JPH08239333A - Production of 1,1,1,3,3-pentachloropropane - Google Patents

Abstract

PURPOSE: To obtain 1,1,1,3,3-pentachloropropane which is useful as a foaming agent or as a starting substance for a refrigerant used in a turbo refrigerator by allowing carbon tetrachloride to react with vinyl chloride in the presence of an iron catalyst in a specific solvent. CONSTITUTION: The reaction of carbon tetrachloride with vinyl chloride is carried out in the presence of a catalyst mainly comprising an elementary iron in an aprotic solvent such as acetonitrile at 80-150 deg.C under a pressure of 1-50kg/cm<2> . A cocatalyst of a halide of a metal in group VII or group IB such as cuprous chloride may be used together with the iron catalyst. The reactor used in the reaction is made of glass or a resin or lined with glass or a resin. The target compound is a foaming agent for polyolefin, polystyrene, polyurethane foam or polyisocyanurate or a starting material for producing 1,1,1,3,3-pentafluoropropane useful as a refrigerant for a turbo refrigerator.

Description

Detailed Description of the Invention

[0001]

The present invention relates to 1,1,1,3,3-
Can be a precursor of pentafluoropropane production1,
The present invention relates to a method for producing 1,1,3,3-pentachloropropane.

[0002]

2. Description of the Related Art The use of chlorofluorocarbon (CFC), which is considered to destroy the ozone layer, is being prohibited or abolished, and alternative substances such as hydrochlorofluorocarbon (HCFC) and hydrofluorocarbon (HFC) are being used. Is being developed and is being used.

1,1,1,3,3-Pentachloropropane is expected as a foaming agent such as polyolefin, polystyrene, polyurethane foam, polyisocyanurate or a refrigerant for turbo refrigerators, 1,1,1,3,3. -A compound that can be a raw material for pentafluoropropane.

As a method for synthesizing chloropropanes, chlorination reaction of propane, radical addition reaction of chlorinated methanes and olefins having 2 carbon atoms, and free reaction between chlorinated methanes and olefins having 2 carbon atoms are similarly conducted. A method based on an ion addition reaction such as a Delcraft reaction or a Prince reaction is known. For example, as a method for obtaining a tetrachloroalkane by reacting an olefinic hydrocarbon with carbon tetrachloride, a method using an organic peroxide as a reaction aid (U
SP 2,440,800), a method of reacting an organic acid metal salt or an inorganic acid metal salt as a catalyst in combination with amines and the like (JP-B-37-18389, JP-B-39-2).
8306, Japanese Patent Publication No. 40-19740, Japanese Patent Publication No. 41-
No. 20692), a method of reacting in the presence of a catalyst comprising metallic copper and an alkali metal halide (JP-A-47-
31907), a polyalkoxy compound and iron chloride in the presence of a catalyst (JP-A-52-5).
No. 9102), and a method of reacting in the presence of a catalyst composed of a phosphorous acid alkyl ester, iron chloride and a nitrile compound (JP-A-52-59103).

As a method for producing 1,1,1,3,3-pentachloropropane, vinylidene chloride and chloroform are reacted in the presence of a copper amine catalyst (M. Kot).
ora et al., React. Kinet. Catal. Le
tt. , 44, No. 2, 415, 1991), a method of reacting carbon tetrachloride and vinyl chloride in the presence of a copper amine catalyst (M. Kotra et al., J. of Mol. C).
atal. 77, p. 51, 1992), a method of reacting carbon tetrachloride and vinyl chloride in an isopropanol solvent in the presence of a ferrous chloride catalyst (EN Zil'berm).
an et al. of Org. Chem. USSR, 3
Vol., 2101, 1967) and the like.

[0006]

[Problems to be Solved by the Invention] The method of Kotora et al. Is low in the stability of the catalyst and requires careful handling, and is not always a satisfactory method as an industrial production method adopted for continuous mass production. In addition, E.
N. The method of Zil'berman et al. Has a problem that the reaction result varies depending on the material of the reactor.

[0007]

In order to solve the above-mentioned problems, the present inventors have found that carbon tetrachloride and vinyl chloride are present in the presence of a catalyst as a method for obtaining 1,1,1,3,3-pentachloropropane. As a result of extensive studies on the method of carrying out the lower telomerization reaction, when a catalyst containing elemental iron as a main component in a specific solvent system is used, the desired yield is 1,1, The inventors have found that 1,3,3-pentachloropropane is produced and have reached the present invention. That is, the present invention is characterized in that carbon tetrachloride and vinyl chloride are reacted in the presence of an aprotic organic solvent using elemental iron as a catalyst.
-A method for producing pentachloropropane.

