JP4011364B2 - Method for producing 2,4'-dihydroxydiphenylsulfone - Google Patents

Description

【００１１】
第１表に見られるように、フェノールとｐ−フェノールスルホン酸を原料とする実施例１においても、フェノールと硫酸を原料とする実施例２においても、原料に４,４'−ジヒドロキシジフェニルスルホンを添加することにより、ほぼ同量の２,４'−ジヒドロキシジフェニルスルホンと４,４'−ジヒドロキシジフェニルスルホンが生成している。これに対して、原料に４,４'−ジヒドロキシジフェニルスルホンを添加していない比較例１〜２においては、２,４'−ジヒドロキシジフェニルスルホンの生成量は４,４'−ジヒドロキシジフェニルスルホンの生成量の約２分の１である。この結果から、原料に４,４'−ジヒドロキシジフェニルスルホンを添加して脱水縮合反応を行うことにより、４,４'−ジヒドロキシジフェニルスルホンの生成を抑制し、２,４'−ジヒドロキシジフェニルスルホンの生成量を増加し得ることが分かる。
【００１２】
【発明の効果】
本発明方法によれば、フェノールとフェノールスルホン酸、又は、フェノールと硫酸、発煙硫酸若しくは無水硫酸との脱水縮合反応に際して、原料に４,４'−ジヒドロキシジフェニルスルホンを添加することにより、４,４'−ジヒドロキシジフェニルスルホンの生成量を抑制し、２,４'−ジヒドロキシジフェニルスルホンの生成量を増加することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing 2,4′-dihydroxydiphenylsulfone. More specifically, in the present invention, 2,4′-dihydroxydiphenylsulfone can be obtained in high yield from phenol and phenolsulfonic acid, or phenol and sulfuric acid, fuming sulfuric acid or sulfuric anhydride. The present invention relates to a method for producing '-dihydroxydiphenylsulfone.
[0002]
[Prior art]
A mixture of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone can be obtained by dehydration condensation reaction of phenol and phenolsulfonic acid, or phenol and sulfuric acid, fuming sulfuric acid or anhydrous sulfuric acid. Of these, 2,4′-dihydroxydiphenylsulfone is used as a color developer for heat-sensitive recording materials, and is particularly useful for obtaining heat-sensitive recording papers that have excellent color developability, little background fogging, and good storage stability. Compound. On the other hand, 4,4′-dihydroxydiphenylsulfone is known as a raw material for polyethersulfone, which is an engineering plastic having high heat resistance, or as a monomer for improving heat resistance such as polycarbonate.
The product of the dehydration condensation reaction of phenol and phenolsulfonic acid, or phenol and sulfuric acid, fuming sulfuric acid or sulfuric anhydride is a mixture of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone, Is separated and purified and used for each application. However, since 2,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxydiphenyl sulfone are co-produced at an almost constant ratio, when the demand for 2,4′-dihydroxydiphenyl sulfone is large, It is desirable to increase the yield of 4'-dihydroxydiphenyl sulfone.
In JP-A-6-107622, as a method for industrially producing 2,4′-dihydroxydiphenylsulfone with high selectivity, phenols and sulfuric acid are mixed and heated to obtain dihydroxydiphenylsulfones. In the production, a method in which phosphonic acid, phosphinic acid or a salt thereof is present as a catalyst in the reaction system has been proposed. Japanese Patent Application Laid-Open No. 10-25277 discloses a method for producing a highly pure 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone industrially advantageously together with phenol. A method of reacting a sulfonating agent in an o-dichlorobenzene solvent, precipitating and separating 4,4′-dihydroxydiphenylsulfone from the reaction solution, and then isolating 2,4′-dihydroxydiphenylsulfone from the filtrate. Proposed. However, even by this method, it is inevitable that 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone are co-produced at a substantially constant rate. It was difficult to adapt to the supply and demand balance of 4,4'-dihydroxydiphenylsulfone.
[0003]
[Problems to be solved by the invention]
The present invention uses 2,4′-dihydroxydiphenylsulfone in a high yield by using phenol and phenolsulfonic acid, or phenol and sulfuric acid, fuming sulfuric acid or anhydrous sulfuric acid as raw materials. The object is to provide a method for producing sulfone.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have determined that 2,4′- by dehydration condensation reaction using phenol and phenolsulfonic acid, or phenol and sulfuric acid, fuming sulfuric acid, or anhydrous sulfuric acid as raw materials. In the production of dihydroxydiphenylsulfone, it was found that the yield of 2,4′-dihydroxydiphenylsulfone can be increased by adding 4,4′-dihydroxydiphenylsulfone to the raw material. It came to be completed.
