JPH0910597A - Alkylation catalyst for aromatic compound, preparation thereof, and preparation of tertiary alkyl phenol - Google Patents

Abstract

PURPOSE: To reduce the quantity of a catalyst without deteriorating productivity and to simplify a post treatment process after a reaction by making a phenol derivative in which a phenolic hydroxyl group forms sulfonic ester. CONSTITUTION: When sulfuric acid and phenol are reacted in a mole ratio of 2-4:1 and at temperature of 50-100 deg.C, an alkylation catalyst for an aromatic compound prepared from a phenol derivative having a sulfo group on an aromatic nucleus and in which a phenolic hydroxyl group forms sulfonic ester is obtained. In the alkylation catalyst, disulfate having two or three sulfo groups on an aromatic nucleus such as trisulfonated phenoldisulfate and disulfonated phenoldisulfate is especially preferable because of its high catalytic activity. A tertiary olefin and phenol are reacted at 50-140 deg.C in the presence of the catalyst to obtain a tertiry alkylphenol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an alkylation catalyst for aromatic compounds, a method for producing the same, and a method for producing tertiary alkylphenols using this alkylation catalyst.

[0002]

2. Description of the Related Art Alkylated phenols are used as various chemical raw materials, and among them, tertiary alkylphenols are condensed with formalin to be widely used as various tackifiers and raw materials for rubber adhesives. It is also used as a resin for ink by reacting with rosin. It is also used as a molecular weight regulator for polycarbonate resins.

Conventionally, regarding a method for producing tertiary alkylphenols by tertiary alkylation of phenols,
It is a known fact that a large amount of sulfuric acid, alkyl-substituted or unsubstituted phenylsulfonic acid, phenolsulfonic acid, toluenesulfonic acid and the like is used as a catalyst, for example, Industrial Engineering Chemistry (Ind. Eng. Chem. ) Magazine 35 (1943
Year) 266, cresol 10 with concentrated sulfuric acid as catalyst
After the reaction was carried out by using a large amount of 5 parts by weight with respect to 0 parts by weight, the mixture was neutralized with an aqueous solution of sodium hydroxide at high temperature, and then the aqueous phase containing the neutralized salt was separated, There is an example in which the concentrated sulfuric acid used as a catalyst is removed by washing the oil phase with warm water and separating the aqueous phase. Further, JP-A-52-91830 discloses that concentrated sulfuric acid is used as a catalyst. , 2 parts by weight with respect to 100 parts by weight of phenol, after the reaction, the catalyst is neutralized, the reaction solution is washed with water, and the oil phase containing the reaction product and the aqueous phase are separated to neutralize. The salt is extracted and separated into an aqueous phase, and the residual acid catalyst in the oil phase is neutralized and washed with an alkaline aqueous solution, and then the oil phase and the alkaline aqueous phase are separated to remove the catalyst, and then the reaction product is contained. An example of transferring the oil phase to a distillation purification step is disclosed.
Further, in Japanese Patent Laid-Open No. 51-113833, cresol 10 is prepared by using an aqueous solution of toluenesulfonic acid as a catalyst.
The reaction was carried out by using a large amount of 5 to 15 parts by weight with respect to 0 parts by weight, and then neutralized with 10 parts by weight of a methanol solution of sodium hydroxide based on 100 parts by weight of the reaction product. An example is described in which toluene sulfonic acid used as a catalyst is removed by washing with warm water, extracting a neutralized salt into an aqueous phase, and separating the aqueous phase.

[0004]

However, in the method of or, etc., in order to prevent dealkylation of the alkylated phenols, which is a reaction product, during distillation and purification, the distillation and purification of the alkylated phenols after the reaction is completed. Before, it is necessary to neutralize the catalyst and remove it from the system. Without removing the neutralization salt of the catalyst, or without removing a part thereof, the alkylated phenols which are the reaction products. In the case of the distillation purification, the reaction solution was concentrated and neutralized salts were precipitated, the fluidity was lowered, the stirring efficiency was lowered, the latent heat of vaporization could not be secured, and the amount of vapor distilled was reduced. Therefore, there is a drawback that the recovery rate of the target product decreases. Further, when the residual liquid containing the neutralizing salt is discharged after the temperature and the vapor pressure are lowered, the neutralizing salt is deposited and the pipe is closed.

