JP6582690B2 - Method for producing sulfonyl alkyl vinyl ether - Google Patents

Description

The present invention relates to a method for producing a sulfonyl chloride alkyl vinyl ether.

CF ₂ = CFOCF ₂ CF ₂ SO ₂ F is a compound useful as an industrial raw material such as an ion exchange membrane material. CF ₂ ═CFOCF ₂ CF ₂ SO ₂ F can be synthesized by fluorinating a sulfonylalkyl vinyl ether represented by CF ₂ ═CFOCF ₂ CF ₂ SO ₂ Cl. As a method for synthesizing CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl, the following methods are known.

For example, in Patent Document 1 and Patent Document 2, CF ₂ ═CFOCF ₂ CF ₂ SO ₃ Na and phosphorus pentachloride are added to a flask and gradually heated, so that mainly POCl ₃ and CF ₂ ═CFOCF ₂ CF It is described that a mixture of ₂ SO ₂ Cl was obtained.

In Patent Document 3, the glass container is heated to 50 ° C., and CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na and PCl ₅ are alternately added little by little. It was described that the obtained fraction was dropped into cold water and the lower part of the liquid separated into two phases was extracted to obtain CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl. Yes.

All of the above methods use phosphorus pentachloride. Alternatively, Patent Document 3, the reactor _{CF 2 = CFOCF 2 CF 2 SO} 3 Na and PCl ₃ and then poured, which also by blowing chlorine gas into _{CF 2} = CFOCF 2 _CF 2 SO it has been suggested _{that 2} Cl can be obtained.

US Pat. No. 3,560,568 Japanese Patent Publication No.47-2083 JP 2004-18454 A

_{CF 2 = CFOCF 2 CF 2 SO} 3 Na has a hydrophilic _-SO 3 Na group, is highly hygroscopic. Therefore, when CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na is charged into the reaction vessel, it is not easy to avoid mixing water into the reaction vessel. Then, phosphorus pentachloride reacts with a small amount of water to generate hydrochloric acid gas, which may cause the reaction liquid to bubble or overflow the reaction liquid from the reaction vessel. In addition, CF ₂ = CFOCF ₂ CF ₂ SO ₃ H reacts with phosphorus pentachloride to produce CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl. In this reaction, hydrochloric acid is used even in the absence of moisture. Gas is generated. However, in either case, phosphorus pentachloride is solid at room temperature, so it is difficult to control the amount of hydrochloric acid gas generated.

Accordingly, a first object of the present invention provides a process for preparing chlorides sulfonyl vinyl ether represented by using phosphorus pentachloride in the _{CF 2 = CFOCF 2 CF 2 SO} 2 Cl, easily controlling the generation amount of hydrochloric acid gas It is to provide a way to do.

Further, when CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na, phosphorus trichloride and chlorine gas are used, there is a problem that phosphorus pentachloride generated by the reaction of phosphorus trichloride and chlorine gas adheres to the reaction vessel. .

Accordingly, a second object of the present invention, three using phosphorous trichloride and chlorine _gas, a process for preparing chlorides sulfonyl vinyl ether represented by _{CF 2 = CFOCF 2 CF 2 SO} 2 Cl, to the reaction vessel five The object is to provide a method for suppressing the adhesion of phosphorus chloride.

The present _invention, CF _{2 =} CFOCF a method for producing a chloride sulfonyl vinyl ether compound represented by the ₂ CF _{2 SO 2} Cl, three phosphorus pentachloride in phosphorus and / or chlorinated solvent (except for phosphorus trichloride) is A step of preparing a dissolved solution, and mixing the above solution with a vinyl ether represented by the general formula: CF ₂ = CFOCF ₂ CF ₂ SO ₃ M (M is H or an alkali metal atom) It is a manufacturing method characterized by including the process with which the said vinyl ether is made to react (henceforth the manufacturing method (1) of this invention).

In the production method (1), it is preferable to prepare a solution in which phosphorus pentachloride is dissolved in phosphorus trichloride by reacting less than 1 mole of chlorine gas with 1 mole of phosphorus trichloride. In the above reaction, it is preferable to generate phosphorus pentachloride so as to have a saturation solubility or less. Moreover, it is preferable to perform the said reaction at 60-150 degreeC.

