JPH04305542A - Production of halogenated hydrocarbon compounds - Google Patents

Abstract

PURPOSE:To produce a highly pure halogenated hydrocarbon compound without passing through multi-stage reaction process and without requiring multi-stage purification process. CONSTITUTION:An olefin such as 1,1-dichlorodifluoroethylene is reacted with a halogeno alkane such as dichlorofluoromethane in the presence of a halide oxide catalyst such as zirconium chloride fluoride oxide, titanium chloride fluoride oxide, gallium chloride fluoride oxide or silicon chloride fluoride oxide to produce a >=3C halogenated hydrocarbon such as tetrachlorotrifluoropropane.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing halogenated hydrocarbons having 3 or more carbon atoms. Halogenated hydrocarbons having 3 or more carbon atoms are expected to be used as blowing agents, refrigerants, cleaning agents, etc., similar to conventionally used fluorocarbons.

0002

BACKGROUND OF THE INVENTION Conventionally known synthetic routes for halogenated hydrocarbons having 3 or more carbon atoms include, for example, the following method.

1) 2,2,3,3-tetrafluoropropanol is produced from tetrafluoroethylene and methanol, then this is reacted with sulfuryl chloride to form a chlorosulfonic acid ester, and then this is reacted with an alkali metal chloride. A method for synthesizing 1-chloro-2,2,3,3-tetrafluoropropane by reaction.

2) Methyl ethyl ketone is reacted with phosphorus pentachloride to form a chloride, then fluorinated with antimony trifluoride to form 2,2-difluorobutane, which is then chlorinated to form 1,1,1,2,2- After forming pentachloro-3,3-difluorobutane, it was further fluorinated with antimony trifluoride to form 1,2,2-trichloro-1,1,3,3-
How to make tetrafluorobutane.

3) Dichlorofluoromethane (R21) is added to tetrafluoroethylene in the presence of aluminum chloride to form 3,3-dichloro-
1,1,1,2,2-ntafluoropropane (R225
ca) and 1,3-dichloro-1,1,2,2,
A method for synthesizing 3-pentafluoropropane (R225cb).

CF2 = CF2 + CHCl2 F→C
F3 CF2 CHCl2 + CClF2 CF2 CHClF (O. Paleta et al., Collect
．． Czech. Chem. Commun. , 3
6, 1867 (1971))

[0007]

[Problems to be Solved by the Invention] Methods 1) and 2) have the drawback that they require multiple steps, making it difficult to improve the yield and making them unsuitable for industrial production. In method 3), a reaction by-product is produced that has a boiling point close to that of the desired product and is difficult to separate using normal methods such as distillation, so multiple purification steps are required to obtain a highly pure product. It has the following drawbacks.

[0008]

[Means for Solving the Problems] As a result of extensive research into efficient production methods for halogenated hydrocarbons having 3 or more carbon atoms, the present inventors have found that:

General formula MXx Fy Oz [where M is one or more elements selected from Groups 4, 5, and 13; X is one or more elements selected from Cl, Br, and I; x is 0<x<5, y is 0<y<5
, z is a real number of 0<z<2.5, x+y +z
/2 = integer of 3 to 5] in the presence of a halogenated oxide,

Olefin R1 R2 C=CR3 R4 shown below [However, R1 is H, Cl, F, Br or CF3
, CF2 Cl group, R2, R3, R4 are either the same or different H, Cl, F or Br] and the following halogenoalkane CYR5 R6 R7 [However, Y is any of Cl, F, Br or I Or R5
is Cl, F, Br, I or Ca Hb Clc F
d Bre If , where a is 0 to 4, b
, c, d are 0 to 2a+1, e, f are integers of 0 to 3, b+c+d+e+f=2a+1, 2a-1 or 2a-3, and b+c+d+e+f ≧1, R6, R
The inventors have discovered that halogenoalkanes can be produced in high yields by reacting H, Cl, F, Br, or I, each of which is the same or different, and have led to the provision of the present invention.