As the iron used as a catalyst in the method of the present invention, iron or steel containing metallic iron, pure iron, soft iron, carbon, etc. or alloys containing iron as a component, such as various stainless steels, ferrosilicone, etc. can be used. Powder, grain, lump, wire,
It can be used in any form such as rods, spheres, plates or metal pieces processed into any shape, for example, Raschig rings, distillation packings such as helices, steel wool, wire mesh, coils, and other amorphous metal pieces. is there. However, in alloys containing a large amount of components having no catalytic activity other than iron, those components are eluted in the reaction system or exist as insoluble components, so that their treatment becomes complicated after the reaction, and as a catalyst, Not preferable.

Further, a metal compound or a metal complex having a co-catalyst action can be used together with the iron catalyst, and a preferable metal as such a metal is VIII of the periodic table.
A metal element of Group I or Group IB can be mentioned. In particular,
For example, nickel, iron, cobalt, palladium, ruthenium, copper, halides such as silver, oxides, nitrates, acetates or acetylacetone complexes and the like, nickel, iron, cobalt and a halide of a metal selected from copper. Especially excellent. Examples of such a halide include a fluoride, a chloride, a bromide, and an iodide, and the chloride is excellent in reactivity, versatility of the substance, and ease of handling. Specifically, ferrous chloride, ferric chloride, nickel chloride, cobalt chloride, cuprous chloride and cupric chloride can be mentioned as preferable ones.

The amount of the iron catalyst used in the present invention should be at least 0.001 mol with respect to 1 mol of carbon tetrachloride. However, since the iron catalyst exists as a solid in the reaction system, the reaction vessel is large. Except for the point, there is no particular inconvenience in being an excessive amount. Therefore, in a batch type reaction or a semi-batch type reaction, it is usually 0.001 to 1 mol,
0.005-0.8 mol is preferable, 0.01-0.5
A molar range is more preferable, but an excess of iron catalyst does not cause any inconvenience in the flow system described later. The amount of catalyst is 0.
If it is less than 001 mol, the reaction yield is lowered, which is not preferable. On the other hand, the amount of the cocatalyst is usually 0.001 to 1 mol per 1 mol of carbon tetrachloride, preferably 0.05 to 0.5 mol, and more preferably 0.01 to 0.1 mol. preferable. If the amount of the co-catalyst is less than 0.001 mol, the reaction rate will decrease, which is not preferable. The amount ratio of the co-catalyst to the iron catalyst is not particularly limited because the amount of the iron catalyst is not limited as described above, but it is usually preferably 0.1 or less.

The aprotic polar organic solvent preferably used in the present invention includes nitriles, amides and other solvents. Examples of the nitriles include acetonitrile, propionitrile, butyronitrile, valeronitrile, benzonitrile, isophthalonitrile, 2-pentenenitrile, and 3-pentenenitrile. Examples of the amides include dimethylformamide and dimethyl. Acetamide, hexamethylphosphoric triamide and the like, and other solvents include dimethyl sulfoxide, N-methyl-2-pyrrolidone,
Examples thereof include 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone. Acetonitrile, dimethylformamide, dimethylformamide, and hexamethylphosphoric triamide are particularly preferable because they are excellent in solubility of the metal compound.

In the present invention, it is also possible to appropriately add an inert solvent to the reaction system in order to improve reactivity and selectivity. Generally, the addition of such a solvent is effective in reducing the production of vinyl chloride higher-order polymers. The addition ratio is not limited and can be appropriately selected. Such a solvent is not limited as long as it is a substance that is inactive in the reaction system and does not function as a radical scavenger.

The aprotic polar organic solvent / carbon tetrachloride molar composition ratio in the reaction system is from 10/1 to 1/10, preferably from 2/1 to 1/2, and around 1/1. Particularly preferred. When this ratio is larger than 10/1, there is no particular inconvenience, but it is not preferable because the reactor becomes large.
When it is less than 0, the reaction rate of carbon tetrachloride or vinyl chloride decreases, which is not preferable.

