,2,3- pentafluoropropane (R225cb) which used to be difficult to obtain in a highly pure form, can be produced in good yield. Example 12
Into a 10 £ Hastelloy C autoclave, 0.05 kg (0.37 mol) of anhydrous aluminum chloride was added, and the autoclave was deaerated. Then, 5 kg (36.4 mol) of Rll was added thereto. The autoclave was cooled to 0°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature between 10 and 20°C. After adding 4 kg (40 mol) of tetrafluoroethylene, stirring was continued for further one hour. Then, the reaction mixture was filtered, and the products were purified by distillation to obtain 7.6 kg of a mixture of R215cb and R215ca (yield: 88%). The ratio of R215cb to R215ca formed was 87:13. Then, into an Inconel 600 U- shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm, 100 £ of a platinum catalyst supported on active carbon (supported rate: 0.5%) was packed to obtain a reactor for reduction, and the reactor was maintained at a temperature of 150°C. To this reactor, a mixture of gasified R215cb and R215ca was supplied at a rate of 96 m^/min and hydrogen gas was supplied at a rate of 144 m^/min, and the reaction was conducted. After removing an acid content, 5.7 kg of the products were recovered in a trap cooled to -78°C, and analyzed by gas chromatography and 19F-NMR. The results are shown in
Table 16.
Table 16
Figure imgf000036_0001
The products were purified by distillation to obtain 4.7 kg of a mixture of R225ca and R225cb (yield: 72%). Example 13
Into a 10 £ Hastelloy C autoclave, 0.5 kg (2.6 mol) of titanium tetrachloride was added, under a nitrogen stream, 5 kg (36.4 mol) of Rll was added thereto. The autoclave was heated to 40°C, and tetrafluoroethylene was continuously added while maintaining the reaction temperature between 40 and 50°C. After adding 4 kg (40 mol) of tetrafluoroethylene, stirring was continued for further one hour. The reaction mixture was washed with water, and the organic solution was purified by distillation to obtain 7.2 kg of a mixture of R215cb and R215ca (yield: 84%). The ratio of R215cb to R215ca formed was 53:47. Then, into an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm, 100 m£ of a platinum catalyst supported on active carbon (supported rate: 0.5%) was packed to obtain a reactor for reduction, and the reactor was maintained at a temperature of 170°C. To this reactor, a mixture of gasified R215cb and R215ca was supplied at a rate of 96 m^/min and hydrogen gas was supplied at a rate of 144 m^/min, and the reaction was conducted. After removing an acid content, 5.6 kg of the products were recovered in a trap cooled to -78°C, and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 17.
Table 17
Figure imgf000038_0001
The products were purified by distillation to obtain 4.2 kg of a mixtuer of R225ca and R225cb (yield: 69%). Example 14
Into a 10 £ Hastelloy C autoclave, 0.1 kg (0.43 mol) of zirconium (IV) chloride was added, under a nitrogen stream and 5 kg (36.4 mol) of Rll was added thereto. The autoclave was cooled to 0°C, and then tetrafluoroethylene was continuously added while maintaining the reaction temperature between 0 and 10°C. After adding 4 kg (40 mol) of tetrafluoroethylene, stirring was continued for further two hours. Then, the reaction mixture was washed with water, and the organic solution was purified by - 37 - distillation to obtain 7.6 kg of a mixture of R215cb and R215ca (yield: 88%). Then, into an Inconel 600 U-shaped reactor with an inner diameter of 2.54 cm and a length of 100 cm, 100 m£ of a platinum catalyst supported on active carbon (supported rate: 0.5%) was packed to obtain a reactor for reduction, and the reactor was maintained at a temperature of 170°C. To this reactor, a mixture of gasified R215cb and R215ca was supplied at a rate of 96 m^/ in and hydrogen gas was supplied at a rate of 144 m^/min, and the reaction was conducted. After removing an acid content, 5.6 kg of the products were recovered in a trap cooled to -78°C, and analyzed by gas chromatography and 19F-NMR. The results are shown in Table 18.
Table 18
Figure imgf000039_0001
The products were purified by distillation to obtain 4.1 kg of a mixture of R225ca and R225cb (yield: 63%). Example 15
The reaction conducted in the same manner as in Example 14 except that instead of zirconium (IV) chloride, 0.5 kg of titanium fluorochloride (TiC-F3) was used. As a results, 7.2 kg of R215 as the reaction intermediate (R215ca : R215cb = 50 : 50) and 5.7 kg of the products of R225 were obtained. The results of the analyses by gaschromatography and 19F-NMR are shown in Table 19.
Table 19
Figure imgf000040_0001
The products were purified by distillation to obtain 4.3 kg of a mixture of R225ca and R225cb (yield: 70%).