That is, the present invention
(1) When producing 2,4′-dihydroxydiphenylsulfone by dehydration condensation reaction using phenol and phenolsulfonic acid, or phenol and sulfuric acid, fuming sulfuric acid or sulfuric anhydride as raw materials, 4,4′-dihydroxydiphenyl is used as the raw material. sulfone phenolsulfonic acid, 0 sulfuric acid, fuming sulfuric acid or sulfuric anhydride. 1 to 0.7 mol per mol method for producing 2,4'-dihydroxydiphenyl sulfone which comprises adding,
(2) The method for producing 2,4′-dihydroxydiphenylsulfone according to item 1, wherein the dehydration condensation reaction is performed in the absence of a solvent or in the presence of an aromatic hydrocarbon solvent having a boiling point of 130 to 200 ° C., and
(3) The method for producing 2,4′-dihydroxydiphenylsulfone according to item 1, wherein the dehydration condensation reaction is performed in the presence of phosphoric acid, phosphonic acid, phosphinic acid or a salt thereof,
Is to provide.
Furthermore, as a preferred embodiment of the present invention,
(4) The method for producing 2,4′-dihydroxydiphenylsulfone according to item 2, wherein the dehydration condensation reaction is carried out by heating at 140 to 170 ° C. under reduced pressure without a solvent,
Can be mentioned.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the method for producing 2,4′-dihydroxydiphenylsulfone of the present invention, 2,4′-dihydroxydiphenylsulfone is obtained by dehydration condensation reaction using phenol and phenolsulfonic acid, or phenol and sulfuric acid, fuming sulfuric acid or sulfuric anhydride. 4,4′-dihydroxydiphenylsulfone is added to the raw material.
Phenol and phenolsulfonic acid form a mixture of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone by a dehydration condensation reaction. Phenol and sulfuric acid produce a mixture of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone by a dehydration condensation reaction. Instead of sulfuric acid, fuming sulfuric acid or anhydrous sulfuric acid can also be used. Usually, the weight ratio of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone produced is about 30:70. According to the method of the present invention, the production of 4,4′-dihydroxydiphenylsulfone is suppressed and the production of 2,4′-dihydroxydiphenylsulfone is increased, and 2,4′-dihydroxydiphenylsulfone and 4,4′- The amount of dihydroxydiphenylsulfone produced can be controlled in the range of about 30:70 to 50:50 by weight.
[0006]
In the method of the present invention, the amount of 4,4′-dihydroxydiphenylsulfone added to the raw material is not particularly limited, but is 0.1 to 0.7 mole times that of phenolsulfonic acid, sulfuric acid, fuming sulfuric acid or sulfuric anhydride. Is preferable, and it is more preferable that it is 0.3-0.5 mol times. However, the number of moles of fuming sulfuric acid is counted as the total number of moles of H ₂ SO ₄ and SO ₃ contained in the fuming sulfuric acid. Whether the amount of 4,4′-dihydroxydiphenylsulfone added to the raw material is less than 0.1 mol times of phenolsulfonic acid, sulfuric acid, fuming sulfuric acid or anhydrous sulfuric acid, or more than 0.7 mol times, There is a possibility that the effect of suppressing the production of 4′-dihydroxydiphenylsulfone and increasing the production of 2,4′-dihydroxydiphenylsulfone may not be sufficiently exhibited.
In the method of the present invention, there is no particular limitation on the reaction method of phenol and phenolsulfonic acid, or phenol and sulfuric acid, fuming sulfuric acid, or anhydrous sulfuric acid. For example, the reaction can be performed without a solvent, or the reaction can be performed in the presence of a solvent. It can also be made. Phenol is preferably charged and reacted in excess of phenol sulfonic acid in an amount that is stoichiometrically required, and more preferably 2 to 4 moles of phenol sulfonic acid is charged and reacted. Phenol is preferably charged in excess of the stoichiometrically required amount with respect to sulfuric acid, fuming sulfuric acid or anhydrous sulfuric acid, and 2-4 mol times sulfuric acid, fuming sulfuric acid or anhydrous sulfuric acid is charged. It is preferable to react.
[0007]
In the method of the present invention, when the dehydration condensation reaction is carried out in the absence of a solvent, it is preferably carried out by heating to 140 to 170 ° C. under a reduced pressure of 80.0 to 6.7 kPa. If the reaction temperature is less than 140 ° C., the reaction rate may be slow and a long time may be required for the dehydration condensation reaction. When the reaction temperature exceeds 170 ° C., 4,4′-dihydroxydiphenylsulfone is often produced, and it may be difficult to increase the production amount of 2,4′-dihydroxydiphenylsulfone. The water produced by the dehydration condensation reaction can be removed out of the reaction system as an azeotrope with phenol. If necessary, phenol can be added during the reaction to supplement phenol distilled out of the system by azeotropy with water. In the reaction, phosphorus compounds such as phosphonic acid, phosphinic acid and phosphoric acid can coexist. By coexisting such a phosphorus compound, the content of 2,4′-dihydroxydiphenylsulfone in the resulting dihydroxydiphenylsulfone isomer mixture can be increased.
