JPS602303B2 - Method for producing bis(4-hydroxyalkoxyphenyl)sulfone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing highly pure bis(4-hydroxyalkoxyphenyl) sulfone in good yield from bis(4-hydroxyphenyl) sulfone and alkylene oxide.

Bis(4-hydroxyalkoxyphenyl) sulfone, as a diol component, is an extremely useful material as a raw material for engineering plastics such as polyester resins, polyurethane resins, polycarbonate resins, and epoxy resins, and it improves the heat resistance, oxidation resistance, and mechanical properties of polymers. etc. will be significantly improved. It is also a useful compound as an intermediate in organic synthetic chemistry, such as a smoothing agent and a surfactant, and therefore there is a demand for a method for producing it with high purity and high yield. Generally, it is known that the method of adding alkylene oxide to a phenolic hydroxyl group is to carry out the reaction in the presence of an alkaline catalyst without a solvent or in an organic solvent, but bis(4-hydroxyphenyl)sulfone has a melting point. Because the temperature is as high as 250°C, it is very difficult to react without a solvent.

In addition, it is necessary to use a large amount of organic solvent, such as methyl alcohol, inpropyl alcohol, benzene, etc., and to conduct the reaction for a long time under pressurized conditions, resulting in wastage of solvent and production of large amounts of by-products. Not suitable for commercial production. The present inventors have arrived at the present invention as a result of intensive research into a method for producing high-purity bis(4-hydroxyalkoxyphenyl) sulfone suitable for industrial production.

The present invention produces high-yield, high-purity pis(4-hydroxyalkoxyphenyl) by a short-time reaction at a temperature of 70 to 90 qo in an aqueous solvent in the presence of a weakly alkaline catalyst without using any general organic solvent. ) Provides a method for industrially producing sulfone.

The bis(4-hydroxyphenyl)sulfone useful in the present invention has the following general formula. Moreover, alkylene oxide is ethylene oxide, propylene oxide, and butylene oxide having an alkylene group having 2 to 4 carbon atoms.

The catalyst used in the present invention is a general weakly alkaline metal catalyst. That is, formates, acetates, propionates, oxalates, and malonates of alkali metals or alkali metals are used alone or in combination. If a highly alkaline catalyst is used, the reactivity will increase, but by-products will be produced and the purity will decrease. When implementing the invention,
Either the normal pressure gas phase method or the autoclave method may be used, but
The reaction temperature is 70-90,000°.

When the temperature exceeds 90:00, the reaction is fast but the purity decreases, and 70:00 is exceeded.
If it is lower than qo, the reaction rate will be slow.

Since the present invention does not use any organic solvent, there is no danger of toxicity or flammability in the factory, and it is safe and economically advantageous, and is extremely suitable for industrial production. The invention will be explained below with examples.

In addition, "%" in the examples indicates weight %. Example 1 500 μl of bis(4-hydroxyphenyl)sulfone, 1000 μl of water, and 20 μl of sodium acetate were placed in a stainless steel 3-guage autoclave equipped with a vacuum cleaner, and the reaction mixture was heated to 85 qo. Under the pressure of the ground, 220 ml of ethylene oxide was introduced at mountain time while offering candlelight.

Further, the reaction is continued for 1 hour while maintaining the reaction temperature at 80 to 90°C. After the reaction was completed, the reaction product was thoroughly washed with water, filtered, and dried to obtain 650 tons of bis(4-hydroxyethoxyphenyl)sulfone. The results are shown in Table 1. Example 2 The method of Example 1 was repeated by changing the type of catalyst.

The results are shown in Table 1. Comparative Example 1 500 g of bis(4-hydroxyphenyl)sulfone, 100 g of isopropanol, and 5 g of sodium hydroxide were placed in a flask equipped with a rope frame machine, and the reaction mixture was heated to 85°C. Ethylene oxide 2 while worshiping
Infuse 20 evenings in 2 hours.

Furthermore, the reaction is continued for 1 hour while maintaining the reaction temperature at 80 to 90 qo. After the reaction is completed, isopropanol is distilled off,
When the reactant is thoroughly washed with water, filtered, and dried, bis(
620 units of 4-hydroxyethoxyphenyl sulfone were obtained. The results are shown in Table 1. Comparative Example 2 The method of Example 1 was repeated except that sodium hydroxide was added as a catalyst and the reaction temperature was changed to 100 to 110 quarts.

The results are shown in Table 1. Table 1 The composition is the result of analysis by gas chromatography.

The 2 molar adduct is the desired reaction product. Example
3-bis(4-hydroxyphenyl) sulfo 500 mg,
750 parts of water and 25 parts of potassium acetate were placed in the autoclave and the reaction mixture was heated to 85°C.
350 kg of propylene oxide is introduced in 1 hour under a pressure of 1.5 kg' and while stirring.

Further, the reaction was continued for 1 hour and 3 seconds while maintaining the reaction temperature at 80 to 90°C. After the reaction was completed, the reaction product was sufficiently washed with water, dehydrated, and dried to obtain 710 ta of bis(4-hydroxybropoxyphenyl) sulfone. Yield 97
．． 0%. The composition was as follows.

Claims (1)

[Claims] 1. When producing bis(4-hydroxyalkoxyphenyl)sulfone by reacting bis(4-hydroxyphenyl)sulfone with alkylene oxide, a formate of an alkali metal or alkaline earth metal, acetic acid is added in an aqueous solvent. A method characterized in that the reaction is carried out at a temperature of 70 to 90°C in the presence of a weakly alkaline catalyst selected from salts, propionates, oxalates and malonates.