JP2001348350A - Method for preparing fixed bed of acidic cation exchange resin for producing bisphenols - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols uniformly neutralized over all of the acidic cation exchange resin filled in a reactor. SOLUTION: This method for preparing the fixed bed of the acidic cation exchange resin for producing the bisphenols comprises filling the acidic cation exchange resin in the reactor, forming the fixed bed, then charging an aqueous solution of an acid, a nitrogen-containing sulfur compound and ketones or aldehydes into the reactor and circulating the aqueous solution before initiating the reaction in the method for preparing the acidic cation exchange resin for producing the bisphenols from a raw material containing a carbonyl compound and phenols.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols. More specifically, the present invention relates to a method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols, which is uniformly neutralized over the entire fixed bed of an acidic cation exchange resin packed in a reactor.

[0002]

2. Description of the Related Art Bisphenols, particularly 2,2-bis (4-hydroxyphenyl) alkane, for example, 2,2-bis (4), used as a raw material for manufacturing engineering plastics such as polycarbonate resin and polyarylate resin or epoxy resin. -Hydroxyphenyl)
Propane [hereinafter abbreviated as bisphenol A. ]
It is produced by the reaction of phenols and carbonyl compounds. In carrying out the reaction between these phenols and carbonyl compounds, a method using an acidic cation exchange resin fixed bed as a catalyst is well known.

When bisphenol A is produced by, for example, reacting phenol with acetone using this fixed bed of acidic cation exchange resin, 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) is produced as a by-product. )
There is a problem in that an isomer of bisphenol A such as propane is generated, and the purity of the target bisphenol A is reduced. Therefore, in order to suppress by-products of these isomers, it is also known to use a catalyst obtained by neutralizing a part of the acidic cation exchange resin with a nitrogen-containing sulfur compound.

For example, Japanese Patent Publication No. Sho 62-748 discloses that
After contacting the fixed bed with an amount of mercaptoamine that neutralizes 2 to 25% of the sulfonic acid groups in the fixed bed of the sulfonic acid cation exchange resin, an acid solution is further brought into contact with the fixed bed to obtain mercaptoamine. A method for producing a fixed bed of a sulfonic acid cation exchange resin in which sulfonic acid groups neutralized with an amine are uniformly distributed in the fixed bed has been proposed. However, according to this method, there is a problem of corrosion of the apparatus due to the use of a strong acid such as hydrochloric acid or sulfuric acid. Also, JP-A-8-4
No. 0961 proposes a method of using an aromatic sulfonic acid and a nitrogen-containing sulfur compound when preparing a fixed bed of an acidic cation exchange resin. In this case, since the aromatic sulfonic acids are used as the acid, there is no problem that the apparatus is corroded. However, when 2-mercaptoethylamine is used as the neutralizing agent, each of the fixed beds of the acidic cation exchange resin packed in the reactor is used. There is a problem that the neutralization rate at the site becomes uneven.

[0005]

SUMMARY OF THE INVENTION The present invention provides a method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols, which is uniformly neutralized over the entire acidic cation exchange resin charged in the reactor. It is intended to provide.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when preparing an acidic cation-exchange resin fixed bed for producing bisphenols, an acidic cation-exchange resin was placed in a reactor. After filling the ion exchange resin to form a fixed bed, before starting the reaction, an aqueous solution in which an acid and a nitrogen-containing sulfur compound and a ketone or aldehyde are dissolved is charged into the reactor and circulated. , Have found that the above objectives can be achieved, and based on these findings,
The present invention has been completed.

That is, the gist of the present invention is as follows. [1] In a method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols from a raw material containing a carbonyl compound and a phenol, a reaction vessel is filled with an acidic cation exchange resin in a reactor to form a fixed bed. Before the start, an aqueous solution in which an acid and a nitrogen-containing sulfur compound and a ketone or an aldehyde are dissolved is charged into the reactor and circulated, wherein an acidic cation exchange resin fixed bed for producing bisphenols is fixed. Preparation method. [2] The method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols according to the above [1], wherein the acidic cation exchange resin is a sulfonic acid type cation exchange resin. [3] The method for preparing an acidic cation exchange resin fixed bed for producing bisphenols according to the above [1] or [2], wherein the nitrogen-containing sulfur compound is 2-mercaptoethylamine. [4] The above [1] to wherein the ketone is acetone.
The method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols according to any one of [3]. [5] The method for preparing an acidic cation exchange resin-fixed bed for producing bisphenols according to any one of [1] to [4], wherein the bisphenol is 2,2-bis (4-hydroxyphenyl) alkane. .

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for preparing a fixed bed of an acidic cation exchange resin used as a catalyst in the production of bisphenols from a raw material containing a carbonyl compound and phenols. After filling the exchange resin to form a fixed bed, before starting the reaction,
In this method, an acidic cation exchange resin fixed bed for producing bisphenols is prepared by charging an aqueous solution in which an acid and a nitrogen-containing sulfur compound and a ketone or an aldehyde are dissolved and circulating the aqueous solution. .