Claims

1. A process for producing a dichloropentafluoropropane, which comprises subjecting CF2=CF2 and CC£3X (wherein X is C£, F or H) to an addition reaction, and reducing and/or fluorinating the resulting C3C^3F4X to obtain
2. A process for producing dichloropentafluoropropane according to Claim 1, which comprises adding trichlorofluoromethane to tetrafluoroethylene to form trichloropentafluoropropane, and then reducing it.
3. The process according to Claim 2, wherein the reaction to form trichloropentafluoropropane by adding trichlorofluoromethane to tetrafluoroethylene, is conducted in the presence of a Lewis acid catalyst.
4. The process according to Claim 2, wherein the reducing reaction is conducted by using hydrogen in the presence of a reducing catalyst, or by using an organic compound having a hydrogen atom bonded thereto in the presence of zinc or under irradiation.
5. A process for producing dichloropentafluoropropane according to Claim 1, which comprises adding chloroform to tetrafluoroethylene to form l,3,3-trichloro-l,l,2,2- tetrafluoropropane, and then fluorinating it to obtain dichloropentafluoropropane. *
6. The process according to Claim 5, wherein the reaction to form l,3,3-trichloro-l,l,2,2- tetrafluropropane by adding chloroform to tetrafluoroethylene, is conducted in the presence of a Lewis acid catalyst.
7. The process according to Claim 5, wherein the fluorination of 1,3,3-trichloro-l,1,2,2- tetrafluoropropane is conducted by using hydrogen fluoride in the presence of a catalyst, in a liquid phase or in a gas phase.
8. A process for producing dichloropentafluoropropane according to Claim 1, which comprises adding carbon tetrachloride to tetrafluoroethylene to form 1,1,1,3- tetrachlorotetrafluoropropane, then reducing it to form 1,3,3-trichloro-l,1,2,2-tetrafluoropropane, and then fluorinating it.
9. The process according to Claim 8, wherein the reaction to form 1,1,1,3-tetrachlorotetrafluoropropane by adding carbon tetrachloride to tetrafluoroethylene, is conducted in the presence of a Lewis acid catalyst.
10. The process according to Claim 8, wherein the reduction of 1,1,1,3-tetrachlorotetrafluoropropane is conducted by using hydrogen in the presence of a reducing catalyst, or by using an organic compound having a hydrogen atom bonded thereto in the presence of zinc or under irradiation.
11. The process according to Claim 8, wherein the fluorination of 1,3,3-trichloro-l,1,2,2- tetrafluoropropane is conducted by using hydrogen fluoride in the presence of a catalyst, in a liquid phase or in a gas phase.
12. The process for producing dichloropentafluoropropane according to Claim 1, which comprises adding carbon tetrachloride to tetrafluoroethylene to form 1,1,1,3- tetrachlorotetrafluoropropane, then fluoriding it to form trichloropentafluoropropane, and then reducing it.
13. The process according to Claim 12, wherein the reaction to form 1,1,1,3-tetrachlorotetrafluoropropane by adding carbon tetrachloride to tetrafluoroethylene, is conducted in the presence of a Lewis acid catalyst.
14. The process according to Claim 12, wherein the fluorination of 1,1,1,3-tetrachlorotetrafluoropropane is conducted by using hydrogen fluoride in the presence of a catalyst, in a liquid phase or in a gas phase.
15. The process according to Claim 12, wherein the reduction of trichloropentafluoropropane is conducted by using hydrogen in the presence of a reducing catalyst, or by using an organic compound having a hydrogen atom bonded thereto in the presence of zinc or under irradiation.
PCT/JP1990/000924 1989-07-21 1990-07-18 Process for producing a dichloropentafluoropropane WO1991001287A1 (en)