The present invention also _{provides a} method of manufacturing the CF _{2 =} CFOCF ₂ CF _{2 SO} chloride sulfonyl vinyl ether compound represented by 2 Cl, and phosphorus trichloride, the general _{formula: CF 2 = CFOCF 2 CF 2} SO 3 M A step of chlorinating the vinyl ether by introducing a vinyl ether represented by (M is H or an alkali metal atom) and chlorine gas into a reaction vessel;
(A) reacting phosphorus trichloride with chlorine gas while refluxing phosphorus trichloride;
(B) The total input amount of chlorine gas is less than 1 mole per mole of phosphorus trichloride, or
(C) It is also a manufacturing method characterized by performing said chlorination at 60-150 degreeC (henceforth the manufacturing method (2) of this invention).

In the production method (2), phosphorus trichloride and chlorine gas can be continuously charged into the reaction vessel.

Since the production method (1) of the present invention has the above configuration, the sulfonyl chloride represented by CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl using phosphorus pentachloride while easily controlling the amount of hydrochloric acid gas generated. Alkyl vinyl ether compounds can be produced.

Since the production method (2) of the present invention has the above-described configuration, CF ₂ = CFOCF ₂ CF ₂ SO ₂ using phosphorus trichloride and chlorine gas while suppressing the adhesion of phosphorus pentachloride to the reaction vessel. A sulfonyl chloride alkyl vinyl ether compound represented by Cl can be produced.

FIG. 1 is a schematic view showing an example of the production method (1).

Hereinafter, the present invention will be specifically described.

The production method (1) of the present invention is a production method that solves the first problem. The production method (1) of the present invention is a method for producing a sulfonylalkylvinylvinyl ether compound represented by CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl, and comprises phosphorus trichloride and / or a solvent (excluding phosphorus trichloride). A step of preparing a solution in which phosphorus pentachloride is dissolved, and the above solution and a vinyl ether represented by the general formula: CF ₂ = CFOCF ₂ CF ₂ SO ₃ M (M is H or an alkali metal atom) And a step of reacting phosphorus pentachloride with the vinyl ether.

As a method of preparing a solution in which phosphorus pentachloride is dissolved in phosphorus trichloride and / or a solvent (excluding phosphorus trichloride), phosphorus pentachloride is changed to phosphorus trichloride and / or a solvent (except phosphorus trichloride). The method of making it melt | dissolve, the method of making chlorine gas less than 1 mol react with respect to 1 mol of phosphorus trichloride, etc. are mentioned.

The solvent (excluding phosphorus trichloride) is not limited as long as it is a solvent capable of dissolving phosphorus pentachloride. Phosphorus oxychloride, monochlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc. And phosphorus oxychloride is preferred. A solution is obtained by adding phosphorus pentachloride to phosphorus trichloride and / or a solvent (excluding phosphorus trichloride) and stirring.

If phosphorus pentachloride solid is present in the solution, it is difficult to control the amount of phosphorus pentachloride introduced and the rate of addition when the solution is introduced into the reaction vessel in order to react with vinyl ether described below. Therefore, the concentration of phosphorus pentachloride in the solution is preferably not more than the saturation solubility of phosphorus pentachloride in phosphorus trichloride and / or a solvent (except phosphorus trichloride). Although a minimum is not specifically limited, 5 weight% may be sufficient.

In the method of reacting less than 1 mol of chlorine gas with 1 mol of phosphorus trichloride, a solution in which phosphorus pentachloride is dissolved in phosphorus trichloride is obtained by the reaction. When chlorine gas is 1 mol or more with respect to 1 mol of phosphorus trichloride, all phosphorus trichloride is consumed in the reaction, and a desired solution cannot be obtained.