The amount of vinyl chloride is preferably, but not necessarily limited to, an equimolar amount or less with respect to carbon tetrachloride. When the amount of vinyl chloride is equal to or more than the equimolar amount, the amount of higher-order polymer of vinyl chloride produced increases, and the amount of vinyl chloride passing through the reactor unreacted increases, which is not preferable. Further, in the case of an equimolar amount or less, a part of carbon tetrachloride will remain unreacted in the reactor,
Since this can be recovered from the reaction solution by a known method such as distillation and recycled, there is no particular problem.

In the method of the present invention, vinyl chloride can be diluted with an inert gas before use. The degree of dilution may be arbitrary, but it is preferable that the proportion of the diluent gas with respect to vinyl chloride is increased because the amount of the vinyl chloride higher-order polymer produced is reduced. However, in that case, since the efficiency of the apparatus is lowered, the volume ratio of vinyl chloride / diluting gas is usually 0.1.
It is preferably about 10 to 10. The diluting gas is not limited as long as it is a substance that is inert in the reaction system and does not act as a radical scavenger, and, for example, nitrogen, hydrogen, argon, helium or the like can be used.

The reaction temperature depends on the amounts of the catalyst and cocatalyst added and the amount of the aprotic polar organic solvent added, and the conversion of vinyl chloride, the selectivity of 1,1,1,3,3-pentachloropropane, the catalyst And affects the life of the promoter,
A range of 80 to 150 ° C, more preferably 100 to 120 ° C is recommended. If it is lower than 80 ° C, the conversion rate is low, and if it exceeds 150 ° C, the pressure in the reactor needs to be high, which is not preferable. The pressure of the reactor is the sum of the partial pressures of carbon tetrachloride and the aprotic polar organic solvent at each temperature, but is usually 1 to 50 kg / cm ² and 3 to 15
kg / cm ² is preferred.

The embodiment of the present invention may be a batch reaction, a semi-flow reaction or a flow reaction. For example, a mixed reaction liquid containing carbon tetrachloride and an aprotic polar organic solvent is mixed with an iron catalyst. It is desirable to optionally allow a metal compound and / or a metal complex to be present, and continuously or intermittently introduce vinyl chloride in the form of a gas or a liquid into it and react it. The batch method, in which the catalyst, solvent, and reaction reagent are preliminarily charged at the beginning of the reaction, and the method in which vinyl chloride is sequentially added as a liquid, both increase the production amount of vinyl chloride higher-order polymer. Therefore, it is preferable to avoid it in the method of the present invention. When the iron catalyst has a relatively small shape, it may be made to float or flow in the system by stirring with the reaction liquid, but it is also preferable to fix the iron catalyst so that only the other reaction reagents flow. . Regardless of which reaction mode is adopted, contact between gas and liquid is an important step in this reaction, and therefore it is preferable to provide a known system or apparatus for establishing contact with the reaction system. Examples of such a device include a stirrer and a sparger, but various known devices may be applied.

The material of the reactor, which is a closed container for carrying out the present invention, is made of glass, resin, or a material lined with glass or resin. The resin used for these is preferably a fluororesin, and examples thereof include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyperfluoroalkyl vinyl ether, polyhexafluoropropylene, and tetrafluoroethylene-peroxide. Examples thereof include fluoroalkyl vinyl ether copolymers, tetrafluoroethylene-ethylene copolymers, hexafluoroethylene-tetrafluoroethylene copolymers, and of course, any resin that is inert in the reaction system of the present invention will be used. be able to.

1,1,1, manufactured by the method of the present invention
After taking out 3,3-pentachloropropane from the reactor, it is subjected to an operation of removing a catalyst, a metal compound and the like, an operation of removing a solvent and unreacted raw materials, and further rectification to obtain highly pure 1,1,1. 1,3,3-Pentachloropropane can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples,% in gas chromatographic analysis is% by weight.

[0021]

Example 1 In a 1000 ml glass autoclave equipped with a stirrer, 3.0 mol of carbon tetrachloride, 3.0 mol of acetonitrile, and 20 g of iron pieces of 2.0 × 25 × 50 mm (JIS.
G. 3141 (SPCC-SB), manufactured by Japan Test Panel Industry Co., Ltd. were charged, and the air in the reactor was replaced with nitrogen gas, then sealed and heated to 110 ° C. for 30 minutes while stirring (300 rpm). Held The pressure at this time became 2.5 kg / cm ² . After 30 minutes, vinyl chloride was injected under pressure to a pressure of 6 kg / cm ^2, and vinyl chloride was gradually added so that the pressure did not decrease as the reaction proceeded. The vinyl chloride introduced into the reactor by the end of the reaction was 3.2 mol in total. After starting to press fit vinyl chloride 3
The heating was stopped at 0 hours to complete the reaction.