Therefore, after neutralizing the catalyst used in the reaction,
When the reaction solution containing the neutralization salt is distilled, as a step of removing the neutralization salt to such an extent that the fluidity can always be maintained, the reaction solution containing the neutralization of the catalyst is repeatedly washed with water and separated, and the complicated post-treatment is performed. A process is required.

Further, since the amount of the catalyst used in the reaction is large, there is a problem that the treatment process of the catalyst becomes more complicated. On the other hand, however, if the amount of the catalyst is reduced to carry out the reaction in order to facilitate the separation and removal of the catalyst, the reaction rate becomes slow and the productivity is significantly impaired.

An object of the present invention is to develop an alkylation catalyst for aromatic compounds which can reduce the amount of the catalyst used without lowering the productivity and can simplify the post-treatment step after the reaction, and to produce the alkylation catalyst. A method, and further, to establish a method for producing alkylphenols using this catalyst.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that they have a sulfonic acid group on an aromatic nucleus and a phenolic hydroxyl group forms a sulfonic acid ester. The phenol derivative has a high activity when used as an alkylation catalyst for aromatic compounds such as phenols, toluene and xylene. This alkylation catalyst is a method of reacting sulfuric acid and phenols. It can be easily produced, and when the catalyst is used in the method for producing an alkylated phenol, the amount of the catalyst used can be greatly reduced because the catalyst activity is high, and the catalyst after the reaction can be reduced accordingly. The neutralization salt produced by the addition can be greatly reduced, and the neutralization salt itself has a property that it can be finely dispersed in the reaction liquid to maintain a slurry state and maintain fluidity. Without removing the neutralized salt of the phenol derivative used in the catalyst after the reaction, even when the distillation separation of the reaction product in the presence of a neutral salt, easier reaction solution retains fluidity,
The inventors have found that a distillation operation is possible and have completed the present invention.

That is, the present invention is characterized by comprising a phenol derivative having a sulfonic acid group on the aromatic nucleus and having a phenolic hydroxyl group forming a sulfonic acid ester. -Catalyst, method for producing alkylation catalyst for aromatic compound characterized by reacting sulfuric acid and phenol, and third reaction of tertiary olefin and phenol in the presence of acid catalyst
A method for producing a primary alkylphenol, wherein the acid catalyst has a sulfonic acid group on an aromatic nucleus, and
It is intended to provide a method for producing a tertiary alkylphenol, which comprises using a phenol derivative in which a phenolic hydroxyl group forms a sulfonate ester.

The alkylation catalyst for aromatic compounds of the present invention has a sulfonic acid group on the aromatic nucleus, and
Any phenol derivative in which the phenolic hydroxyl group forms a sulfonic acid ester may be used, and examples thereof include monosulfonated phenol, disulfonated phenol or disulphonic acid ester of trisulfonated phenol; monosulfonated phenol, disulfonated phenol or trisulfonated. Phenol monosulfate; monosulfonated cresol, disulfonated cresol or trisulfonated cresol disulfate; monosulfonated cresol, disulfonated cresol, or trisulfonated cresol monosulfate; monosulfonated xylenol, disulfonated Xylenol or trisulfonated xylenol disulfate; monosulfonated xylenol, disulfonated xylenol or trisulfonated xylenol monosulfate They include phenol derivatives such as Le, these may be used alone or in combination of two or more.

Among these alkylation catalysts, sulfonic acid groups such as trisulfonated phenol disulfate, disulfonated phenol disulfate, trisulfonated phenol monosulfate, etc. Or, those having three units are particularly preferable because of high catalytic activity, and among these, disulfuric acid esters such as trisulfonated phenol disulfuric acid ester and disulfonated phenol disulfuric acid ester are more preferable.

The phenol derivative includes phenols and
An aromatic compound such as toluene, benzene or xylene can be used as a catalyst for a reaction such as alkylation at a reaction temperature of 50 to 140 ° C. using a tertiary olefin.

The method for producing the alkylation catalyst for aromatic compounds of the present invention is not particularly limited, but for example, it is produced by the method of the present invention, that is, a method characterized by reacting sulfuric acid and phenols. can do.