When the amount of phosphorus pentachloride generated with respect to phosphorus trichloride exceeds the saturation solubility of phosphorus pentachloride with respect to phosphorus trichloride, solids of phosphorus pentachloride precipitate and react with the above solution to react with the vinyl ether described below. When charging into the container, it is difficult to control the amount of phosphorus pentachloride and the rate of charging. For example, when only the above solution is charged into the reaction vessel and solid phosphorus pentachloride remains in the original vessel without being charged, or when the above solution is charged into the reaction vessel through a pipe, There is a risk of blocking the piping. Therefore, in the above reaction, it is preferable to produce phosphorus pentachloride so that it is not higher than the saturation solubility of phosphorus pentachloride with respect to phosphorus trichloride. By making the amount of chlorine gas used for the above reaction less than the saturation solubility of phosphorus pentachloride with respect to phosphorus trichloride, the amount of phosphorus pentachloride generated is less than the saturation solubility. Can be adjusted as follows.

Chlorine gas is more preferably 0.85 mol or less, and 0.60 mol or less with respect to 1 mol of phosphorus trichloride, since the adjustment of the input amount and rate of phosphorus pentachloride becomes easier. More preferably, the lower limit is not particularly limited, but may be 0.45 mol in view of the efficiency of reaction with vinyl ether described below.

It is preferable to perform the said reaction at 60-150 degreeC. When the reaction is carried out at a temperature lower than 60 ° C., the saturation solubility of phosphorus pentachloride is lowered, so that a large amount of phosphorus trichloride and / or a solvent may be required. The reaction temperature is more preferably 70 ° C. or higher.
The above reaction is usually carried out at normal pressure, but can be carried out at -0.05 to 0.6 MPaG.

Since the vinyl ether has high hygroscopicity, when the vinyl ether is introduced into the reaction vessel, moisture in the air may also be introduced into the reaction vessel. In this case, phosphorus pentachloride reacts with water to generate hydrochloric acid gas, which may cause the reaction liquid to bubble or overflow from the reaction vessel. Also, hydrochloric acid gas is generated by the reaction of CF ₂ = CFOCF ₂ CF ₂ SO ₃ H and phosphorus pentachloride. Accordingly, it is preferable to control the amount of hydrochloric acid gas generated by controlling the amount and rate of addition of phosphorus pentachloride or the vinyl ether. Since the production method (1) includes a step of preparing a solution in which phosphorus pentachloride is dissolved in phosphorus trichloride and / or a solvent (excluding phosphorus trichloride), it is easy to control the amount of hydrochloric acid gas generated. It is.

In the production method (1), the method in which the vinyl ether is gradually introduced into the reaction vessel after the solution is introduced into the reaction vessel, the method in which the solution is gradually introduced into the reaction vessel after the vinyl ether is introduced into the reaction vessel, For example, a method of gradually charging the solution and the vinyl ether alternately into the reaction vessel can be used.

The reaction of phosphorus pentachloride with the vinyl ether can be carried out at 60 to 150 ° C. The above reaction is usually carried out at normal pressure, but can be carried out at -0.05 to 0.6 MPaG. The above reaction can be performed in a reaction vessel, and can be performed while refluxing phosphorus trichloride.

The reaction vessel is preferably charged with 1 mol or more of phosphorus pentachloride per 1 mol of the vinyl ether. Thereby, the said vinyl ether can fully be chlorinated. Moreover, since the process of collect | recovering the said vinyl ether from a reaction liquid can be simplified by reducing the quantity of the said unreacted said vinyl ether, it is economically advantageous.

The reaction vessel is preferably reacted with 2 mol or less of phosphorus pentachloride per 1 mol of the vinyl ether. When there is too much phosphorus pentachloride, there is a possibility that a yield corresponding to the amount added cannot be obtained.