The starting carbonyl compound used in producing bisphenols from the starting materials containing the carbonyl compound and phenols includes acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-propyl ketone, methyl phenyl ketone, acetophenone, Examples include ketones such as benzophenone and cyclohexanone, and aldehydes such as formalin, acetaldehyde and benzaldehyde.

The phenols used herein include those having a structure in which the chemical structure has no substituent at the para position with respect to the bonding position of the hydroxyl group on the benzene ring, for example, phenol, o-cresol, m-phenol. -Cresol, o-tert-butylphenol, o-phenylphenol, m-phenylphenol, 2,6-xylenol, 3,5-xylenol, 2,6-di-tert
Alkylphenols and arylphenols such as -butylphenol and 3,5-di-tert-butylphenol; halogenated phenols such as o-chlorophenol, m-chlorophenol, 2,6-dichlorophenol and 2,6-dibromophenol And the like.

The bisphenols produced from raw materials containing these carbonyl compounds and phenols are basically bisphenols having a chemical structure in which two hydroxyphenyl groups are bonded via a carbon atom, For example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) phenylmethane,
Bis (3-methyl-4-hydroxyphenyl) methane,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3-fluoro-4) -Hydroxyphenyl) methane, bis (2-tert-butyl-4-hydroxyphenyl) phenylmethane, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenyl) methane, bis (2-hydroxy-4)
Bis (hydroxyphenyl) methanes such as methylphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl)
Ethane, 1,1-bis (4-hydroxyphenyl) -1
-Phenylethane, 1,1-bis (4-hydroxy-3
Bis (hydroxyphenyl) ethanes such as -methylphenyl) -1-phenylethane and 1,1-bis (2-hydroxy-4-methylphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane, , 1-bis (4-hydroxyphenyl) propane, 2,2-bis (2-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl)
Propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec
-Butyl-4-hydroxyphenyl) propane, 2,2
-Bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-
4-hydroxyphenyl) propane, 2,2-bis (3
-Fluoro-4-hydroxyphenyl) propane, 2,
2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (2-tert-
Butyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-
3,5-difluorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (2-hydroxy-4-sec-butylphenyl) propane, 2,2 Bis (hydroxyphenyl) propanes such as -bis (2-hydroxy-4,6-dimethylphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane, 2,2- (3-methyl-4
-Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -2-methylpropane, 1,1-bis (2
-Butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 2,2-bis (4
-Hydroxy-3,5-dichlorophenyl) butane;
Bis (hydroxyphenyl) butanes such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) butane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4- (Hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane,
1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-methyl-4-
Bis (hydroxyphenyl) cycloalkanes such as (hydroxyphenyl) -3,3,5-trimethylcyclohexane; Among these, 2,2-bis (4-hydroxyphenyl) alkanes are preferable,
Further, 2,2-bis (4-hydroxyphenyl) propane is a particularly preferred compound because of its high utility as a resin raw material.

The acidic cation exchange resin used as a catalyst in the reaction between these carbonyl compounds and phenols is preferably a sulfonic acid-based resin, and the base resin is a styrene-divinylbenzene copolymer,
A perfluoroethylene copolymer system, a phenol-formaldehyde polymer system, or the like can be used. Among these, a styrene-divinylbenzene copolymer system is preferably used. Examples of the acidic cation exchange resin include a sulfonated styrene-divinylbenzene copolymer and a sulfonated phenol formaldehyde resin. The acidic cation exchange resin may be a gel type or a porous type. Further, those having a relatively low degree of crosslinking of 2 to 8% are preferred. The acidic cation exchange resin is charged into a reactor to form a fixed bed.

After forming the fixed bed of acidic cation exchange resin filled in the reactor in this way, before starting the above reaction, an aqueous solution in which an acid and a nitrogen-containing sulfur compound and a ketone or aldehyde are dissolved. Is charged to the reactor and circulated to uniformly neutralize the acidic cation exchange resin partially with the nitrogen-containing sulfur compound throughout the fixed bed. In this case, 2 to 50%, preferably 5%, of the sulfonic acid groups bound to the acidic cation exchange resin.
It is preferred to neutralize up to 30% with a nitrogen-containing sulfur compound.

The acid used here may be an aromatic sulfonic acid such as benzenesulfonic acid, paratoluenesulfonic acid, or xylenesulfonic acid, or an alkylsulfonic acid such as methanesulfonic acid or ethanesulfonic acid. There may be. In addition to these organic acids, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid may be used. These acids are preferably used in the form of an aqueous solution, and in this case, the concentration is usually desirably 0.1 to 500 mmol / L. If the concentration is less than 0.1 mmol / L, a sufficient effect may not be obtained. If the concentration exceeds 500 mmol / L, it may be uneconomical. Is more likely to occur.

Examples of the nitrogen-containing sulfur compound used herein include, for example, mercaptoalkylamines such as 2-mercaptoethylamine and 3-mercaptobutylamine, aminothiophenols such as 1,4-aminothiophenol, Examples thereof include mercaptoalkylpyridines such as mercaptomethylpyridine, 3-mercaptoethylpyridine, and 3-mercaptoethylpyridine. Among these compounds, mercaptoalkylamines are particularly preferred. The concentration of the aqueous nitrogen-containing sulfur compound solution is preferably 1 to 10% by mass.