Examples of the phenols used in the method for producing an alkylation catalyst for aromatic compounds include phenols substituted or unsubstituted with a lower alkyl group such as phenol, cresol and xylenol, sulfonated phenols and sulfonated cresols. Sulfonated xylenol and the like, phenols substituted with a sulfonic acid group and the like can be used. Among them, phenol,
Or, it is preferable to use monosulfonated phenol, disulfonated phenol, or trisulfonated phenol, which is a phenol substituted with 1 to 3 sulfonic acid groups, and among them, it is industrially easy to use phenol. It is preferable because it can be obtained.

Further, the sulfuric acid used in the method for producing the alkylation catalyst for aromatic compounds may satisfy the standard of industrially available general-purpose products, among which concentrated sulfuric acid and fuming sulfuric acid are preferable. Although it is used, it is usually preferable to use 98% by weight or more of sulfuric acid.

In the reaction, the molar ratio of sulfuric acid to phenols is preferably 2: 1 to 4: 1. Among them, the molar ratio is 2.5: 1 to 3.5: 1. It is particularly preferable to carry out.

The reaction temperature of sulfuric acid and phenols in the reaction is preferably 50 to 100 ° C, and particularly preferably 80 to 100 ° C.

In the method for producing an alkylation catalyst for aromatic compounds of the present invention, in the reaction between sulfuric acid and phenols, first, the aromatic nucleus of phenols is sequentially sulfonated,
Next, the phenolic hydroxyl group becomes a sulfonic acid ester, which is 3640 to 360 by infrared absorption spectrum analysis.
The reaction was completed by confirming the end point of the reaction by the disappearance of OH absorption at 0 cm ^-1 , but the mixture ratio of the sulfonate ester of monosulfonated phenols was low in the resulting mixture, and trisulfonated phenol disulfate ester was obtained. , Disulfonated phenol disulfate, trisulfonate phenol disulfate, etc., sulfonates of disulfonated phenols, or sulfonates of trisulfonated phenols are produced at a high mixing ratio. Although it may be used after being purified, the mixture can be directly used as a catalyst without being purified.

The phenols used in the method for producing the tertiary alkylated phenols of the present invention can be arbitrarily selected from the phenols that can be used for producing the phenol derivative used as the catalyst, Among these, lower alkyl group-substituted or unsubstituted phenols such as phenol, meta-cresol, para-cresol, mixed meta-para-cresol, and 2,4-xylenol are preferable. Among them, phenol is particularly preferable.

As the tertiary olefin used in the present invention, isobutylene, 2-methyl-1-butene, 2-
Methyl-2-butene, diisobutylene, α-methylstyrene and the like can be mentioned, but among them, isobutylene and diisobutylene are particularly preferable.

The tertiary alkylphenols, which are the target products of the present invention, include, for example, monotertiary alkylphenols such as paratertiary butylphenol, paratertiary octylphenol and paracumylphenol; 2,4-ditertiary. Examples include ditertiary alkylphenols such as butylphenol. In each production method, the amount of the tertiary olefin used is 1 mole of the phenol when producing monotertiary alkylphenols. 0.2 to 0.
The range of 8 mol is preferable because both the conversion rate and the selectivity are good and a high-purity product can be obtained with a high yield.
~ 0.6 mol is particularly preferred. Further, in the case of producing ditertiary alkylphenols, the range of 1.2 to 2.0 mol is preferable with respect to 1 mol of phenols, and the range of 1.5 to 1.7 mol is particularly preferable.

The phenol derivative used as the acid catalyst in the present invention is based on 100 parts by weight of phenols.
It is preferably used within the range of 0.05 to 1 part by weight, and among them, 0.05 parts by weight based on 100 parts by weight of phenols.
It is particularly preferable to use it within a range of from 0.5 to 0.5 parts by weight.

In the reaction step of the tertiary olefin and phenols of the present invention, an addition reaction of an alkyl group and then a disproportionation reaction are carried out. The addition reaction is usually 60 to 110. ℃, among them 70-100 ℃
The disproportionation reaction is usually performed at 90 ° C.
It is preferably carried out at ˜160 ° C., and especially at 100˜150 ° C.