Manufacturing method (1)
Charging the reaction vessel 1 with phosphorus trichloride and the above vinyl ether;
Vaporizing phosphorus trichloride in the reaction vessel 1 by heating phosphorus trichloride;
Supplying vaporized phosphorus trichloride from the reaction vessel 1 to the condenser and liquefying in the condenser;
Supplying liquefied phosphorus trichloride from the condenser to the reaction vessel 2,
Introducing chlorine gas into the reaction vessel 2 and reacting with phosphorus trichloride to prepare a solution in which phosphorus pentachloride is dissolved in phosphorus trichloride;
The solution is supplied from the reaction vessel 2 to the reaction vessel 1, the solution and the vinyl ether are mixed in the reaction vessel 1 to react phosphorus pentachloride with the vinyl ether, and CF ₂ = CFOCF ₂ CF ₂ SO step to produce ₂ Cl and,
Recovering CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl from the reaction vessel 1,
It is one of the preferred embodiments that includes

FIG. 1 is a schematic diagram for explaining the above aspect. After charging phosphorus trichloride and the vinyl ether into the reaction vessel 1, the phosphorus trichloride is heated to be vaporized. Phosphorus trichloride or the vinyl ether can be continuously charged into the reaction vessel 1. The vaporized phosphorus trichloride moves to the condenser 3 and is condensed in the condenser 3 to produce liquefied phosphorus trichloride. Cooling water can be circulated in the condenser 3. The liquefied phosphorus trichloride moves to the reaction vessel 2. The reaction vessel 2 is charged with chlorine gas and reacts with phosphorus trichloride to produce phosphorus pentachloride. Since phosphorus trichloride is continuously supplied from the condenser 3 to the reaction vessel 2, phosphorus pentachloride is obtained in a state dissolved in phosphorus trichloride. A solution in which phosphorus pentachloride is dissolved in phosphorus trichloride moves to the reaction vessel 1. In the reaction vessel 1, the reaction between phosphorus pentachloride and the vinyl ether proceeds, and the target CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl is generated. The produced CF ₂ ═CFOCF ₂ CF ₂ SO ₂ Cl can be finally or continuously recovered from the reaction vessel 1.

Phosphorus trichloride having a temperature close to the boiling point can be supplied from the condenser 3 to the reaction vessel 2, and high-temperature phosphorous trichloride can dissolve a relatively large amount of phosphorous pentachloride. Therefore, since a high concentration solution of phosphorus pentachloride can be supplied from the reaction vessel 2 to the reaction vessel 1, the reaction between phosphorus pentachloride and the vinyl ether proceeding in the reaction vessel 1 is highly efficient.
Since phosphorus trichloride is always boiling in the reaction vessel 1, the temperature of the reaction solution in the reaction vessel 1 is kept constant, and the reaction between phosphorus pentachloride and the vinyl ether in the reaction vessel 1 is maintained. Proceeds extremely stably.
In addition, the rate at which phosphorus trichloride and chlorine gas are charged into the reaction vessel 2 and the rate at which the solution is supplied from the reaction vessel 2 to the reaction vessel 1 can be appropriately adjusted. Accordingly, the amount of phosphorus pentachloride supplied to the reaction vessel 1 can be controlled to easily control the amount of hydrochloric acid gas generated in the reaction vessel 1 without depositing phosphorus pentachloride.

You may add the said solvent (however, except phosphorus trichloride) to the reaction container 1 or 2. FIG. The solvent may be phosphorus oxychloride produced by a reaction between phosphorus pentachloride and the vinyl ether.

The production method (2) of the present invention is a production method that solves the second problem. Production method of the present invention (2) _is, CF _{2 =} CFOCF a ₂ CF 2 _SO 2 process for preparing chlorides sulfonyl vinyl ether compound represented by Cl, three and phosphorus trichloride, the general _formula: CF 2 = CFOCF ₂ CF ₂ It includes a step of chlorinating the vinyl ether by introducing a vinyl ether represented by SO ₃ M (M is H or an alkali metal atom) and chlorine gas into a reaction vessel. In the above process, phosphorus trichloride reacts with chlorine gas, and the produced phosphorus pentachloride reacts with the vinyl ether.

In the above step, since phosphorus trichloride functions as a solvent, a solvent other than phosphorus trichloride is not essential. However, the above solvents (excluding phosphorus trichloride) can also be used. By using the above solvents (excluding phosphorus trichloride), phosphorus pentachloride produced by the reaction of phosphorus trichloride with chlorine gas. Is advantageous in that it is difficult to precipitate in the reaction vessel. The solvent (excluding phosphorus trichloride) is not limited as long as it is a solvent capable of dissolving phosphorus pentachloride. Phosphorus oxychloride, monochlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc. And phosphorus oxychloride is preferred.