[0008]
In the method of the present invention, when the dehydration condensation reaction is performed in the presence of a solvent, the solvent is preferably an aromatic hydrocarbon solvent having a boiling point of 130 to 200 ° C. When the boiling point of the solvent is less than 130 ° C., the reaction temperature is low and there is a possibility that a long time is required for the dehydration condensation reaction. When the boiling point of the solvent exceeds 200 ° C., it may be difficult to remove the solvent from the produced dihydroxydiphenyl sulfones. Aromatic hydrocarbons are inert, and do not react with phenolsulfonic acid, sulfuric acid, fuming sulfuric acid or anhydrous sulfuric acid under the conditions for producing 2,4′-dihydroxydiphenylsulfone, and are not compatible with water produced by dehydration condensation reaction. Since it can boil and water can be removed out of a reaction system, it can be used conveniently. Examples of the hydrocarbon having a boiling point of 130 to 200 ° C. include xylene, ethylbenzene, cumene, pseudocumene, mesitylene, and cymene.
A mixture of 2,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxydiphenyl sulfone produced by the method of the present invention was purified from 2,4′-dihydroxydiphenyl sulfone and 4,4 by purification using an organic solvent or the like. It can be separated into '-dihydroxydiphenylsulfone.
The weight of each component contained in the reaction mixture was 2,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfone, p-phenolsulfonic acid, phenol determined by high performance liquid chromatography of the reaction mixture after completion of the reaction. And the weight of the reaction mixture determined from the weight of the azeotropic mixture of water and phenol distilled during the reaction.
[0009]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The contents of 2,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfone, p-phenolsulfonic acid and phenol were quantified by high performance liquid chromatography.
Example 1
In a reactor, 670 g (7.13 mol) of phenol, 418 g (2.40 mol) of p-phenolsulfonic acid, 250 g (1.00 mol) of 4,4′-dihydroxydiphenylsulfone and 17 g (0.21 mol) of phosphonic acid ) And a dehydration condensation reaction was carried out at 150 to 165 ° C. for 6 hours while reducing the pressure from 74.6 kPa to 34.7 kPa. The reaction was terminated when 252 g of a mixture of phenol and water was distilled.
The reaction mixture was 1,094 g, 21% by weight of 2,4′-dihydroxydiphenylsulfone (230 g), 45% by weight of 4,4′-dihydroxydiphenylsulfone (492 g), and 8% by weight of p-phenolsulfonic acid (88 g). The content of phenol was 23% by weight (252 g), and other impurities were 3% by weight (33 g).
The yield of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone produced by the dehydration condensation reaction with respect to 330 g (1.90 mol) of consumed p-phenolsulfonic acid was 2,4′-dihydroxy. It was 49% of diphenylsulfone and 51% of 4,4′-dihydroxydiphenylsulfone.
Example 2
A reactor was charged with 605 g (6.44 mol) of phenol, 235 g (2.40 mol) of sulfuric acid, 950 mL of xylene, 16.5 g (0.20 mol) of phosphonic acid, and 250 g (1.00) of 4,4′-dihydroxydiphenylsulfone. The reaction mixture was subjected to a dehydration condensation reaction under reflux for 6 hours, the temperature was lowered to 80 ° C., and xylene was distilled off under reduced pressure to obtain 1,074 g of a reaction mixture.
The reaction mixture was 2,4′-dihydroxydiphenylsulfone 20% by weight (215 g), 4,4′-dihydroxydiphenylsulfone 42% by weight (451 g), p-phenolsulfonic acid 8% by weight (86 g), phenol 23% by weight. (247 g) and 7% by weight (75 g) of other impurities.
The yield of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone produced by the dehydration condensation reaction with respect to sulfuric acid was 36% of 2,4′-dihydroxydiphenylsulfone, and 4,4′-dihydroxydiphenylsulfone 34. %Met.
Comparative Example 1
A reactor was charged with 949 g (10.10 mol) of phenol, 591 g (3.40 mol) of p-phenolsulfonic acid and 17 g (0.21 mol) of phosphonic acid, and the pressure was increased from 150 to 165 ° C. at a pressure of 80.0 kPa. The dehydration condensation reaction was carried out for 6 hours while reducing the pressure to 6.7 kPa. The reaction was terminated when 548 g of a mixture of phenol and water had distilled out.