After completion of the reaction, the reactor was cooled to room temperature, the autoclave was opened and the contents were taken out. The acetonitrile and carbon tetrachloride were distilled off under reduced pressure, and the solid content was separated by filtration.
85.3 g of liquid was obtained. When analyzed by gas chromatography, it was found that 1,1,1,3,3-hexachloropropane 70.1%, 1,1,1,3,5,5-hexachloropropane 16.4%, 1,1,3 , 3,5,5-hexachloropropane 13.0% and carbon tetrachloride 0.5
%, 1,1,1, relative to the charged vinyl chloride
The yield of 3,3-hexachloropropane was 49.1%.

Example 2 In a 1000 ml glass autoclave equipped with a stirrer, 3.0 mol of carbon tetrachloride, 3.0 mol of acetonitrile, 0.06 mol of cuprous chloride, the same iron piece 3 as used in Example 1 10 sheets were charged while the air in the reactor was replaced with nitrogen gas, then sealed and stirred (300 rpm) while stirring.
It was heated to 0 ° C. and kept for 30 minutes. The pressure at this time is 2.
It became 5 kg / cm ² . After 30 minutes, vinyl chloride was injected under pressure to a pressure of 3 kg / cm ^2, and vinyl chloride was gradually added so that the pressure did not decrease as the reaction proceeded. The total vinyl chloride introduced into the reactor by the end of the reaction was 2.4.
It was a mole. The heating was stopped 8 hours after the injection of vinyl chloride was started, and the reaction was completed.

After completion of the reaction, the reactor was cooled to room temperature, the autoclave was opened and the contents were taken out. The acetonitrile and carbon tetrachloride were distilled off under reduced pressure, and the solid content was separated by filtration.
28.0 g of liquid was obtained. When analyzed by gas chromatography, it was found that 1,1,1,3,3-hexachloropropane 96.6%, 1,1,1,3,5,5-hexachloropropane 1.6%, 1,1,3 , 3,5,5-hexachloropropane 1.5% and carbon tetrachloride 0.3%, 1,1,1,3,3 relative to the charged vinyl chloride
-The yield of hexachloropropane was 79.6%.

Example 3 Nickel chloride 0.0 instead of cuprous chloride as a co-catalyst
Reaction and recovery were conducted in the same manner as in Example 2 except that 3 mol was used.
Analysis was carried out. The time required for the reaction was 5 hours. As a result, the recovered organic matter was 475.1 g.
1,3,3-hexachloropropane 95.2%, 1,
1,1,3,5,5-hexachloropropane 1.3%,
1,1,3,3,5,5-hexachloropropane 3.4
% And carbon tetrachloride 0.1%, and the yield of 1,1,1,3,3-hexachloropropane based on the charged vinyl chloride was 87.0%.

EXAMPLE 4 Ferrous chloride 0.03 instead of cuprous chloride as co-catalyst
The reaction, recovery and analysis were carried out in the same manner as in Example 2 except that the mole was used. The time required for the reaction was 4 hours. As a result, the recovered organic matter was 468.5 g, which was 1,1,1,
3,3-hexachloropropane 94.5%, 1,1,
1,3,5,5-hexachloropropane 3.9%, 1,
1,3,3,5,5-hexachloropropane was 1.5% and carbon tetrachloride was 0.1%, and the yield of 1,1,1,3,3-hexachloropropane based on the charged vinyl chloride was 85. It was 0.2%.

Example 5 Instead of cuprous chloride as a cocatalyst, palladium chloride
Reaction, recovery, and analysis were conducted in the same manner as in Example 2 except that 06 mol was used. The time required for the reaction was 7 hours. As a result, the recovered organic matter was 452.5 g.
1,1,3,3-hexachloropropane 85.6%,
1,1,1,3,5,5-hexachloropropane 7.2
%, 1,1,3,3,5,5-hexachloropropane 5.0% and carbon tetrachloride 1.2%, and the yield of 1,1,1,3,3-hexachloropropane relative to the charged vinyl chloride. The rate was 74.5%.