In the above process, the production method (2) of the present invention comprises:
(A) reacting phosphorus trichloride with chlorine gas while refluxing phosphorus trichloride;
(B) The total input amount of chlorine gas is less than 1 mole per mole of phosphorus trichloride, or
(C) The chlorination is performed at 60 to 150 ° C.

(A) In the above step, by reacting phosphorus trichloride with chlorine gas while refluxing phosphorus trichloride, phosphorus pentachloride generated during the reaction adheres to the reaction vessel, and the feed port of each raw material is It is possible to avoid the disadvantage of blocking or making a large amount of phosphorus pentachloride adhering to be dropped at once to make the reaction unstable. The reflux can be carried out by installing a reflux condenser in a reaction vessel such as a flask.

Regarding (B), in the above process, the total amount of chlorine gas added to less than 1 mole of phosphorus trichloride is less than 1 mole, so that phosphorus trichloride is not exhausted by reaction with chlorine gas, and the reaction vessel It continues to function as a solvent. Therefore, even if the above-mentioned solvent (excluding phosphorus trichloride) is not used, phosphorus pentachloride generated during the reaction adheres to the reaction vessel and closes the supply port of each raw material, or a large amount of adhered pentachloride It is possible to avoid the disadvantage that phosphorus falls off at once and makes the reaction unstable.
Also it is suppressed progression of secondary reactions that produce _{CF 2 Cl-CFCl-OCF 2} CF 2 SO 2 Cl by chlorine is added to a vinyl group.

(C) In the above process, by performing the chlorination at 60 to 150 ° C., phosphorus pentachloride generated during the reaction adheres to the reaction vessel and blocks the supply port of each raw material, It is possible to avoid the disadvantage that phosphorus pentachloride falls off at once and makes the reaction unstable. The chlorination temperature is preferably 70 ° C. or higher, and preferably 140 ° C. or lower.
Also it is suppressed progression of secondary reactions that produce _{CF 2 Cl-CFCl-OCF 2} CF 2 SO 2 Cl by chlorine is added to a vinyl group.

Since adhesion of phosphorus pentachloride can be further suppressed, it is preferable to implement so as to satisfy all of the above (A) to (C).

The reaction vessel is preferably charged with 1 mol or more of chlorine gas per 1 mol of the vinyl ether. Thereby, the said vinyl ether can fully be chlorinated. Moreover, since the process of collect | recovering the said vinyl ether from a reaction liquid can be simplified by reducing the quantity of the said unreacted said vinyl ether, it is economically advantageous.

The reaction vessel is preferably charged with 2 mol or less of chlorine gas per 1 mol of the vinyl ether. When there is too much chlorine gas, there is a possibility that the yield corresponding to the addition amount cannot be obtained. In addition, excessive phosphorus pentachloride may be generated, and the amount of waste may increase.

In the production method (2), either phosphorus trichloride or chlorine gas can be continuously charged into the reaction vessel, and both phosphorus trichloride and chlorine gas can be continuously charged into the reaction vessel. This makes it possible to continuously can be produced _{CF 2 = CFOCF 2 CF 2 SO} 2 Cl.

In addition, it is preferable to control the production rate of phosphorus pentachloride in accordance with the rate at which phosphorus pentachloride reacts with the vinyl ether. As a result, excessive phosphorus pentachloride is generated and adheres to the reaction vessel to block the feed port of each raw material, or a large amount of adhered phosphorus pentachloride falls off at a time and makes the reaction unstable. Profit can be avoided.

Moreover, it is preferable to control the abundance ratio of chlorine gas and phosphorus trichloride in the reaction vessel by controlling the charging ratio of phosphorus trichloride and chlorine gas. As a result, an excessive amount of chlorine gas is present in the reaction vessel, and chlorine is added to the vinyl group of the vinyl ether, so that a side reaction that generates CF ₂ Cl—CFCl—OCF ₂ CF ₂ SO ₂ Cl is also progressed. Can be suppressed.

CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl obtained by the production method (1) or (2) of the present invention is fluorinated by a known method to produce CF ₂ = CFOCF ₂ CF ₂ SO ₂ F. Can do. The obtained CF ₂ ═CFOCF ₂ CF ₂ SO ₂ F is a compound useful as a raw material monomer for the polymer constituting the electrolyte membrane or ion exchange membrane.

Examples of electrolyte membranes or ion exchange membranes include electrolyte membranes for solid polymer electrolyte fuel cells, membranes for lithium batteries, membranes for salt electrolysis, membranes for water electrolysis, membranes for hydrohalic acid electrolysis, membranes for oxygen concentrators, humidity It can be used as a sensor film, a gas sensor film, or the like.

Next, the present invention will be described with reference to experimental examples.

Experimental example 1
The example of a manufacturing method (1) is shown.
Phosphorus trichloride 97.1 g (0.706 mol) was put into a 200 ml glass container equipped with a reflux condenser, a thermometer and a stirrer. Thereafter, the glass container was heated to 90 ° C. in an oil bath while stirring, and 30.0 g (0.423 mol) of chlorine gas was supplied over 9 hours under reflux. The produced phosphorus pentachloride was dissolved in phosphorus trichloride, and there was no adhesion of solid phosphorus pentachloride to the wall surface of the glass container.
On the other hand, CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na 78.4 g (0.261 mol) was charged into a 300 ml glass container equipped with a reflux condenser, a thermometer and a stirrer. Thereafter, the 300 mL glass container was heated to 90 ° C. in an oil bath while stirring, and the entire amount of the above solution in which phosphorus pentachloride was dissolved in phosphorus trichloride was added dropwise over 2 hours. At this time, although hydrochloric acid gas was generated, it was dropped while adjusting the dropping speed, so that the reaction liquid did not overflow due to foaming. After holding for 1 hour under reflux, excess phosphorus trichloride was extracted. Thereafter, the glass container was gradually heated to 140 ° C., and a fraction at around 105 ° C. was extracted. The obtained fraction was dropped into 253 g of cold water, and the lower part of the liquid separated into two phases was extracted to obtain 57.9 g (0.195 mol) of CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl.

Experimental example 2
The example of a manufacturing method (2) is shown.
CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na 10.0 g (0.033 mol) and phosphorus trichloride 40.0 g (0.291 mol) were charged into a 100 ml glass container equipped with a reflux condenser, a thermometer and a stirrer. . Thereafter, the glass container was heated to 90 ° C. in an oil bath while stirring, and 4.0 g (0.056 mol) of chlorine gas was supplied over 1 hour under reflux. The produced phosphorus pentachloride was dissolved in phosphorus trichloride, and there was no adhesion of solid phosphorus pentachloride to the wall surface of the glass container.
After supplying chlorine gas, the mixture was kept under reflux for 1 hour, and then excess phosphorus trichloride was extracted. Thereafter, the glass container was gradually heated to 150 ° C., and a fraction at around 105 ° C. was extracted. The obtained fraction was dropped into 30 g of cold water, and the lower part of the liquid separated into two phases was extracted to obtain 7.0 g (0.024 mol) of CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl.

Experimental example 3
The example of a manufacturing method (1) is shown.
Phosphorus trichloride 97.1 g (0.706 mol) was put into a 200 ml glass container equipped with a reflux condenser, a thermometer and a stirrer. Thereafter, the glass container was heated to 90 ° C. in an oil bath while stirring, and 30.0 g (0.423 mol) of chlorine gas was supplied over 9 hours under reflux. The produced phosphorus pentachloride was dissolved in phosphorus trichloride, and there was no adhesion of solid phosphorus pentachloride to the wall surface of the glass container.
Meanwhile, 78.4 g (0.261 mol) of CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na and 38.8 g of phosphorus oxychloride were charged into a 300 ml glass container equipped with a reflux condenser, a thermometer and a stirrer. Thereafter, the 300 mL glass container was heated to 90 ° C. in an oil bath while stirring, and the entire amount of the above solution in which phosphorus pentachloride was dissolved in phosphorus trichloride was added dropwise over 2 hours. At this time, although hydrochloric acid gas was generated, it was dropped while adjusting the dropping speed, so that the reaction liquid did not overflow due to foaming. After holding for 1 hour under reflux, excess phosphorus trichloride was extracted. Thereafter, the glass container was gradually heated to 140 ° C., and a fraction at around 105 ° C. was extracted. The resulting fraction was dropped into cold water 300 g, extracted portion of the liquid which is divided into two phases _to obtain _{CF 2 = CFOCF 2 CF 2 SO} 2 Cl 66.3g (0.224 mol).

