JPH10314595A - Ion exchange resin and method for producing bisphenol using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce bisphenol A by a condensation reaction between phenol and acetone, which has a high conversion of acetone, a high selectivity for 4,4'-bisphenol A, and a good stability. To provide a modified strongly acidic sulfonic acid type ion exchange resin useful as a catalyst for the production and a method for producing bisphenol using the same. [MEANS FOR SOLVING PROBLEMS] A modified strongly acidic sulfonic acid type ion exchange resin in which a quinoline having a mercapto group represented by the following general formula (I) is ionically bonded to a strongly acidic sulfonic acid type ion exchange resin. Embedded image (Wherein, X and Y each independently represent a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, a cycloalkyl group or an aryl group having 5 to 10 carbon atoms, and n represents 2 to 4
Represents an integer. Further, the bonding position of the substituent having a mercapto group is any one of positions 2, 3, 4, 6, and 8 of quinoline.) In the presence of the modified strong acidic sulfonic acid type ion exchange resin described in section 2.1. And a reaction between a phenol and a ketone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ion exchange resin and a method for producing bisphenol using the same. More specifically, the present invention relates to a modified strongly acidic sulfonic acid type ion exchange resin in which quinolines having a mercapto group are ionically bonded, and a method for producing bisphenol using the same. The ion exchange resin is useful as a catalyst for producing bisphenol A by a condensation reaction of bisphenol, for example, phenol and acetone. Bisphenol A is
It is a useful compound that is a raw material for epoxy resins and polycarbonate resins.

[0002]

2. Description of the Related Art There have been proposed various methods of using a compound having a mercapto group together with a strongly acidic sulfonic acid type ion exchange resin as a catalyst for producing bisphenol A by a condensation reaction of phenol and acetone. For example, a method of coexisting a compound having a mercapto group in a reaction system in addition to a strongly acidic sulfonic acid type ion exchange resin (Japanese Patent Publication No. 45-10337, French Patent No. 1)
373796), a method of covalently bonding a compound having a mercapto group to a strongly acidic sulfonic acid type ion exchange resin (JP-B-37-14721, JP-A-56-21)
650, JP-A-57-87846, JP-A-59-1
09503), and a method of ion-bonding an amine having a mercapto group to a strongly acidic sulfonic acid type ion exchange resin.

[0003] Among these, methods using a modified strong acidic ion exchange resin in which amines having a mercapto group are ion-bonded include 1) mercaptoamines are not mixed in a product, and 2) catalyst preparation is easy. This is a method superior to a method of covalently bonding a compound having a mercapto group or a method of simply allowing a compound having a mercapto group to coexist in a reaction system.

[0004] As a method of using a modified strong acid sulfonic acid type ion exchange resin in which mercaptoamines are ion-bonded, 2-mercaptoethylamine (Japanese Patent Publication No. 46-1)
9953, JP-A-62-298454), N
-Propylmercaptoalkylamine (JP-A-60-1)
No. 37440) has been proposed in which a modified strongly acidic sulfonic acid type ion exchange resin having an ion-bonded ion-exchange resin is used. As a method of using a denatured strongly acidic sulfonic acid type ion exchange resin in which the quaternary ammonium salt is ion-bonded, N, N, N-trimethyl-2-mercaptoethylammonium, N- (2-hydroxyl- 3-mercaptopropyl) pyridinium, N-methyl-N-
(2-Hydroxy-3-mercaptopropyl) morpholium and N-benzyl-N, N-dimethyl-2-mercaptoethylammonium (Czechoslovakia Patent No. 184988) modified ionically strong acid sulfonic acid type A method using an ion exchange resin has been proposed.

[0005]

However, both methods have a drawback that the acetone conversion is only about 50 to 75%. An object of the present invention is to provide a condensation reaction of acetone and phenol, which is useful as a catalyst for the production of bisphenol by the reaction of phenols and ketones, in particular, has a high conversion of acetone, and has good selectivity and stability. To provide a modified strong acidic sulfonic acid type ion exchange resin suitable as a catalyst for producing bisphenol A by the method.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that a modified strong acidic sulfonic acid type ion exchange resin obtained by ion-bonding a quinoline having a specific mercapto group is a phenol. The present invention has been found to be an excellent catalyst in the production of bisphenol A by the condensation reaction of phenol and acetone, thereby completing the present invention. That is, the present invention provides: A modified strongly acidic sulfonic acid type ion exchange resin in which a quinoline having a mercapto group represented by the following general formula (I) is ionically bonded to a strongly acidic sulfonic acid type ion exchange resin.

[0007]

Embedded image

Wherein X and Y are each independently:
A hydrogen atom, an alkyl group having 1 or 2 carbon atoms, a cycloalkyl group or an aryl group having 5 to 10 carbon atoms,
Represents an integer of 2 to 4. Further, the bonding position of the substituent having a mercapto group is any one of positions 2, 3, 4, 6 and 8 of quinoline.) In the presence of the modified strong acidic sulfonic acid type ion exchange resin described in section 2.1. And a reaction between a phenol and a ketone. ,It is in. Hereinafter, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The quinolines having a mercapto group of the formula (I) used in the modified strongly acidic sulfonic acid type ion exchange resin of the present invention are, for example, halogenated hydroxyalkyl quinolines and potassium thioacetate added thereto. It can be synthesized by reacting to thioacetate and then saponifying or reducing. Among the substituents of the quinolines having a mercapto group of the formula (I), X and Y
Is preferably a hydrogen atom and / or an alkyl group having 1 or 2 carbon atoms. Further, as a mercaptoalkyl group,
The alkyl portion of the main chain excluding X and Y has 2 to 4 carbon atoms, and a mercaptoalkyl group having 2 to 3 carbon atoms is more preferable.