The details of the present invention will be explained below along with examples. That is, the olefins R1 and R2 shown below
C=CR3 R4 [However, R1 is H, Cl, F, Br or CF3
, CF2 Cl group, R2, R3, R4 are each the same or different H, Cl, F or Br],
Halogenoalkane CYR5 R6 R7 shown below [However, Y is Cl, F, Br or I, R5
is Cl, F, Br, I or Ca Hb Clc F
d Bre If , where a is 0 to 4, b,
c, d are 0 to 2a+1, e, f are integers from 0 to 3, b+c+d+e+f=2a+1, 2a-1 or 2
a-3 and b+c+d+e+f ≧1, R6, R7
are the same or different H, Cl, F, Br or I
as a catalyst when carrying out an addition reaction with

General formula MXx Fy Oz [where M is one or more elements selected from Groups 4, 5, and 13; X is one or more elements selected from Cl, Br, and I; x is 0<x<5, y is 0<y<
5. z is a real number with 0<z<2.5, x+y+z/2
= an integer of 3 to 5] is used.

[0013] By carrying out the reaction under reaction conditions in which the molar ratio of the olefin present is at least equivalent, preferably in excess, to the halogenoalkane to be added, the addition reaction proceeds with good yield. The reaction conditions are particularly preferred.

The halogenated oxide catalyst used in the present invention is
For example, Ti, Zr, Hf, V, Nb, Ta, B, Al,
An oxide containing one type of element selected from Ga, In, etc., or a composite oxide containing two or more types, with a suitable halogenating agent,
For example, chlorofluorocarbons such as trichlorofluoromethane (R11), dichlorodifluoromethane (R12), and trichlorotrifluoroethane (R113), hydrochlorofluorocarbons such as dichlorofluoromethane (R21), and chlorodifluoromethane (R22), or chlorine, fluorocarbons, etc. It can be easily prepared by treatment with hydrogen oxide (HF), fluorine gas, etc.

When making a composite oxide, group 4, group 5, group 13
Metal elements other than groups such as Si, Zn, Mg, Cr, C
Of course, it is also possible to add at least one of u, Sn, Bi, Mo, Sb, Fe, Ni, Co, etc.

The conditions for preparing the catalyst vary depending on the oxide and halogenating agent used, but the halogenating agent is usually used in an excess amount relative to the oxide.

[0017] When the preparation temperature is carried out in the gas phase, it is usually 100
A temperature of 500°C to 500°C, preferably 200 to 450°C is suitable, and when carried out in a liquid phase, a temperature of 0 to 200°C, preferably room temperature to 120°C is suitable.

Examples of the olefin used in the reaction include tetrafluoroethylene, chlorotrifluoroethylene, 1,1-dichlorodifluoroethylene, cis-1,
2-dichlorodifluoroethylene, trans-1,2
-dichlorodifluoroethylene, trichlorofluoroethylene, tetrachloroethylene, trifluoroethylene, 1-chloro-2,2-difluoroethylene, 1,1
-dichloro-2-fluoroethylene, 1,2-dichloro-2-fluoroethylene, trichlorethylene, 1
, 1-difluoroethylene, 1,2-difluoroethylene, 1-chloro-1-fluoroethylene, cis-1-
Chloro-2-fluoroethylene, trans-1-
Chloro-2-fluoroethylene, 1,1-dichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, fluoroethylene, chloroethylene, ethylene, hexafluoropropene, 3,
3,3-trifluoropropene, 1-bromo-2,2-
difluoroethylene, bromotrifluoroethylene,
Examples include 2-chloropentafluoropropene, 1,1-dichlorotetrafluoropropene-1, 1,1-dibromodifluoroethylene, and the like.

Further, examples of the halogenoalkane used in the reaction include carbon tetrachloride, chloroform, R11, R11,
12, trifluorobromomethane, methylene chloride, R2
1, R22, methyl chloride, bromotrichloromethane, bromodichlorofluoromethane, bromodifluoromethane, iodotrifluoromethane, pentachlorofluoroethane, tetrachloro-1,2-difluoroethane, 1,1,1-trichloroethane, 1-chloro- 2-
iodotetrafluoroethane, 3,3-dichloro-1
,1,1,2,2-pentafluoropropane, 1,3
-dichloro-1,1,2,2,3-pentafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,3-trichloropentafluoropropane,
1-chloro-3-iodoperfluoropropane, 1-
Examples include iodoperfluoropropane.