Experimental Example 4
The example of a manufacturing method (2) is shown.
In a 100 ml glass container equipped with a reflux condenser, thermometer and stirrer, CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na 10.0 g (0.033 mol), phosphorus oxychloride 6.0 g and phosphorus trichloride 40.0 g (0 .291 mol) was charged. Thereafter, the glass container was heated to 90 ° C. in an oil bath while stirring, and 4.0 g (0.056 mol) of chlorine gas was supplied over 1 hour under reflux. The produced phosphorus pentachloride was dissolved in phosphorus trichloride, and there was no adhesion of solid phosphorus pentachloride to the wall surface of the glass container.
After supplying chlorine gas, the mixture was kept under reflux for 1 hour, and then excess phosphorus trichloride was extracted. Thereafter, the glass container was gradually heated to 150 ° C., and a fraction at around 105 ° C. was extracted. The obtained fraction was dropped into 40 g of cold water, and the lower part of the liquid separated into two phases was extracted to obtain 8.1 g (0.027 mol) of CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl.

Experimental Example 5
The example of a manufacturing method (2) is shown. (B) and (C) are performed.
In a 200 ml glass container equipped with a reflux condenser, a thermometer and a stirrer, CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na 10.0 g (0.033 mol), phosphorus oxychloride 34.0 g and phosphorus trichloride 13.7 g (0 .100 mol) was charged. Thereafter, the glass container was heated to 70 ° C. in an oil bath while stirring, and 4.0 g (0.056 mol) of chlorine gas was supplied over 1 hour. The produced phosphorus pentachloride was dissolved in phosphorus oxychloride, and solid phosphorus pentachloride did not adhere to the glass container wall.
After supplying chlorine gas, the glass container was kept at 90 ° C. for 1 hour, and then the glass container was gradually heated to 150 ° C., and a fraction around 105 ° C. was extracted. The obtained fraction was dropped into 65 g of cold water, and the lower part of the liquid separated into two phases was extracted to obtain 7.4 g (0.025 mol) of CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl.

Experimental Example 6
The example of a manufacturing method (2) is shown. (B) is carried out.
CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na 68.6 g (0.229 mol), phosphorus oxychloride 34.0 g and phosphorus trichloride 49.6 g (0) in a 200 ml glass container equipped with a reflux condenser, thermometer and stirrer .361 mol) was charged. Thereafter, the glass container was cooled in an ice bath while stirring, and 20.0 g (0.282 mol) of chlorine gas was supplied over 6 hours. At that time, the glass vessel wall and the reflux condenser were covered with the produced white crystals of phosphorus pentachloride. After supplying the chlorine gas, the temperature of the glass container was gradually raised to 90 ° C. with an oil bath and kept under reflux for 1 hour. As a result, white crystals on the wall surface of the glass container disappeared. After excess phosphorus trichloride was extracted, the glass container was gradually heated to 150 ° C., and a fraction at around 105 ° C. was extracted. The obtained fraction was added dropwise to 147 g of cold water, and the lower part of the liquid separated into two phases was extracted to obtain 14.8 g (0.050 mol) of CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl.

