JPS6116385B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing diarylsulfones.

More specifically, it relates to a method for producing diarylsulfone, which is characterized by reacting an aromatic sulfochloride and an aromatic hydrocarbon in the presence of a perfluorosulfonic acid type resin (hereinafter referred to as super acidic resin). .

Diarylsulfone generally has excellent heat resistance,
It is a compound useful as a raw material for various heat-resistant resins and as a resin stabilizer.

Conventionally, methods for producing diarylsulfones include (1) performing a Friedel-Crafts reaction between an aromatic sulfochloride and an aromatic hydrocarbon under a Lewis acid catalyst such as anhydrous aluminum chloride or anhydrous ferric chloride; (FRJensen, G.
Goldman “Friedel Crafts and Related
Reactions”Vol., P1319, ed.byG.A.Olah,
John Wiley (1964)] (2) A method of reacting aromatic sulfochloride and aromatic hydrocarbon in the coexistence of aromatic sulfonic acid (German Patent No. 1950394), (3) Aromatic sulfonic acid and aromatic hydrocarbon A method of reacting in the presence of a phosphorus oxide-based dehydrating agent
24662), (4) A method of reacting aromatic hydrocarbons with a mixture of sulfuric anhydride and dimethyl sulfate (methyl pyrosulfate) (British Patent No. 895464 and Japanese Patent Publication No. 1987-
11817), (5) 4-chlorobenzenesulfonic acid and chlorobenzene at a temperature of 220-260°C for 30~
A method of reacting by maintaining the pressure above atmospheric pressure of 1100KN/m ² (Japanese Unexamined Patent Publication No. 49-76834), (6) Reacting aromatic sulfochloride and aromatic hydrocarbon in the coexistence of a sulfone-type ion exchange resin. Method (Unexamined Japanese Patent Publication 1973-
53345) are known. However, in method (1), an equimolar amount of Lewis acid catalyst is required for the aromatic sulfochloride, and separation of the catalyst is complicated, and furthermore, it cannot be reused.
Additionally, equipment that is resistant to corrosion is required. In method (2), the aromatic sulfonic acid needs to be equimolar to the aromatic sulfochloride, and recovery of the aromatic sulfonic acid is complicated, and moreover, it is generally hydrated. In method (3), a dehydrating agent is used to treat aromatic sulfonic acids.
Normally, 0.5 to 1.0 mol is required and cannot be reused. In method (4), a large amount of highly toxic dimethyl sulfate is used, which increases the processing load for pollution-free treatment such as waste liquid treatment. In method 5), the reaction is carried out at extremely high temperatures and under pressure, and a high-pressure device is required.
In the method (6), the ion exchange resin has the disadvantage that desulfonation occurs at temperatures above 170°C, making it unsuitable for reuse.

As a result of intensive studies aimed at providing an industrially advantageous method for producing diarylsulfone, the present inventors discovered that aromatic sulfochloride and aromatic hydrocarbon were reacted in the presence of a super acidic resin. The present invention was achieved by discovering that diarylsulfone can be produced extremely easily by the following steps.

According to the present invention, diarylsulfone can be produced in high yield by reacting an aromatic sulfochloride with an aromatic hydrocarbon in the presence of a super-strongly acidic resin, and the super-strongly acidic resin is It can be recovered by operation and used as it is in the next reaction. Therefore, in this production method, there is no loss of resin, and diarylsulfone can be produced very easily.

The aromatic sulfochloride used in the method of the present invention includes, for example, benzenesulfochloride,
O- and P-toluenesulfochloride, O- and P-ethylbenzenesulfochloride, 2,4
-2,5- and 3,5-xylene sulfochloride, 2,4,5-, 2,4,6- and 3,4,
5-trimethylbenzenesulfochloride, P-methoxybenzenesulfochloride, O- and P-
Chlorobenzene sulfochloride, O- and P-
Examples include bromobenzene sulfochloride, 2,4-dichlorobenzene sulfochloride, P-nitrobenzene sulfochloride, and naphthalene sulfochloride.