Examples of the halogenated hydrocarbons obtained by the present invention include tetrachlorotetrafluoropropanes such as 1,1,1,3-tetrachlorotetrafluoropropane, 1,3,3-trichloro-1,1,2, Trichlorotetrafluoropropane such as 2-tetrafluoropropane, trichloropentafluoropropane such as 1,1,1-trichloropentafluoropropane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, etc. Dichlorohexafluoropropanes such as dichloropentafluoropropane and 3,3-dichlorohexafluoropropane, 1,1,3,3-tetrachloro-1,2,2-
Tetrachlorotrifluoropropane such as trifluoropropane, pentachlorotrifluoropropane such as 1,1,1,3,3-pentachlorotrifluoropropane,
Dichlorotrifluoropropane such as 3,3-dichloro-1,1,1-trifluoropropane, trichlorotrifluoropropane such as 1,1,1-trichloro-3,3,3-trifluoropropane, 3,3- dichloro-1
, dichlorotetrafluoropropane such as 1,1,2-tetrafluoropropane, bromodichloropentafluoropropane such as 1-bromo-1,3-dichloropentafluoropropane, 1-iodoheptafluoromethane, 1
, 1,1,2,2,3,3-heptachloropropane, 1,3-dichloro-1,1,2
, chlorofluorobutanes such as 2,3-pentafluorobutane, 1,3-dichloro-1,1,2,2,4,4,
Chlorofluoropentanes such as 5,5,5-nonafluoropentane, chlorofluorohexane such as 3,3-dichlorododecafluorohexane, 3,3-dichloro-
Chlorofluoroheptanes such as 1,1,1,2,2,4,4,5,5-nonafluoroheptane can be mentioned.

The reaction solvent is not particularly limited as long as it can appropriately dissolve the raw materials, olefin and halogenoalkane. For example, perfluorooctane, perfluorobutyltetrahydrofuran, trichloropentafluoropropane (R215), dichloropentafluoropropane (R225), tetrachlorotetrafluoropropane (
Solvents such as R224) can be used. Of course, it is also possible to carry out the reaction without a solvent in order to facilitate purification.

The amount of catalyst varies depending on the catalyst used, but is usually 0. 01-50% by weight, preferably 0.01-50% by weight.
Used in an amount of 1 to 10% by weight. The catalyst may be present in the reactor in advance, or in continuous operation it is continuously fed to the reactor at the same time as the olefin and halogenoalkane.
It may also be an operation for continuously extracting the product from the reactor at the same time as the product. In this case, the removed catalyst can be recycled.

The reaction temperature is generally -80 to 200°C, preferably -20 to 100°C. The reaction pressure varies depending on the olefin and halogenoalkane used and is not particularly limited, but is usually slightly pressurized to 10 kg/cm2.
(gauge pressure) is preferable.

Although the amount of olefin to be added depends on the amount of catalyst, it is appropriate to add at least equimolar amount to the amount of halogenoalkane to be added. Particularly when olefin and halogenoalkane are continuously fed, Preferably, the molar ratio of olefin and halogenoalkane is 1.01≦olefin/halogenoalkane≦10, particularly 1.01≦
Olefin/halogenoalkane≦5, more preferably 1
．． 01≦olefin/halogenoalkane≦3.

The reactor used for continuous operation may be a so-called continuous reactor, and either a complete mixing tank type or a piston flow type may be used. In the case of continuous operation, the residence time of the reaction solution depends on the reaction temperature, the type of Lewis acid, the olefin used, and the halogenomethane, but is usually 0. A suitable time period is 1 minute to 24 hours, particularly 1 minute to 10 hours.

[0026]

[Examples] Examples of the present invention will be shown below. [Preparation Example 1] After drying 1000 g of commercially available γ-alumina to remove moisture, it was dried in a mixed gas flow of HF/nitrogen.
After fluorination at 300 to 450°C, chlorination and fluorination were further carried out at 250 to 300°C in an R11 gas stream.

[Preparation Example 2] Zirconium oxide 100 prepared from aqueous ammonia with zirconium nitrate aqueous solution
After drying 0 g to remove water, it was fluorinated at 300 to 450°C in a mixed gas flow of HF/nitrogen, and then further chlorinated and fluorinated at 350 to 400°C in a R11 gas flow.

[Preparation Example 3] After drying 1000 g of titanium oxide prepared from an aqueous titanium tetrachloride solution and aqueous ammonia to remove moisture, it was dried in a mixed gas stream of HF/nitrogen.
After fluorination at 300 to 450°C, chlorination and fluorination were further carried out at 350 to 400°C in an R11 gas stream.