The reaction time in the present invention is preferably 2 to 6 hours as the addition reaction time, and preferably 5 to 10 hours as the disproportionation reaction time. The order of supplying the phenols, the tertiary olefins, and the phenol derivative used as the catalyst in the reaction of the tertiary olefin with the phenols of the present invention is usually the addition of the phenol derivative used as the catalyst to the phenol and then the tertiary Preference is given to supplying olefins. The tertiary olefin to be used may be supplied in liquid form, or may be vaporized using a vaporizer or the like and supplied to the reaction.

The reaction can be carried out under any of normal pressure, reduced pressure and increased pressure, but it is usually preferable to carry out under normal pressure which is economically advantageous. The reaction mode in the present invention includes, for example, a batch system and a continuous system, but industrially, for example, under normal pressure, a phenol derivative continuously used is added to a phenol compound continuously supplied, and then a phenol derivative used as a catalyst is added. A continuous method such as continuously supplying a liquid or vaporized tertiary olefin therein to carry out an addition reaction is preferable.

In the post-treatment step after the reaction of the present invention, usually, after neutralizing the phenol derivative used as a catalyst, the produced neutralization salt is treated with 30 to 30 times the amount of the neutralization salt in water.
Washing at 100 ° C., extracting the neutralized salt into a water tank, separating the aqueous phase, and distilling the reaction solution. Alternatively, after neutralizing the acid catalyst, the reaction is carried out with the neutralized salt still contained. A method of directly distilling the liquid can be mentioned. Usually, a method of directly distilling the reaction liquid while containing the neutralized salt is preferable because the process is simple.

When the reaction solution is directly subjected to the distillation treatment while containing the neutralized salt, it is usually carried out at 140 to 200 ° C. for 3 to 7 hours. Industrially, after neutralizing the catalyst in the reaction solution, while still containing the neutralized salt, it is distilled in a simple distillation pot to recover the active ingredient as a top fraction, and a non-volatile component as a bottom component. A method of taking out a slurry which is a mixture of neutralized salt and tar (high boiling point material) is preferable.

[0028]

EXAMPLES The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to the Examples. In addition,% in an example represents weight%.

Example 1 2 with thermometer, reflux condenser, dropping funnel and stirrer
Disulfonated phenol 40 in a 00 ml 4-neck flask
g, and stirred at 70 ° C. 3 g of concentrated sulfuric acid 16g
It was added dropwise in 0 minutes. After completion of the dropping, the temperature is raised to 95 ° C., the reaction is carried out for 1 hour, the reaction is cooled to room temperature, and the phenolic hydroxyl group having two or three sulfonic acid groups on one aromatic nucleus. As a result, 56 g of a mixture of phenol derivatives in which sulfonic acid ester was formed (hereinafter referred to as alkylation catalyst 1) was obtained. When the IR absorption of the obtained alkylation catalyst 1 was examined, the absorption peak of 3640 to 3600 cm ⁻¹ , which is the absorption of the phenolic hydroxyl group, was not recognized.

Example 2 2 with thermometer, reflux condenser, dropping funnel and stirrer
Put 40 g of phenol in a 00 ml four-necked flask, and
Stirred at 0 ° C. 120 g of concentrated sulfuric acid was added dropwise thereto in 60 minutes. After the dropping, the temperature is raised to 100 ° C. and the reaction is performed for 3 hours.
After the reaction, the mixture is cooled to room temperature, and 160 g of a mixture of a phenol derivative having two sulfonic acid groups on one aromatic nucleus or one having three sulfonic acid groups, in which a phenolic hydroxyl group forms a sulfonate ester. Was obtained (hereinafter referred to as alkylation catalyst 2). The IR absorption of the alkylation catalyst 2 was examined, and it was found that the absorption of the phenolic hydroxyl group was 3640-
No absorption peak at 3600 cm ^-1 was observed.