Example 6 The reaction operation was performed in the same manner as in Example 2 except that 3.0 mol of dimethylacetamide was used as the solvent instead of acetonitrile. The time required for the reaction was 6 hours. After completion of the reaction, the reactor was cooled to room temperature, the autoclave was opened, the contents were taken out, 200 ml of water was added, the mixture was vigorously shaken and the aqueous layer was removed, and the organic matter was recovered. 43
6.4 g of liquid was obtained. When this was analyzed by gas chromatography, 1,1,1,3,3-hexachloropropane 98.1%, 1,1,1,3,5,5-hexachloropropane 0.5%, 1,1,3 , 3,5,5-hexachloropropane and carbon tetrachloride of 5.2%, and the yield of 1,1,1,3,3-hexachloropropane based on the charged carbon tetrachloride was 82.4%. .

Example 7 The reaction, recovery and analysis were carried out in the same manner as in Example 7 except that 3.0 mol of hexamethylphosphoric triamide was used as the solvent instead of acetonitrile. The time required for the reaction was 7 hours. As a result, the collected organic matter was 435.
3 g, 1,1,1,3,3-hexachloropropane 90.6%, 1,1,1,3,5,5-hexachloropropane 1.5%, 1,1,3,3,5, 5-hexachloropropane 7.7% and carbon tetrachloride 0.2%, 1,1,1,3,3-based on the charged vinyl chloride
The yield of hexachloropropane was 75.9%.

Comparative Example 1 A glass autoclave of 1000 ml equipped with a stirrer was charged with 3.0 mol of carbon tetrachloride, 3.0 mol of acetonitrile and 0.3 mol of ferrous chloride, and the air in the reactor was replaced with nitrogen. After substituting with gas, it was sealed and heated to 110 ° C. while stirring (300 rpm), and kept for 30 minutes. The pressure at this time became 2.5 kg / cm ² . After 30 minutes, vinyl chloride was injected under pressure to a pressure of 6 kg / cm ^2, and vinyl chloride was gradually added so that the pressure did not decrease as the reaction proceeded. The total amount of vinyl chloride introduced into the reactor by the end of the reaction was 0.72 mol. The heating was stopped 6 hours after the injection of vinyl chloride was started, and the reaction was completed.

After completion of the reaction, the reactor was cooled to room temperature, the autoclave was opened and the contents were taken out. The acetonitrile and carbon tetrachloride were distilled off under reduced pressure, and the solid content was separated by filtration.
5.0 g of liquid was obtained. When this was analyzed by gas chromatography, it was found that 1,1,1,3,3-hexachloropropane 93.4%, 1,1,1,3,5,5-hexachloropropane 5.3%, 1,1,3 , 3,5,5-Hexachloropropane 0.8% and carbon tetrachloride 0.1%, 1,1,1,3,3-based on the charged vinyl chloride
The yield of hexachloropropane was 27.1%.

[0032]

INDUSTRIAL APPLICABILITY The method for producing 1,1,1,3,3-hexachloropropane of the present invention has a high yield as is clear from the results of the examples, so that an industrially advantageous production method can be used. Can be provided.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasuo Hibino 2805 Imafuku Nakadai, Kawagoe City, Saitama Central Glass Co., Ltd.

Claims (7)

[Claims] 1. A method for producing 1,1,1,3,3-pentachloropropane, which comprises reacting carbon tetrachloride and vinyl chloride with an iron catalyst in the presence of an aprotic polar organic solvent. 2. As a co-catalyst, VIII of the periodic table of the elements
The method for producing 1,1,1,3,3-pentachloropropane according to claim 1, wherein one or more compounds selected from Group I or Group IB metal halides are added. 3. The aprotic polar organic solvent is one or more kinds of compounds selected from nitriles or amides, and 1,1,1,3,3-
Method for producing pentachloropropane. 4. The 1,1,1,3,3-pentachloropropane of claim 1, wherein the nitriles or amides are acetonitrile, hexamethylphosphoric triamide or dimethylacetamide. Production method. 5. The method for producing 1,1,1,3,3-pentachloropropane according to claim 1, wherein the iron catalyst is elemental iron. 6. The method according to claim 1, wherein an iron catalyst is present in a mixed solution of carbon tetrachloride and an aprotic organic solvent, and vinyl chloride is introduced therein to react. , 1,3,3-Pentachloropropane production method. 7. The reaction of 1, 1, 1, 3 according to claim 1, wherein the reaction is carried out in a reactor whose material is glass, fluororesin, or a material lined with glass or fluororesin. , A method for producing 3-pentachloropropane.