The reaction mixture was 1,009 g, 2,4′-dihydroxydiphenylsulfone 23% by weight (232 g), 4,4′-dihydroxydiphenylsulfone 43% by weight (434 g), p-phenolsulfonic acid 12% by weight (121 g) And 19% by weight of phenol (192 g) and 3% by weight of other impurities (30 g).
The yield of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone produced by the dehydration condensation reaction with respect to 470 g (2.70 mol) of consumed p-phenolsulfonic acid was 2,4′-dihydroxy. It was 34% diphenylsulfone and 64% 4,4′-dihydroxydiphenylsulfone.
Comparative Example 2
A reactor was charged with 1,296 g (13.79 mol) of phenol, 529 g (5.40 mol) of sulfuric acid and 38 g (0.46 mol) of phosphonic acid, and a pressure of 74.6 kPa to 34.40 at 150-165 ° C. The dehydration condensation reaction was carried out for 6 hours while reducing the pressure to 7 kPa. When 56 g of the mixed liquid of phenol and water was distilled, 267 g (2.84 mol) of phenol was added, and dehydration reaction was performed at 150 to 165 ° C. while reducing the pressure from 34.7 kPa to 13.3 kPa. It was. When the total amount of the distillate of the mixture of phenol and water reached 675 g, 267 g (2.84 mol) of phenol was added, and the pressure was reduced from 34.7 kPa to 13.3 kPa at 150 to 165 ° C. for 2 hours. A dehydration condensation reaction was performed. When the total amount of the distillate of the mixture of phenol and water reached 812 g, 267 g (2.84 mol) of phenol was further added, and the pressure was reduced from 34.7 kPa to 13.3 kPa at 150 to 165 ° C. for 2 hours. A dehydration condensation reaction was performed, and the reaction was terminated when the amount of the distillate of the mixed solution of phenol and water reached 966 g.
The reaction mixture was 1,698 g, 20% by weight of 2,4′-dihydroxydiphenylsulfone (340 g), 44% by weight of 4,4′-dihydroxydiphenylsulfone (747 g), and 10% by weight of p-phenolsulfonic acid (170 g). , 24% by weight of phenol (408 g) and 2% by weight of other impurities (34 g).
The yield of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone produced by the dehydration condensation reaction with respect to sulfuric acid was 25% of 2,4′-dihydroxydiphenylsulfone, and 4,4′-dihydroxydiphenylsulfone 55. %Met.
The results of Examples 1-2 and Comparative Examples 1-2 are shown in Table 1.
[0010]
[Table 1]

[0011]
As seen in Table 1, in Example 1 using phenol and p-phenolsulfonic acid as raw materials, and in Example 2 using phenol and sulfuric acid as raw materials, 4,4′-dihydroxydiphenylsulfone was used as the raw material. By the addition, approximately the same amounts of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone are formed. In contrast, in Comparative Examples 1 and 2 in which 4,4′-dihydroxydiphenylsulfone was not added to the raw material, the amount of 2,4′-dihydroxydiphenylsulfone produced was 4,4′-dihydroxydiphenylsulfone produced. About half of the amount. From this result, the production of 4,4′-dihydroxydiphenylsulfone is suppressed by adding 4,4′-dihydroxydiphenylsulfone to the raw material and carrying out a dehydration condensation reaction to suppress the production of 4,4′-dihydroxydiphenylsulfone. It can be seen that the amount can be increased.
[0012]
【The invention's effect】
According to the method of the present invention, in the dehydration condensation reaction of phenol and phenolsulfonic acid, or phenol and sulfuric acid, fuming sulfuric acid, or sulfuric anhydride, 4,4′-dihydroxydiphenylsulfone is added to the raw material to produce 4,4. The production amount of '-dihydroxydiphenylsulfone can be suppressed, and the production amount of 2,4'-dihydroxydiphenylsulfone can be increased.

Claims (3)

Phenol and phenolsulfonic acid, or phenol and sulfuric acid, when the fuming sulfuric acid or sulfuric anhydride to produce a 2,4'-dihydroxydiphenyl sulfone by dehydration condensation reaction as a raw material, the raw material 4,4'-dihydroxydiphenylsulfone phenol 0 sulfonic acid, sulfuric acid, fuming sulfuric acid or sulfuric anhydride. 1 to 0.7 molar times the production method of 2,4'-dihydroxydiphenyl sulfone which comprises adding.   The method for producing 2,4'-dihydroxydiphenylsulfone according to claim 1, wherein the dehydration condensation reaction is carried out in the absence of a solvent or in the presence of an aromatic hydrocarbon solvent having a boiling point of 130 to 200 ° C.   The method for producing 2,4'-dihydroxydiphenylsulfone according to claim 1, wherein the dehydration condensation reaction is carried out in the presence of phosphoric acid, phosphonic acid, phosphinic acid or a salt thereof.