[Preparation Example 4] Commercially available gallium oxide 1000
After drying g to remove moisture, it was fluorinated at 300 to 450°C in a mixed gas flow of HF/nitrogen, and then further chlorinated and fluorinated at 250 to 300°C in a R11 gas flow.

[Preparation Example 5] Commercially available γ-alumina 100
After drying 0 g to remove moisture, it was fluorinated at 300 to 450°C in a mixed gas flow of HF/nitrogen, and then further chlorinated and fluorinated at 250 to 300°C in a R11 gas flow. The catalyst thus obtained was mixed with 50% of AlCl3
After impregnating g in an aqueous solution dissolved in 2 liters of water,
It was dried to remove moisture. It was activated again by chlorination and fluorination at 250 to 300° C. in an R11/nitrogen mixed gas flow.

[Preparation Example 6] Instead of γ-alumina,
A catalyst was prepared in the same manner as in Preparation Example 5, except that 1000 g of zirconium oxide was impregnated with an aqueous solution of aluminum chloride and then chlorinated and fluorinated at 350 to 400°C in a R11/nitrogen mixed gas stream, and Activated.

[Preparation Example 7] A catalyst was prepared and activated in the same manner as in Preparation Example 6, except that 1000 g of titanium oxide was used instead of zirconium oxide.

[Preparation Example 8] A catalyst was prepared and activated in the same manner as in Preparation Example 6, except that 1000 g of gallium oxide was used instead of zirconium oxide.

[Preparation Example 9] A catalyst was prepared and activated in the same manner as in Preparation Example 6, except that 1000 g of silicon oxide was used instead of zirconium oxide.

[Preparation Example 10] Commercially available γ-alumina 10
00g, niobium pentaethoxide (Nb(OEt)
5) was impregnated with a solution dissolved in 2 liters of ethanol, dried to remove the solvent, and further soaked in 60 g of ethanol.
It was fired at 0°C. Next, in the R11/nitrogen mixed gas stream, 1
It was activated by chlorination and fluorination at 00 to 400°C.

[Preparation Example 11] Instead of niobium pentaethoxide, tantalum pentaethoxide (Ta(OE
A catalyst was prepared and activated in the same manner as in Preparation Example 10, except that 50 g of t)5) was used.

[Preparation Example 12] A catalyst was prepared and activated in the same manner as in Preparation Example 10, except that 50 g of hafnium tetrachloride was used instead of niobium pentaethoxide.

[Preparation Example 13] A catalyst was prepared and activated in the same manner as in Preparation Example 10, except that 50 g of boron trichloride was used instead of niobium pentaethoxide.

[Preparation Example 14] Except that 50 g of zirconium tetrachloride was used instead of niobium pentaethoxide,
A catalyst was prepared and activated in the same manner as in Preparation Example 10.

[Preparation Example 15] A catalyst was prepared and activated in the same manner as in Preparation Example 10, except that 50 g of indium trichloride was used instead of niobium pentaethoxide.

[Preparation Example 16] Activated carbon was immersed in pure water to impregnate the inside of the pores with water. An aqueous solution containing 0.5% of the total weight of metal components dissolved in AlCl3 based on the weight of activated carbon was added dropwise little by little to cause the ionic components to be adsorbed onto the activated carbon. After washing with pure water, it was heated to 150
It was dried at ℃ for 5 hours. Next, after drying in nitrogen at 250°C for 4 hours, chlorination and fluorination was carried out at 250 to 300°C in R11/nitrogen gas flow.

[Preparation Example 17] 176g of GaCl3 dissolved in 200g of ice-cooled water, 4ml of concentrated sulfuric acid and 210g of ammonium sulfate dissolved in 320ml of water, and 190g of it dissolved in 300ml of ice-cooled water. T of
Add iCl4 to the dissolved solution. The solution is heated on a water bath for 1 hour and 400 ml of 30% ammonia water is added to obtain a coprecipitate. After heating this for another hour,
The precipitate was filtered, dried, and baked at 500℃ for 3 hours.
a2 O3 -TiO2 is obtained. Add this to HF/
After fluorination at 300 to 450°C in a nitrogen mixed gas flow, chlorination and fluorination was further carried out at 350 to 400°C in an R11 gas flow.