Example 3 5 equipped with a thermometer, reflux condenser, dropping funnel and stirrer
300 g of phenol and 0.7 g of alkylation catalyst 1 (0.2 part by weight relative to 100 parts by weight of phenol) were placed in a 00 ml four-necked flask, and the temperature was raised to 95 ° C. with stirring.
72 g of isobutylene was added thereto for 3 hours to carry out an addition reaction, and after the completion of the supply of isobutylene, stirring was continued at 130 ° C. for 7 hours to carry out a disproportionation reaction, and 372.7 g of a reaction product.
I got

After adding 1.6 g of 20% aqueous sodium hydroxide solution to the reaction product to neutralize the catalyst, the catalyst was transferred to the refining step while containing the neutralized salt without removal, and the temperature was changed to 150 ° C.
Was vacuum distilled for 6 hours. A low boiling component and a high boiling component containing para-tertiary butylphenol were separated by distillation. Higher boiling point 2,4-ditertiary butylphenol was separated from the bottom of the kettle by distillation to obtain 173 g of para-tertiary butylphenol having a purity of 99.8%.

At this time, the remaining amount of the pot containing the neutralized salt is 2.5 g.
(0.7 parts by weight relative to 100 parts by weight of the reaction product), the residual liquid in the kettle was in a slurry state and maintained fluidity until the temperature was lowered to 50 ° C. It was possible to let it out of the system.

Example 4 5 equipped with a thermometer, reflux condenser, dropping funnel and stirrer
300 g of phenol and 0.9 g of alkylation catalyst 2 (0.3 parts by weight per 100 parts by weight of phenol) were placed in a 00 ml four-necked flask, and the temperature was raised to 75 ° C. with stirring.
72 g of isobutylene was added thereto for 5 hours to carry out an addition reaction, and after the supply of isobutylene, stirring was continued at 120 ° C. for 8 hours to carry out a disproportionation reaction to obtain a reaction product 372.9.

To the reaction product, 2.1 g of 20% aqueous sodium hydroxide solution was added to neutralize the catalyst. 150 ° C. in the same manner as in Example 3 while containing the neutralized salt without removing it.
Was distilled for 6 hours to obtain 170 g of para-tertiary butylphenol having a purity of 99.0%.

At this time, the remaining amount of the kettle containing the neutralized salt was 4.4 g (1.2 parts by weight relative to 100 parts by weight of the reaction product) after the completion of the distillation, and the remaining liquid in the kettle was cooled to 50 ° C. Since the fluidity was maintained until it was allowed to flow, it could be flowed out of the distillation system from the distillation pot through the pipe.

Example 5 5 equipped with a thermometer, reflux condenser, dropping funnel and stirrer
300 g of phenol and 0.3 g of alkylation catalyst 1 (0.1 part by weight relative to 100 parts by weight of phenol) were placed in a 00 ml four-necked flask, and the temperature was raised to 80 ° C. with stirring.
Then, 286 g of isobutylene was fed thereto for 5 hours to carry out an addition reaction, and after feeding isobutylene, the mixture was stirred at 110 ° C. for 9 hours to carry out a disproportionation reaction to obtain a reaction product 586.3.
g was obtained.

The catalyst was neutralized by adding 0.7 g of a 20% aqueous sodium hydroxide solution to the reaction product. The neutralized salt was transferred to the purification step without being removed, and distilled under reduced pressure at 180 ° C. for 4 hours. By distillation, a low boiling point component having a lower boiling point than paratertiary butylphenol, which is lower than that of the target product 2,4-ditert-butylphenol, is separated.
Compared with ditert-butylphenol, high-boiling components including high boiling point 2,4,6-tritert-butylphenol were separated and collected to obtain 400 g of 2,4-ditert-butylphenol having a purity of 98.9%.

At this time, the remaining amount of the pot containing the neutralized salt was 3.9 g.
(0.7 parts by weight with respect to 100 parts by weight of the reaction product), and the residual liquid in the kettle was in a slurry form and maintained fluidity until the temperature was lowered to 50 ° C. It was possible to make it flow out of the distillation system.

Example 6 5 equipped with a thermometer, reflux condenser, dropping funnel and stirrer
300 g of phenol and 0.3 g of alkylation catalyst 1 (0.1 part by weight relative to 100 parts by weight of phenol) were placed in a 00 ml four-necked flask, and the temperature was raised to 80 ° C. with stirring. Diisobutylene (179 g) was supplied thereto for 5 hours to carry out an addition reaction, followed by stirring at 110 ° C. for 9 hours to carry out a disproportionation reaction to obtain 479.3 g of a reaction product.

