JPH0889819A - Ion exchange resin - Google Patents

Abstract

PURPOSE: To prepare economically an ion exchange resin used as a catalyst when bisphenol A is produced by using a strongly acidic sulfonic acid type ion exchange resin wherein N,N,N-trimethyl-3-mercaptopropylammonium is ionically bound. CONSTITUTION: As a catalyst for producing bisphenol A, a strongly acidic ion exchange resin consisting of a styrene-divinylbenzene copolymer prepd. by binding ionically N,N,N-trimethyl-3-mercaptopropylammonium and being sulfonated, is used. In this case, N,N,N-trimethyl-3-mercaptopropylammonium is synthesized by reacting hydrochloric acid salt of N,N-dimethyl-3-chloropropylamine with sodium thiosulfate to prepare a Bunte salt, decomposing this to synthesize disulfide of N,N-dimethyl-3-mercaptopropylamine, performing methylation with a methylation agent and reducing it furthermore.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a strongly acidic sulfonic acid type ion exchange resin, and more particularly to an ion exchange resin used as a catalyst for producing bisphenol A by a condensation reaction of phenol and acetone. Bisphenol A is a useful compound as a raw material for epoxy resins and polycarbonate resins.

[0002]

2. Description of the Related Art As a catalyst for producing bisphenol A by a condensation reaction of phenol and acetone, a method of using a compound having a mercapto group together with a strongly acidic sulfonic acid type ion exchange resin is known. A method in which a compound having a mercapto group is allowed to coexist in the reaction system (Japanese Patent Publication No. 45-10337, French Patent 13).
No. 73796, etc.), a method of covalently binding a compound having a mercapto group to a strongly acidic ion exchange resin (Japanese Patent Publication No. 37-14721, Japanese Patent Laid-Open No. 56-21650, Japanese Patent Laid-Open No. 21650).
7-87864, JP-A-59-109503, etc.), a method of ion-bonding an amine having a mercapto group to a strongly acidic ion exchange resin, and the like.

Among these, the method of using a strongly acidic ion exchange resin in which mercaptoamines are ion-bonded is as follows:
1) Mercaptoamines are not mixed in the product 2)
This method is superior to the method of covalently bonding a compound having a mercapto group and the method of simply allowing a compound having a mercapto group to coexist in the reaction system in that the catalyst can be easily prepared.

As a method of using a strongly acidic ion exchange resin in which mercaptoamines are ion-bonded, 2-mercaptoethylamine (Japanese Patent Publication No. 46-199353, JP-A No. 62-298454), N-propyl-3- A method using a strongly acidic ion exchange resin to which mercaptoalkylamine (JP-A-60-137440) is ionically bonded is known.

Further, as a method of using a strongly acidic ion exchange resin having a quaternary ammonium salt ion-bonded thereto,
N, N, N-trimethyl-2-mercaptoethylammonium, N- (2-hydroxyl-3-mercaptopropyl) pyridinium, N-methyl-N- (2-hydroxyl-3-mercaptopropyl) morpholium, and N -Benzyl-N, N-dimethyl-2-mercaptoethylammonium ion-bonded strong acid ion-exchange resin (Chiekoslovakia Patent 1849)
No. 88) is known. However, any of the methods has a drawback that the conversion rate of acetone is only about 50 to 75%.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a strongly acidic sulfonic acid type ion exchange resin catalyst for producing bisphenol A by the condensation reaction of acetone and phenol, which has a high conversion rate of acetone and is economically advantageous. The purpose is to do.

[0007]

According to the present invention, N, N, N-trimethyl-3-mercaptopropylammonium, which has excellent performance as a catalyst for producing bisphenol A by the condensation reaction of acetone and phenol, is ionized. Provided is a strongly acidic ion exchange resin comprising a bound, sulfonated styrene-divinylbenzene copolymer.

Used in the ion exchange resin of the present invention,
N, N, N-trimethyl-3-mercaptopropylammonium can be obtained by, for example, reacting N, N-dimethyl-3-chloropropylamine hydrochloride with sodium thiosulfate to give a Bunte salt, which is acid-decomposed to give N, N-dimethyl-3
-Synthesizing a disulfide of mercaptopropylamine,
It can be synthesized by methylating with a methylating agent such as dimethylsulfate and further reducing it.