[Preparation Example 18] Ga2 O3 --ZrO2 was obtained in the same manner as Preparation Example 13 except that 340 g of Zr(NO3)4 was used instead of 190 g of TiCl4. This was heated to 300~
After fluorination at 450°C, further in R11 gas stream,
Chlorination and fluorination were carried out at 350-400°C.

[Preparation Example 19] 82 g of ZnCl2 and 4
ml concentrated sulfuric acid and 210g ammonium sulfate in 320ml
Dissolve in 1 liter of water and add 13 to 300 ml of ice-cold water.
Add 6 g of AlCl3 to the dissolved solution. The solution is heated on a water bath for 1 hour and 400 ml of 30% ammonia water is added to obtain a coprecipitate. After further heating this for 1 hour, the precipitate is filtered, dried, and calcined at 500°C for 3 hours to obtain Al2O3-ZnO. Add this to HF
After fluorination at 300 to 450°C in a mixed gas flow of /nitrogen, chlorination and fluorination was further carried out at 350 to 400°C in an R11 gas flow.

[Example 1] 50 g of the catalyst prepared in Preparation Example 1 was added to a 1 liter Hastelloy C autoclave and degassed under reduced pressure, and then 500 g (3.76 mol) of 1,1-dichlorodifluoroethylene was added. While keeping the autoclave at 0°C, add 370 g (3.57 mol) of R.
21 was added, and stirring was continued for an additional hour after the addition was complete. The reaction solution was filtered, 830 g of crude reaction solution was recovered, and gas chromatography (
GC) and NMR. The results are shown in Table 1.

[0046]

[Table 1]

[Example 2] The reaction was carried out in the same manner as in Example 1 except that the catalyst prepared in Preparation Example 2 was used.
30g was obtained. Table 2 shows the results of analysis using GC and NMR.

[0048]

[Table 2]

[Example 3] After adding 50 g of the catalyst prepared in Preparation Example 3 to a 1 liter Hastelloy C autoclave and degassing under reduced pressure, 3,3-dichloro-1,1,1,2
,2-pentafluoropropane (R225ca) 15
Added 0g. After cooling to 0°C, the reaction temperature was increased from 0 to 1
Chlorotrifluoroethylene and R21 while keeping at 0℃
was continued to be added as appropriate so that chlorotrifluoroethylene was in excess. 500g of chlorotrifluoroethylene (
4.3 mol) and 400 g (3.9 mol) of R21 were added, the supply of raw materials was stopped and stirring was continued for an additional 4 hours. After returning the pressure to normal pressure, the reaction solution was washed with water, and about 830 g of crude reaction solution was recovered. Table 3 shows the results of analysis using GC and NMR.

[0050]

[Table 3]

[Example 4] The reaction was carried out in the same manner as in Example 3 except that the catalyst prepared in Preparation Example 18 was used to obtain 890 g of a crude reaction liquid. Table 4 shows the results of analysis using GC and NMR.

[0052]

[Table 4]

[Example 5] Using the catalyst prepared in Preparation Example 12, 350 g of chlorotrifluoroethylene was used instead of chlorotrifluoroethylene.
The reaction was carried out in the same manner as in Example 3, except that (4.3 mol) of trifluoroethylene and 530 g (3.9 mol) of R11 were used instead of R21, and 920 g of crude reaction liquid was obtained.
I got it. Table 5 shows the results of analysis using GC and NMR.

[0054]

[Table 5]

[Example 6] Using the catalyst prepared in Preparation Example 4, 400 g (3.9 mol) of R2 was added instead of R11.
The reaction was carried out in the same manner as in Example 5, except that 1 was used, and 760 g of crude reaction liquid was obtained. Table 6 shows the results of analysis using GC and NMR.

[0056]

[Table 6]

[Example 7] The reaction was carried out in the same manner as in Example 6 except that the catalyst prepared in Preparation Example 13 was used to obtain 800 g of a crude reaction liquid. Table 7 shows the results of analysis using GC and NMR.

[0058]

[Table 7]

[Example 8] The reaction was carried out in the same manner as in Example 6 except that the catalyst prepared in Preparation Example 15 was used to obtain 800 g of a crude reaction liquid. Table 8 shows the results of analysis using GC and NMR.