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JP1187523A JP2738042B2 (en) 1989-07-21 1989-07-21 Method for producing 3,3-dichloro-1,1,1,2,2-pentafluoropropane
JP1/187523 1989-07-21
JP1/217554 1989-08-25
JP21755489A JP2734670B2 (en) 1989-08-25 1989-08-25 Method for producing 1,3-dichloro-1,1,2,2,3-pentafluoropropane
JP21755589A JP2734671B2 (en) 1989-08-25 1989-08-25 Method for producing dichloropentafluoropropane
JP21755389A JP2734669B2 (en) 1989-08-25 1989-08-25 Manufacturing method of dichloropentafluoropropane
JP1/217555 1989-08-25
JP1/217553 1989-08-25
JP1/263098 1989-10-11
JP26309889A JP2849129B2 (en) 1989-10-11 1989-10-11 Method for producing 1,3-dichloro-1,1,2,2,3-pentafluoropropane

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WO1992013817A1 (en) * 1991-02-01 1992-08-20 E.I. Du Pont De Nemours And Company Process for the manufacture of halogen-substituted propanes containing hydrogen and at least five fluorine substituents
US6191327B1 (en) * 1990-11-27 2001-02-20 Asahi Glass Company Ltd. Method for producing dichloropentafluoropropanes
WO2002059230A2 (en) 2001-01-24 2002-08-01 Honeywell International Inc. Azeotrope-like composition of 1,2,2-trichloro-1,3,3,3-tetrafluoropropane and hydrogen fluoride
WO2008060614A2 (en) * 2006-11-15 2008-05-22 E. I. Du Pont De Nemours And Company Process for producing 2,3,3,3-tetrafluoropropene
WO2010001768A1 (en) * 2008-07-01 2010-01-07 Daikin Industries, Ltd. Process for producing fluorine-containing propene compounds
US7906693B2 (en) * 2006-10-31 2011-03-15 E.I. Du Pont De Nemours And Company Processes for producing 2,3,3,3-tetrafluoropropene, a process for producing 1-chloro-2,3,3,3-pentafluoropropane and azeotropic compositions of 1-chloro-2,3,3,3-tetrafluoropropene with HF
US20110237847A1 (en) * 2006-09-05 2011-09-29 E.I. Du Pont De Nemours And Company process for the manufacture fluorocarbons
US8618040B2 (en) 2003-11-04 2013-12-31 Honeywell International Inc. Solvent compositions containing chlorofluoroolefins or fluoroolefins
WO2017146190A1 (en) * 2016-02-26 2017-08-31 旭硝子株式会社 Method for producing purified 1-chloro-2,3,3,3-tetrafluoropropene and purified 1-chloro-2,3,3,3-tetrafluoropropene (z)
CN109563010A (en) * 2016-08-09 2019-04-02 Ａｇｃ株式会社 The manufacturing method of the chloro- 2,3,3,3- tetrafluoropropene of 1-
JP2019156732A (en) * 2018-03-08 2019-09-19 ダイキン工業株式会社 PROCESS FOR REFINING HCFC-224ca AND/OR CFO-1213ya, PROCESS FOR PRODUCING HCFC-224ca, AND PROCESS FOR PRODUCING CFO-1213ya

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Cited By (21)