Examples of aromatic hydrocarbons used in the method of the present invention include benzene, toluene, ethylbenzene, xylene, trimethylbenzene, chlorobenzene, bromobenzene, anisole, naphthalene, biphenyl, diphenyl ether, and the like.

The super acidic resin used in the method of the present invention is
Perfluorosulfonic acid type resin (Nafion H: manufactured by Dupont) consisting of a copolymer of sulfonyl fluoride vinyl ether and tetrafluoroethylene
So far, sulfonic acid type ion exchange resins (obtained by sulfonating polymers or copolymers of aromatic vinyl compounds) are generally
While it decomposes at temperatures above 140°C, this super acidic resin (Nafion H) is characterized by its heat resistance of 200°C or above.

In the method of the present invention, aromatic sulfochloride
For 1.0 mol, aromatic hydrocarbons usually have 1.0
~20 mol is used. Preferably, it is about 1.0 to 10 mol. Further, the super acidic type resin is used in an amount of 1 to 200% by weight, preferably about 5 to 100% by weight, based on the sulfochloride.

However, the amount of superacidic resin is not limited to these amounts, and should be determined in consideration of yield and economic efficiency.

The reaction is generally carried out at 80-200°C. When carrying out the method of the present invention, the aromatic sulfochloride, aromatic hydrocarbon, and superacid type resin are generally heated while being stirred. Hydrogen chloride gas is observed to be generated from around 80°C and the reaction progresses. The reaction time is usually 3 to 30 hours. After the reaction is completed, the superacidic resin is removed by filtration, washed with the aromatic hydrocarbon used, and dried to be used in the next reaction. The diarylsulfone is obtained by combining the liquid and the washing liquid and distilling after washing with water or by direct steam distillation.

Diarylsulfones obtained by the method of the present invention include diphenylsulfone, 4-methyldiphenylsulfone, 4,4'-dimethylsulfone, 2,4'-dimethylsulfone, 2,4,4'-trimethyldiphenylsulfone. enylsulfone, 2,4,6-trimethyl-4'-chlorodiphenylsulfone, 4-chlorodiphenylsulfone, 4-bromodiphenylsulfone, 4,4'-dichlorodiphenylsulfone, 4,4'-dibromodif enylsulfone, 4-
Chloro-4'-methyldiphenyl sulfone, 2,
4,4'-trichlorodiphenylsulfone, 4-methoxydiphenylsulfone, 4-methoxy-4'-
Chlorodiphenylsulfone, 4-methyl-4'-methoxydiphenylsulfone, 4-nitrodiphenylsulfone, 4-chloro-4'-nitrodiphenylsulfone, 2-naphthyl-4'-chlorodiphenylsulfone, 4- Examples include phenoxy-diphenylsulfone and 4-phenylsulfone.

Hereinafter, the present invention will be explained in more detail by giving examples.

Preparation of super acidic resin (perfluorosulfonic acid resin) 50 g of potassium perfluorosulfonate type resin (trade name: Nafion Du'pont) was stirred with 40 ml of 4N hydrochloric acid at room temperature for 4 hours. and washed with distilled water until neutral. This operation was repeated four more times, and then dried at 80 to 90°C under a reduced pressure of 10 mmHg to obtain a perfluorosulfonic acid type resin.

Example 1 17.7 g (0.1 mol) of benzene sulfochloride, 23 g (0.3 mol) of benzene, and 5.3 g of the perfluorosulfonic acid type resin prepared above (hereinafter simply referred to as perfluorosulfonic acid type resin) were mixed under reflux of benzene. When the mixture was heated and stirred, generation of hydrogen chloride gas was observed. After heating under reflux for 6 hours, the mixture is allowed to cool to room temperature. The reaction mixture is filtered to remove the perfluorosulfonic acid type resin, and the perfluorosulfonic acid type resin is washed with a small amount of benzene. When the liquid and the washing liquid are combined and subjected to azeotropic distillation while adding water, a precipitate is deposited. After filtering, washing with water, and drying, diphenyl sulfone was obtained. A pure product was obtained by recrystallization from water-ethanol with a yield of 19.6 g (yield 90.0%) and a melting point of 123-125°C. Melting point 127-128℃.