[0060]

[Table 8]

[Example 9] The reaction was carried out in the same manner as in Example 6 except that the catalyst prepared in Preparation Example 16 was used to obtain 720 g of a crude reaction liquid. Table 9 shows the results of analysis using GC and NMR.

[0062]

[Table 9]

[Example 10] Using the catalyst prepared in Preparation Example 6, 270 g of chlorotrifluoroethylene was used.
(4.3 mol) of difluoroethylene was used.
The reaction was carried out in the same manner as in Example 3 to obtain 730 g of crude reaction liquid. Table 10 shows the results of analysis using GC and NMR.

[0064]

[Table 10]

[Example 11] The reaction was carried out in the same manner as in Example 1, except that the catalyst prepared in Preparation Example 9 was used and 1,2-dichlorodifluoroethylene was used instead of 1,1-dichlorodifluoroethylene. 830 g of crude reaction liquid was obtained. Table 11 shows the results of analysis using GC and NMR.

[0066]

[Table 11]

[Example 12] The reaction was carried out in the same manner as in Example 11 except that the catalyst prepared in Preparation Example 10 was used to obtain 830 g of a crude reaction liquid. Table 12 shows the results of analysis using GC and NMR.

[0068]

[Table 12]

[Example 13] The reaction was carried out in the same manner as in Example 11, except that the catalyst prepared in Preparation Example 11 was used, and 830 g of a crude reaction liquid was obtained. Table 13 shows the results of analysis using GC and NMR.

[0070]

[Table 13]

[Example 14] The reaction was carried out in the same manner as in Example 11 except that the catalyst prepared in Preparation Example 17 was used to obtain 840 g of a crude reaction liquid. Table 14 shows the results of analysis using GC and NMR.

[0072]

[Table 14]

[Example 15] Using the catalyst prepared in Preparation Example 5, 1,2-dichlorodifluoroethylene was used instead of 1,1-dichlorodifluoroethylene, and 430 g (3.57 mol) of R12 was used instead of R21. Others are
The reaction was carried out in the same manner as in Example 1 to obtain 800 g of crude reaction liquid. Table 15 shows the results of analysis using GC and NMR.

[0074]

[Table 15]

[Example 16] Using the catalyst prepared in Preparation Example 19, 310 g (3.57 mol) was added in place of R12.
The reaction was carried out in the same manner as in Example 15 except that R22 was used to obtain 700 g of a crude reaction liquid. Table 16 shows the results of analysis using GC and NMR.

[0076]

[Table 16]

[Example 17] 1 liter of Hastelloy C
After adding 50 g of the catalyst prepared in Preparation Example 7 to a manufactured autoclave and degassing under reduced pressure, 500 g of tetrachlorethylene (
3.0 mol) was added. Autoclave for 60~80
360 g (3.0 mol) of chloroform while keeping at ℃
) was added. After the addition was complete, stirring was continued for an additional 6 hours. The reaction solution was filtered, and 850 g of crude reaction solution was collected and analyzed using GC and NMR. The results are shown in Table 17.

[0078]

[Table 17]

[Example 18] 1 liter of Hastelloy C
After adding 50 g of the catalyst prepared in Preparation Example 8 to a manufactured autoclave and degassing under reduced pressure, 400 g of trichlorethylene (3
．． 0 mol) was added. Autoclave at 60-80℃
While maintaining the temperature, 460 g (3.0 mol) of carbon tetrachloride was added. After the addition was complete, stirring was continued for an additional 6 hours. The reaction solution was filtered, and 840 g of crude reaction solution was collected and analyzed using GC and NMR. The results are shown in Table 18.

[0080]

[Table 18]

[Example 19] 0.4 of the catalyst prepared in Preparation Example 14 was placed in a 10 liter Hastelloy C autoclave.
kg was added and degassed under reduced pressure, and then 10 kg of 1,1,1-trichloropentafluoropropane (R215cb) was added. After cooling the autoclave to -10°C, the reaction temperature was reduced to 0.
120°C of tetrafluoroethylene while maintaining the temperature at ~10°C.
0 g/hr, R11 at 1300 g/hr, and the catalyst prepared in Preparation Example 14 at a rate of 40 g/hr, and the reaction mixture was continuously withdrawn in an amount equal to the amount charged. Table 19 shows the reaction solution composition after 40 hours.