The ion exchange resin is preferably a strongly acidic ion exchange resin composed of a sulfonated styrene-divinylbenzene copolymer, and the content of divinylbenzene units in the copolymer is 2 to 40%. preferable.
The exchange capacity of ion exchange resin is 0.5 to 2.5 when water is contained.
Meq./ml is preferably 3.0 to 7.0 meq./ml in the dry state. The particle size distribution of ion exchange resin is 200
It is preferable that 95% or more of particles having a particle size of ˜1500 μm are contained. Specifically, for example, Amberlyst 15, 31, 32 (trade name of Rohm & Haas Co., Ltd.), Dowex 50W, 88 (trade name of Dow Chemical Co., Ltd.), Diaion SK1B, SK102, SK10
4, PK208, PK212, RCP160H, RCP
170H (trade name of Mitsubishi Kasei Co., Ltd.) and the like can be exemplified.

These ion exchange resins are used in acid form. In the case of the sodium type, it is treated with an acid such as hydrochloric acid to be used as the acid type. These ion exchange resins are commercially available in the state of containing water, but can be used as they are without any special treatment such as dehydration.

To ion bond N, N, N-trimethyl-3-mercaptopropylammonium to the sulfonic acid group of the strongly acidic ion exchange resin, the proton of the sulfonic acid group of the ion exchange resin and N, N, N-trimethyl are used. The ion of the -3-mercaptopropylammonium cation may be exchanged. Specifically, N dissolved in ion-exchanged water,
A strong acid prepared by previously converting a counter anion of N, N-trimethyl-3-mercaptopropylammonium into an anion that easily ion-exchanges with a sulfonate anion such as acetate anion, carbonate anion, and hydroxide anion, and dispersing the anion in water. It is made by adding it to the cationic ion exchange resin and stirring it for 0.1 to 2 hours.

For strongly acidic ion exchange resins, N, N,
The amount of N-trimethyl-3-mercaptopropylammonium used is usually 5 to 40 mol%, preferably 8 to 30 mol% based on the total sulfonic acid groups of the strongly acidic ion exchange resin. When the ionic bond amount is 5 mol% or less, N, N, N
-Trimethyl-3-mercaptopropylammonium is not preferable because the catalytic effect is not sufficiently exhibited, and when it is 40% or more, the catalytic activity decreases due to the decrease of the amount of sulfonic acid. The strongly acidic ion-exchange resin of the present invention to which N, N, N-trimethyl-3-mercaptopropylammonium is ion-bonded has a very high acetone conversion rate as compared with other resins.

The strongly acidic ion-exchange resin (hereinafter abbreviated as modified resin) ion-bonded with N, N, N-trimethyl-3-mercaptopropylammonium obtained as described above is a condensation reaction of acetone and phenol. When used as a pretreatment, the volume of the modified resin is 5 to 20 as a pretreatment.
0 times ion-exchanged water was passed at a liquid hourly space velocity (LHSV) of 0.5 to 50 hr ^-1 at a temperature of 20 to 80 ° C., and phenol of 5 to 200 times the volume of the modified resin was added to the solution.
LHSV of 0.5 to 50 hr ⁻¹ is passed at a temperature of ˜110 ° C. By this treatment, the modified resin is solvent-exchanged from water to phenol so that it can be used in the reaction.

This reaction is usually carried out in a fixed bed flow reaction system in which a raw material mixture containing phenol and acetone is continuously supplied to a reactor filled with a modified resin to carry out the reaction. The feed of the raw material mixture is LHSV 0.1 to 20 hr ^-1 ,
It is preferably carried out in the range of 0.5 to 10 hr ^-1 . The reaction temperature is in the range of 40 to 120 ° C, preferably 60 to 100 ° C. When the reaction temperature is 40 ° C or lower, the reaction rate is slow,
Further, at a temperature of 120 ° C. or higher, the modified resin is significantly deteriorated and by-products are increased, which is not preferable.

The molar ratio of phenol to acetone is in the range of 3 to 30 mol, preferably 5 to 20 mol of phenol per 1 mol of acetone. If the amount of phenol used is less than this range, by-products increase, which is not preferable, and even if it is used in an amount of 30 mol or more, its effect is hardly affected, and rather the amount of phenol to be recovered and reused increases, which is not economical.

The separation and purification of the target substance, bisphenol A, from the reaction mixture is known, for example, by recovering unreacted phenol, separating the adduct of bisphenol A and phenol as crystals, and recovering phenol from the adduct by an operation such as distillation. Can be done in any way.