Example 2 17.7 g (0.1 mol) of benzene sulfochloride, 22.5 g (0.2 mol) of chlorobenzene, and 3.5 g of perfluorosulfonic acid type resin were heated and stirred for 1 hour under reflux of chlorobenzene. After 1 hour, the temperature of the reaction mixture gradually increases. Heat for a further 7 hours, maintaining the temperature at 145-150°C. After cooling to 50°C, the perfluorosulfonic acid type resin is separated and further washed with a small amount of chlorobenzene.
After combining the liquid and washing liquid, chlorobenzene was removed by steam distillation to yield 4-chlorodiphenylsulfone. Yield 23.2g (yield 91.5
%). A pure product was obtained by recrystallization from water-ethanol with a melting point of 91-93°C. Melting point 95-96℃.

Example 3 Benzene sulfochloride was added to the total amount of perfluorosulfonic acid type resin used in Example 2.
17.7 g (0.1 mol) and 22.5 g of chlorobenzene were added, and the mixture was heated and stirred in the same manner as in Example 2. The same treatment was performed to obtain 4-chlorodiphenylsulfone. Yield: 22.8g (90.8% yield). Melting point 91-93℃.

Example 4 4-chloro- 4'-methyldiphenyl sulfone was obtained.

A pure product was obtained by recrystallization from ethanol, yield 23.9 g (yield 89.8%), melting point 119-121°C. Melting point 124~
125℃.

Example 5 P-methoxybenzenesulfochloride 20.7g
(0.1 mol), 64.5 g (0.7 mol) of toluene, and 10.3 g of perfluorosulfonic acid type resin were heated under reflux at 110°C for 10 hours. After the perfluorosulfonic acid type resin was separated, it was washed with a small amount of Torcon.

Combine the solution and cleaning solution and steam distillate.
-Methyl-4'-methoxydiphenyl sulfone was obtained. Yield 22.5g (yield 86.5%). Melting point 100-101℃,
A pure product was obtained by recrystallization from water-ethanol. melting point
104-105℃.

Example 6 P-chlorobenzenesulfochloride 21.2g (0.1
mol), 16.8 g (0.15 mol) of chlorobenzene, and 4.2 g of perfluorosulfonic acid type resin are heated and stirred.
After 2 hours the reflux temperature reached 150°C and was kept at the same temperature for a further 3 hours. After cooling to room temperature, 20ml
of dichloroethane was added, and the perfluorosulfonic acid type resin was separated and further washed with a small amount of dichloroethane. Steam distillation to remove dichloroethane and chlorobenzene yielded 4,4'-dichlorodiphenyl sulfone.

Yield: 25.5g (89% yield). Melting point 145-148℃. water-
A pure product was obtained by recrystallization from ethanol. Melting point 148
~149℃.

Example 7 Based on the total amount of perfluorosulfonic acid type resin used in Example 6, 21.2 g (0.1 mol) of P-chlorobenzene sulfochloride and 16.8 g of chlorobenzene
(0.15 mol) was heated and stirred in the same manner as in Example 6. 4,4'-dichlorodiphenyl sulfone was obtained by the same treatment.

Yield 25.1g (yield 87.5%), melting point 145-148℃.

Example 8 P-nitrobenzene sulfochloride 25.7g (0.1
mol), 39 g (0.5 mol) of benzene, and 7.7 g of perfluorosulfonic acid type resin were heated under reflux for 15 hours.
After cooling to room temperature, the perfluorosulfonic acid type resin was separated and washed with a small amount of benzene. The liquid and washing liquid were combined, water was added, and azeotropic distillation was performed to obtain 4-nitrodiphenylsulfone.

Yield: 23.9g (91% yield). Melting point 136-138℃. A pure product was obtained by recrystallization from ethanol. Melting point 140-141
℃.

Claims (1)

[Claims] 1. A method for producing diarylsulfone, which comprises reacting an aromatic sulfochloride and an aromatic hydrocarbon in the presence of a perfluorosulfonic acid type resin.