[0082]

[Table 19] By distilling and purifying 85 kg of the recovered reaction crude liquid, R
76 kg of 215 was obtained (yield 89%).

[Example 20] Using the catalyst prepared in Preparation Example 1, 1,1-dichlorodifluoroethylene was used at 1450 g/hr in place of tetrafluoroethylene, and dichlorofluoromethane (R21) was added at 1030 g/hr in place of R11.
The reaction was carried out in the same manner as in Example 19 except that the addition was carried out at a feed rate of g/hr. Table 20 shows the reaction crude liquid after 40 hours.

[0084]

Table 20 78 kg of R223 was obtained by distilling and purifying 95 kg of the recovered reaction crude liquid (yield: 83%).

[Example 21] 1,2-dichlorodifluoroethylene was used instead of 1,1-dichlorodifluoroethylene, and 850 g (3.58 mol) of 1,1,3-trichloropentafluoropropane was used instead of R21.
The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 10°C. The reaction solution was filtered, and 1300 g of crude reaction solution was collected and analyzed using GC and NMR. The results are shown in Table 21.

[0086]

[Table 21]

[Example 22] Using the catalyst prepared in Preparation Example 14, 275 g (2.75 mol) of tetrafluoroethylene was used instead of chlorotrifluoroethylene.
), R21 was replaced with 600 g (2.5 mol) of 1,1,3-trichloropentafluoropropane, and the reaction was carried out in the same manner as in Example 3, except that the reaction temperature was 10 to 20°C. The reaction solution was filtered, and 950 g of crude reaction solution was collected and analyzed using GC and NMR. The results are shown in Table 22.

[0088]

[Table 22]

[0089]

As shown in the examples, the present invention has the effect that halogenated hydrocarbons, for which it has been difficult to obtain high-purity products, can be easily produced in high yield.

Claims (7)

[Claims] Claim 1: General formula MXx Fy Oz [where M is one or more elements selected from Group 4, Group 5, and Group 13, and X is one or two elements selected from Cl, Br, and I. Above, x is 0<x<5, y is 0<y<5
, z is a real number of 0<z<2.5, x+y +z
/2 = an integer of 3 to 5] In the presence of a halogenated oxide, the following olefin R1 R2 C=CR3 R4 [However, R1 is H, Cl, F, Br or CF3
, CF2 Cl group, R2, R3, R4 are either the same or different H, Cl, F or Br] and the following halogenoalkane CYR5 R6 R7 [However, Y is any of Cl, F, Br or I Or R5
is Cl, F, Br, I or Ca Hb Clc F
d Bre If , where a is 0 to 4, b
, c, d are 0 to 2a+1, e, f are integers of 0 to 3, b+c+d+e+f=2a+1, 2a-1 or 2a-3, and b+c+d+e+f ≧1, R6, R
7 are the same or different H, Cl, F, Br or I] A method for producing halogenated hydrocarbons. Claim 2: The olefin is tetrachlorethylene, trichlorethylene, chlorotrifluoroethylene, 1,1
2. The method according to claim 1, wherein the compound is selected from the group of -dichlorodifluoroethylene, 1,2-dichlorodifluoroethylene, tetrafluoroethylene, trifluoroethylene, and 1,1-difluoroethylene. 3. The method according to claim 1, wherein the halogenoalkane is selected from the group of carbon tetrachloride, chloroform, trichlorofluoromethane, dichlorodifluoromethane, dichlorofluoromethane, and chlorodifluoromethane. 4. The method according to claim 1, wherein the reaction is carried out under reaction conditions in which the molar ratio of the olefin to the halogenoalkane to be added is 1 or more. Claim 5: Claim 1, wherein the molar ratio of the olefin and halogenoalkane is 1≦olefin/halogenoalkane, the olefin and halogenoalkane are continuously supplied to the reactor, and the reaction product is continuously extracted from the reactor. manufacturing method. [Claim 6] The molar ratio of olefin and halogenoalkane to be supplied is 1≦olefin/halogenoalkane, and the halogenated oxide, olefin, and halogenoalkane are continuously supplied to the reactor, and the reaction product and the halogenated oxide are 2. The method according to claim 1, wherein the reactor is continuously withdrawn. Claim 7: The supply molar ratio of olefin and halogenoalkane is 1.01≦olefin/halogenoalkane≦1.
7. The manufacturing method according to claim 5 or 6, wherein