Further, examples of ketones used together with these acids and nitrogen-containing sulfur compounds include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone. Of these, acetone is particularly preferred. The use ratio of the ketones is desirably in the range of 0.1 to 5 moles per mole of the nitrogen-containing sulfur compound. This is because if the use ratio of ketones is less than this range, the effect may not be sufficiently obtained, and if it exceeds this range, ketones may be heavier. Aldehydes may be used in place of the ketones. As the aldehydes, formalin, acetaldehyde and benzaldehyde are preferably used.

Next, when the acid and the aqueous solution of the nitrogen-containing sulfur compound and the ketones or aldehydes are charged into the fixed bed of the acidic cation exchange resin filled in the reactor and circulated, these acids and The effluent may be charged as an aqueous solution in which a nitrogen-containing sulfur compound and a ketone or aldehyde are mixed, or may be charged first with an aqueous acid solution and passed through the fixed bed of the acidic cation exchange resin. , A mixed aqueous solution of a nitrogen-containing sulfur compound and a ketone or aldehyde may be charged. The circulation operation for distributing the aqueous solution containing these compounds to the acidic cation exchange resin fixed bed may be performed until the neutralization ratio of the acidic cation exchange resin reaches a desired value. The temperature at which the neutralization is performed may be room temperature or may be heated to a temperature range of 30 to 100 ° C. The higher the temperature at the time of the neutralization, the higher the reaction rate, so that the reaction time can be shortened.
If the temperature exceeds 0 ° C., the possibility of corrosion of the device by the acid increases, and the elimination of the sulfone group of the acidic cation exchange resin increases.

In the neutralization treatment of the fixed bed of acidic cation exchange resin filled in the reactor, the conventional method uses an aqueous solution of an acid and a nitrogen-containing sulfur compound. In some cases, the neutralization rate of the entire fixed bed from the upstream to the downstream of the acidic cation exchange resin fixed bed was not uniform, but in the present invention, the acid and the nitrogen-containing sulfur compound And the use of ketones or aldehydes, the uniformity of the neutralization rate of the entire fixed bed from the upstream part to the downstream part of the acidic cation exchange resin fixed bed filled in the reactor is high, and therefore, the carbonyl compound And a fixed bed of acidic cation exchange resin for the production of bisphenols, suitable for use as a catalyst for producing bisphenols from raw materials containing phenols and phenols. Cormorants effect can be obtained.

[0019]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

[Example 1] As a reactor, an inner diameter of 25 m was used.
Using a glass column having a length of 20 cm and a length of 20 cm, this reactor was filled with 100 ml of a water-swelled sulfonic acid type cation exchange resin (Diaion SK-104, manufactured by Mitsubishi Chemical Corporation). A fixed bed of ion exchange resin was formed. Then, at room temperature, 100 ml of a 1% by mass aqueous solution of paratoluenesulfonic acid was charged into the reactor, and allowed to flow through a fixed bed of a sulfonic acid type cation exchange resin.

Next, 1.4 g of 2-mercaptoethylamine and 2.8 g of acetone were added to and dissolved in the aqueous solution flowing out of the reactor. The aqueous solution obtained here was charged into the reactor at a supply rate of 200 ml / hr, circulated at room temperature for 72 hours, and the sulfone groups in the sulfonic acid type cation exchange resin were neutralized with 2-mercaptoethylamine. .

After completion of the neutralization treatment, the sulfonic acid type cation exchange resin was equally divided into five parts in the axial direction of the fixed bed and was taken out of the reactor. And these 5
The neutralization rate of each of the samples was measured. Table 1 shows the results.

Here, the neutralization ratio was calculated by the following equation.

[0024]

(Equation 1)

[The acid equivalent in the formula was measured by a titration method using an aqueous solution of sodium hydroxide. Comparative Example 1 Example 1 was repeated except that acetone was not used.
Same as. Table 1 shows the results.

[0026]

[Table 1]

[0027]

According to the present invention, there is provided a method for producing bisphenols from a raw material containing a carbonyl compound and phenol, which is neutralized with good uniformity throughout the acidic cation exchange resin charged in the reactor. A method for preparing an acidic cation exchange resin fixed bed suitable for use as a catalyst can be provided.

Claims (5)

[Claims] 1. A method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols from a raw material containing a carbonyl compound and phenols, wherein the fixed bed is formed by filling an acidic cation exchange resin in a reactor. An acidic cation exchange resin for producing bisphenols, wherein an aqueous solution in which an acid and a nitrogen-containing sulfur compound and a ketone or an aldehyde are dissolved is charged into the reactor and circulated before the start of the reaction. How to prepare the floor. 2. The method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols according to claim 1, wherein the acidic cation exchange resin is a sulfonic acid type cation exchange resin. 3. The method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols according to claim 1, wherein the nitrogen-containing sulfur compound is an aminoalkylthiol. 4. The method according to claim 1, wherein the ketone is acetone.
3. The method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols according to any one of 3). 5. The method according to claim 1, wherein the bisphenol is 2,2-bis (4
The method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols according to any one of claims 1 to 4, which is -hydroxyphenyl) alkane.