To the reaction product, 0.7 g of 20% aqueous sodium hydroxide solution was added to neutralize the catalyst. The neutralized salt was transferred to the purification step without being removed, and distilled under reduced pressure at 180 ° C. for 4 hours. By distillation, a low boiling component was separated from the target product paratertiary octylphenol, and a higher boiling component was separated and recovered from the kettle residue containing the target product by distillation to obtain a purity of 9%.
8.5% paratertiary octylphenol 290
g was obtained.

The residual amount of the kettle containing the neutralized salt after the distillation of the high boiling substance in the kettle residue was 3.1 g (0.7 parts by weight based on 100 parts by weight of the reaction product). It was a slurry and kept fluidity until the temperature was lowered to 50 ° C., so that it could be flowed out of the distillation system from the distillation pot through the pipe.

Comparative Example 1 378 g of a reaction product was obtained in the same manner as in Example 3 except that 6.0 g of concentrated sulfuric acid (2.0 parts by weight based on 100 parts by weight of phenol) was used in place of the alkylation catalyst 1. Obtained.

To the reaction product, 9.0 g of a 20% aqueous sodium hydroxide solution was added to neutralize the acid catalyst. Distillation was carried out at 150 ° C in the same manner as in Example 3 without removing the neutralized salt, but the stirring efficiency was lowered in the latter half of the distillation, the fluidity of the reaction liquid was lowered, and the thermal conductivity was reduced. Since it became difficult and the amount of vapor distilled out became small, the distillation operation was terminated at that point, and 145 g of paratertiarybutylphenol having a purity of 99.8% was obtained.

At this time, the remaining amount of the pot containing the neutralized salt is 20.0.
g (5.4 parts by weight per 100 parts by weight of reaction product). Since the distillation step was blocked during the process, the reaction product after neutralization obtained in the same manner was purified using a long step as follows.

The reaction product was cooled to 80 ° C. and 50 g
After adding water and stirring, the mixture was allowed to stand for 30 minutes and separated into an upper layer and a lower layer. 77 g of an aqueous solution of the lower layer of pH 11 was separated and removed. The aqueous solution separated after washing with water contained 15 g of phenol, sodium sulfate and sodium phenolsulfonate.

30 g of water was added again, washed with water and allowed to stand, and p
35 g of a lower aqueous solution of H7 was separated. 5 g of phenol was dissolved in the aqueous solution separated after washing with water. In order to recover phenol from these lower aqueous solutions, it is sent to a recovery device (solvent extraction equipment) and treated to 20 g of phenol.
Collected. The recovered phenol was added to the upper layer.

The upper layer was sent to the refining step and distilled at 150 ° C. for 6 hours to obtain 173 g of para-tert-butylphenol having a purity of 99.8%. At the end of distillation,
The remaining amount of the kettle is 1.5 g (0.
4 parts by weight).

Comparative Example 2 In place of the alkylation catalyst 1, 1 part of paratoluenesulfonic acid was used.
387 g of a reaction product was obtained in the same manner as in Example 3 except that 5.0 g (5.0 parts by weight based on 100 parts by weight of phenol) was used.

To the reaction product, 9.0 g of a 20% aqueous sodium hydroxide solution was added to neutralize the acid catalyst. Distillation was carried out at 150 ° C in the same manner as in Example 3 without removing the neutralized salt, but the stirring efficiency was lowered in the latter half of the distillation, the fluidity of the reaction liquid was lowered, and the thermal conductivity was reduced. Since it became difficult and the amount of vapor distilled out became small, the distillation operation was terminated at that point, and 140 g of paratertiarybutylphenol having a purity of 99.8% was obtained.

At this time, the remaining amount of the pot containing the neutralized salt is 25.0.
g (6.5 parts by weight based on 100 parts by weight of reaction product). Comparative Example 3 Instead of the alkylation catalyst 1, 1.0 g of concentrated sulfuric acid (0.3 parts by weight relative to 100 parts by weight of phenol) was used, and 20 hours were required to complete the disproportionation reaction at 130 ° C. after the supply of isobutylene. Other than the above, the reaction was performed in the same manner as in Example 3 to obtain the desired product, paratertiary butylphenol (PT
373 g of a reaction product containing a small amount of BP) and a large amount of other by-products was obtained. The composition ratio of the reaction product is shown in Table 1 in comparison with Example 3.