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US6191327B1 (en) * 1990-11-27 2001-02-20 Asahi Glass Company Ltd. Method for producing dichloropentafluoropropanes
WO1992013817A1 (en) * 1991-02-01 1992-08-20 E.I. Du Pont De Nemours And Company Process for the manufacture of halogen-substituted propanes containing hydrogen and at least five fluorine substituents
WO2002059230A2 (en) 2001-01-24 2002-08-01 Honeywell International Inc. Azeotrope-like composition of 1,2,2-trichloro-1,3,3,3-tetrafluoropropane and hydrogen fluoride
WO2002059230A3 (en) * 2001-01-24 2002-09-26 Honeywell Int Inc Azeotrope-like composition of 1,2,2-trichloro-1,3,3,3-tetrafluoropropane and hydrogen fluoride
US6534467B2 (en) 2001-01-24 2003-03-18 Honeywell International Inc. Azeotrope-like composition of 1,2,2-trichloro-1,3,3,3-tetrafluoropropane and hydrogen fluoride
CN100406535C (en) * 2001-01-24 2008-07-30 霍尼韦尔国际公司 Azeotrope-like composition of 1,2,2-trichloro-1,3,3,3-tetrafluoropropane and hydrogen fluoride
US10066140B2 (en) 2003-11-04 2018-09-04 Honeywell International Inc. Compositions containing chlorofluoroolefins or fluoroolefins
US9586071B2 (en) 2003-11-04 2017-03-07 Honeywell International Inc. Compositions containing chlorofluoroolefins or fluoroolefins
US9095737B2 (en) 2003-11-04 2015-08-04 Honeywell International Inc. Compositions containing chlorofluoroolefins or fluoroolefins
US8618040B2 (en) 2003-11-04 2013-12-31 Honeywell International Inc. Solvent compositions containing chlorofluoroolefins or fluoroolefins
US8354039B2 (en) * 2006-09-05 2013-01-15 E I Du Pont De Nemours And Company Process for the manufacture fluorocarbons
US20110237847A1 (en) * 2006-09-05 2011-09-29 E.I. Du Pont De Nemours And Company process for the manufacture fluorocarbons
US7906693B2 (en) * 2006-10-31 2011-03-15 E.I. Du Pont De Nemours And Company Processes for producing 2,3,3,3-tetrafluoropropene, a process for producing 1-chloro-2,3,3,3-pentafluoropropane and azeotropic compositions of 1-chloro-2,3,3,3-tetrafluoropropene with HF
US7872161B2 (en) 2006-11-15 2011-01-18 E. I. Du Pont De Nemours And Company Process for producing 2,3,3,3-tetrafluoropropene
WO2008060614A3 (en) * 2006-11-15 2008-09-04 Du Pont Process for producing 2,3,3,3-tetrafluoropropene
WO2008060614A2 (en) * 2006-11-15 2008-05-22 E. I. Du Pont De Nemours And Company Process for producing 2,3,3,3-tetrafluoropropene
WO2010001768A1 (en) * 2008-07-01 2010-01-07 Daikin Industries, Ltd. Process for producing fluorine-containing propene compounds
WO2017146190A1 (en) * 2016-02-26 2017-08-31 旭硝子株式会社 Method for producing purified 1-chloro-2,3,3,3-tetrafluoropropene and purified 1-chloro-2,3,3,3-tetrafluoropropene (z)
US10370313B2 (en) 2016-02-26 2019-08-06 AGC Inc. Manufacturing method of purified 1-chloro-2,3,3,3-Tetrafluoropropene and purified 1-chloro-2,3,3,3-tetrafluoropropene (Z)
CN109563010A (en) * 2016-08-09 2019-04-02 Ａｇｃ株式会社 The manufacturing method of the chloro- 2,3,3,3- tetrafluoropropene of 1-
JP2019156732A (en) * 2018-03-08 2019-09-19 ダイキン工業株式会社 PROCESS FOR REFINING HCFC-224ca AND/OR CFO-1213ya, PROCESS FOR PRODUCING HCFC-224ca, AND PROCESS FOR PRODUCING CFO-1213ya

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