Experimental Example 7
The example of a manufacturing method (1) is shown. Compared to Experimental Example 1, the amount of phosphorus pentachloride input to vinyl ether is decreased.
Phosphorus trichloride 97.1 g (0.706 mol) was put into a 200 ml glass container equipped with a reflux condenser, a thermometer and a stirrer. Thereafter, the glass container was heated to 90 ° C. in an oil bath while stirring, and 18.4 g (0.259 mol) of chlorine gas was supplied over 9 hours under reflux. The produced phosphorus pentachloride was dissolved in phosphorus trichloride, and there was no adhesion of solid phosphorus pentachloride to the wall surface of the glass container.
On the other hand, a reflux condenser, was charged with _{CF 2 = CFOCF 2 CF 2 SO} 3 Na 78.4g (0.261 mol) in a glass container 300ml equipped with a thermometer and a stirrer. Thereafter, the 300 mL glass container was heated to 90 ° C. in an oil bath while stirring, and the entire amount of the above solution in which phosphorus pentachloride was dissolved in phosphorus trichloride was added dropwise over 2 hours. After holding for 1 hour under reflux, excess phosphorus trichloride was extracted. Thereafter, the glass container was gradually heated to 140 ° C., and a fraction at around 105 ° C. was extracted. The obtained fraction was dropped into 253 g of cold water, and the lower part of the liquid separated into two phases was extracted to obtain 38.7 g (0.131 mol) of CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl.

Experimental Example 8
The example of a manufacturing method (2) is shown. (A) and (C) are performed.
In a 100 ml glass vessel equipped with a reflux condenser, thermometer and stirrer, CF ₂ = CFOCF ₂ CF ₂ SO ₃ Na 10.0 g (0.033 mol), phosphorus oxychloride 34.0 g and phosphorus trichloride 4.6 g (0 0.033 mol) was charged. Thereafter, the glass container was heated to 90 ° C. in an oil bath while stirring, and 4.0 g (0.056 mol) of chlorine gas was supplied over 1 hour under reflux. As the phosphorus trichloride was consumed, the reflux disappeared. The produced phosphorus pentachloride was dissolved in phosphorus oxychloride, and solid phosphorus pentachloride did not adhere to the glass container wall.
After supplying chlorine gas, the glass container was kept at 90 ° C. for 1 hour, and then the glass container was gradually heated to 150 ° C., and a fraction around 105 ° C. was extracted. The obtained fraction was dropped into 65 g of cold water, and the lower part of the liquid separated into two phases was extracted to obtain 4.9 g (0.017 mol) of CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl.

Claims (6)

A method for producing a sulfonyl chloride alkyl vinyl ether compound represented by CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl,
Preparing a solution in which phosphorus pentachloride is dissolved in phosphorus trichloride and / or a solvent (excluding phosphorus trichloride); and
Including mixing the solution with a vinyl ether represented by the general formula: CF ₂ = CFOCF ₂ CF ₂ SO ₃ M (M is H or an alkali metal atom) and reacting phosphorus pentachloride with the vinyl ether. The manufacturing method characterized by this. The production method according to claim 1, wherein a solution in which phosphorus pentachloride is dissolved in phosphorus trichloride is prepared by reacting less than 1 mole of chlorine gas with 1 mole of phosphorus trichloride. The manufacturing method of Claim 2 which produces | generates phosphorus pentachloride so that it may become below saturation solubility. The method according to claim 2 or 3, wherein the reaction between phosphorus trichloride and chlorine gas is performed at 60 to 150 ° C. A method for producing a sulfonyl chloride alkyl vinyl ether compound represented by CF ₂ = CFOCF ₂ CF ₂ SO ₂ Cl,
Phosphorus trichloride, a vinyl ether represented by the general formula: CF ₂ = CFOCF ₂ CF ₂ SO ₃ M (M is H or an alkali metal atom), and chlorine gas are introduced into a reaction vessel, whereby the vinyl ether is chlorine Including the step of
(A) reacting phosphorus trichloride with chlorine gas while refluxing phosphorus trichloride;
(B) The total input amount of chlorine gas is less than 1 mole per mole of phosphorus trichloride, or
(C) The manufacturing method characterized by performing the said chlorination at 60-150 degreeC. 6. The method according to claim 5, wherein phosphorus trichloride and chlorine gas are continuously charged into the reaction vessel.

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