[0052]

[Table 1] * 1 Paratertiary butylphenol * 2 Orthotertiary butylphenol * 3 2,6-Ditertiary butylphenol * 4 2,4-Ditertiary butylphenol

To the reaction product, 3.0 g of a 20% aqueous sodium hydroxide solution was added to neutralize the acid catalyst. Distillation was carried out at 150 ° C. in the same manner as in Example 3 without removing the neutralized salt, while keeping it contained.

Distillation recovery rate 90% with respect to reaction liquid charge
From the time of (10% remaining in the kettle), crystals of sodium sulfate began to adhere to the kettle, the stirring efficiency decreased, and the amount of steam started to decrease. Distillation is continued for 10 hours to obtain 98.0% pure para-tertiarybutylphenol 150.
g was obtained.

At this time, the remaining amount of the pot containing the neutralized salt was 6.4 g.
(1.5 parts by weight based on 100 parts by weight of reaction product).

[0056]

EFFECTS OF THE INVENTION According to the present invention, since the catalytic activity is high, it is possible to greatly reduce the amount of the catalyst used, and accordingly, the neutralized salt produced by neutralizing the catalyst after the reaction is formed. Since the neutralization salt itself can be significantly reduced, and the neutralization salt itself can be finely dispersed in the reaction solution to maintain a slurry state and maintain fluidity, distillation can be performed with the neutralization salt contained in the reaction solution. Even if it goes, the fluidity can always be maintained during the distillation, so there is no obstacle to the heat transfer of the amount of heat required for evaporation (latent heat of vaporization), and the distillation can be carried out continuously with the amount of vapor distilled kept, Even when removing the residual liquid containing the neutralized salt, since it can be discharged without retaining the fluidity and causing the pipe to be closed, the post-treatment step after the reaction is simplified, and an alkylation catalyst for an aromatic compound, Production method and third method using this alkylation catalyst
A method for producing a primary alkylphenol can be provided.

Claims (13)

[Claims] 1. Having a sulfonic acid group on an aromatic nucleus,
Also, an alkylation catalyst for aromatic compounds, which comprises a phenol derivative in which a phenolic hydroxyl group forms a sulfonate ester. 2. A phenol derivative having a sulfonic acid group of 1
The alkylation catalyst according to claim 1, which has 2 or 3 on each aromatic nucleus. 3. A method for producing an alkylation catalyst for aromatic compounds, which comprises reacting sulfuric acid with phenols. 4. Sulfuric acid and phenols are used in a ratio of 2: 1 to 4:
The method according to claim 3, wherein the reaction is carried out at a molar ratio of 1. 5. Sulfuric acid and phenols at 50 to 100 ° C.
The method according to claim 4, wherein the reaction is carried out under the temperature condition of. 6. The production method according to claim 3, wherein the phenol is phenol. 7. A tertiary olefin and a phenolic compound,
A method for producing a tertiary alkylphenol which is reacted in the presence of an acid catalyst, wherein the acid catalyst has a sulfonic acid group on an aromatic nucleus and the phenolic hydroxyl group forms a sulfonic acid ester. The method for producing tertiary alkylphenols is characterized by using the phenol derivative described above. 8. The method according to claim 7, wherein the phenol derivative used as the acid catalyst has two or three sulfonic acid groups on one aromatic nucleus. 9. The amount of the phenol derivative used as the acid catalyst is 0.05 based on 100 parts by weight of the phenols.
The manufacturing method of Claim 7 or 8 which is -1 part by weight. 10. The production method according to claim 9, wherein the reaction temperature is 50 to 140 ° C. 11. The method according to claim 7, wherein the phenol is phenol. 12. The production method according to claim 7, wherein the tertiary olefin is isobutylene or diisobutylene. 13. The production method according to claim 7, wherein the reaction product is neutralized with an aqueous alkaline solution and then distilled in the presence of a neutralized salt.