[0017]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Reaction Examples. In addition, acetone conversion in the reaction example, 4,4'-bisphenol A (BPA) selectivity,
The modification rate and the residual sulfonic acid rate were calculated by the following formulas (units are%).

[0018]

[Equation 1]

Example A N- (3-chloropropyl) -N, N-dimethylammonium chloride (15.8 g), sodium thiosulfate (17.4 g) and distilled water (50 ml) were placed in a 100 ml eggplant-shaped flask and heated under reflux for 2 hours. 35% hydrochloric acid (10.4 g) was added and heating under reflux was continued for another hour. While cooling with an ice bath, gradually add 10 g of sodium hydroxide to make it basic,
Extraction was performed twice with 50 ml of ethyl acetate. After dehydration with anhydrous potassium carbonate, the solvent was distilled off and vacuum distillation was performed.
7.5 g of colorless and transparent bis (N, N-dimethyl-3-aminopropyl) disulfide was obtained. This disulfide was dissolved in 70 ml of isopropanol, 8.8 g of dimethylsulfate was added, and the mixture was heated with stirring at 60 ° C. for 2 hours, the solvent was distilled off, and bis (N, N, N-trimethyl-3-propylammonium) disulfide bis ( 17.5 g of white crystals of methylsulfate) salt were obtained.

This crystal was dissolved in 130 ml of ion-exchanged water, and 200 ml of a strongly basic ion-exchange resin Diaion PA306 (trade name of Mitsubishi Kasei Co., Ltd.), which had been ion-exchanged into an acetate type in advance, was packed in a column and LHSV was about 0.5 h.
The solution was passed through at r ⁻¹ and then 250 ml of ion-exchanged water was passed through to exchange the disulfide counter anion from methyl sulfate to acetate. 650 ml of 1,4-dioxane and 16.8 g of triphenylphosphine were added to the recovered aqueous solution of disulfide, and the mixture was heated and stirred at 70 ° C. for 3 hours under a nitrogen atmosphere.

This solution was previously added to 1,4-dioxane 200
Amberlyst 31 (manufactured by Rohm & Haas Co., exchange capacity 1.
80 meq / wet-g) was added to the slurry containing 146 g, and the mixture was stirred at room temperature for 30 minutes. The ion exchange resin is filtered and packed in a glass column, 1,4-dioxane /
700 ml of a mixed solution of ion-exchanged water = 1/1 was passed through to completely wash away triphenylphosphine and its oxide in the resin. Furthermore, 1500 ml of deionized water is added to the LH
The solution was replaced with SV1 hr ⁻¹ to replace the solvent. When recovered by filtration, 145 g of modified amberlyst 31 was obtained. From the analysis of mercapto group and acid amount, the modification rate is 2
At 1.0%, the residual ratio of sulfonic acid was 79.0%.

30 ml of this modified amberlyst 31 was packed in a stainless steel column having an inner diameter of 10.7 mm and a total length of 600 mm, and phenol was added at 70 ° C. for 2 hours with LHSV 5 hr ^-1 .
It was run for 4 hours. Next, phenol / acetone = 10/1
The mixed solution (molar ratio) was passed at 70 ° C. and LHSV of 1.0 hr ⁻¹ , and a continuous reaction was performed for 2000 hours. Acetone conversion after 50 and 2000 hours and 4,4'-BPA
The selectivity is shown in Table 1.

Comparative Examples 1-2 In the same manner as in Examples, N, N-dimethyl-2-chloroethylammonium hydrochloride and the corresponding mercaptoammonium or mercaptoamine synthesized using 2-chloroethylamine were ionized. Bound denatured Amberlyst 31 was prepared. Using these, the reaction was carried out under the same conditions as in the examples. The reaction results after 50 hours and 2000 hours are shown in Table 1 together with the results of the examples.

[0024]

[Table 1]

[0025]

When the ion exchange resin of the present invention is used as a catalyst, the condensation reaction between phenol and acetone produces
Bisphenol A can be efficiently produced with a high acetone conversion rate.

Claims (3)

[Claims] 1. A strongly acidic sulfonic acid type ion exchange resin in which N, N, N-trimethyl-3-mercaptopropylammonium is ion-bonded. 2. Bonded N, N, N-trimethyl-3-
The ion exchange resin according to claim 1, wherein the amount of mercaptopropylammonium is 5 to 40 mol% of the sulfonic acid group. 3. The ion exchange resin according to claim 1, wherein the ion exchange resin is a styrene-divinylbenzene copolymer.