Specific examples of the quinolines having a mercapto group of the formula (I) include 2- (2-mercaptoethyl) quinoline, 2- (3-mercaptopropyl) quinoline,
-(4-mercaptobutyl) quinoline, 3- (2-mercaptoethyl) quinoline, 3- (3-mercaptopropyl) quinoline, 3- (4-mercaptobutyl) quinoline, 4- (2-mercaptoethyl) quinoline, -(3
-Mercaptopropyl) quinoline, 4- (4-mercaptobutyl) quinoline, 6- (2-mercaptoethyl) quinoline, 6- (3-mercaptopropyl) quinoline, 6
-(4-mercaptobutyl) quinoline, 8- (2-mercaptoethyl) quinoline, 8- (3-mercaptopropyl) quinoline, 8- (4-mercaptobutyl) quinoline and the like.

As the ion exchange resin for ion-bonding a quinoline having a mercapto group, a strongly acidic sulfonic acid type ion conversion resin having a skeleton composed of a styrene-divinylbenzene copolymer and a sulfonic acid group bonded thereto is preferable. The content of divinylbenzene units in the copolymer is preferably from 2 to 40%. The exchange capacity of the ion exchange resin is 0.5 to 2.5 meq / ml in a hydrated state.
As the dry resin, a resin having a weight of 3.0 to 7.0 meq / g is preferable. The particle size distribution of the ion exchange resin is 200 to 1500 μm.
It is preferred that m occupies 95% or more.

Specific examples of such an ion exchange resin include Diaion SK1B, SK102, SK104,
PK208, PK212, RCP160H, RCP17
0H (Mitsubishi Chemical's product, Diaion is a registered trademark of Mitsubishi Chemical Corporation), Amberlist 15, 31, 32 (ROHM &
Haas products), Dowex 50w, 88 (Dow Chemical products) and the like. These ion exchange resins are in an acid form and are used for binding to the above-mentioned quinolines having a mercapto group. Since commercially available products are usually in the sodium form, they are treated with an acid such as hydrochloric acid and used in the acid form. These ion exchange resins are commercially available containing water, but can be used as they are without special treatment such as dehydration.

The sulfonate of a strongly acidic sulfonic acid type ion exchange resin
A quinoline having a mercapto group is bonded to a phonic acid group.
First, a suitable solvent such as water, alcohols,
Dissolve the quinolines in ethers, etc., and add this solution
Strongly acidic sulfonic acid type ion exchange tree dispersed in the same solvent
The mixture is stirred for an appropriate time, for example, 0.1 to 10 hours.
Just do it. For example, to bind in an aqueous solvent, quinolines
Than sulfonic acid _aLarge acids such as acetic acid, tri
Dissolve in aqueous solution of fluoroacetic acid, monochloroacetic acid, etc.
And the solution was pre-dispersed in water
Into the ion-exchange resin and stir for 0.1 to 10 hours
I just need.

The binding amount of the quinoline having a mercapto group to the strongly acidic sulfonic acid type ion exchange resin is usually 2 to 30 mol%, preferably 2 to 30 mol%, based on all the sulfonic acid groups of the strongly acidic sulfonic acid type ion exchange resin. , 5 to 20 mol%. If the amount of ionic bonds is less than 2 mol%, the catalytic effect of the quinoline having a mercapto group will not be sufficiently exhibited, and if it exceeds 30 mol%, the catalytic activity will decrease due to the decrease in the amount of free sulfonic acid. The modified strongly acidic sulfonic acid type ion exchange resin to which the quinolines having a mercapto group according to the present invention are ion-bonded has a very high conversion of acetone and a 4,4'-bisphenol A which are much higher than those of other resins.
Shows selectivity.

The modified strongly acidic sulfonic acid type ion exchange resin (hereinafter abbreviated as modified resin) obtained by ion-bonding a quinoline having a mercapto group obtained as described above is used for the condensation reaction between acetone and phenol. When performing the pretreatment, a container filled with the denatured resin is pre-treated with ion-exchanged water having a volume of 5 to 200 times the volume of the denatured resin at a temperature of 20 to 80 ° C. and a liquid hourly space velocity (LHSV) of 0.5 to 50 hr ^{− 1} and then pass phenol 5 to 200 times the volume of the modified resin at a temperature of 40 to 110 ° C. and an LHSV of 0.5 to 50.
Pass through at hr ^-1 . After the water contained in the modified resin is replaced with phenol by this treatment, it is subjected to the reaction.

The condensation reaction between phenol and acetone is usually carried out in a fixed bed flow reaction in which a raw material mixture containing phenol and acetone is continuously supplied to a reactor filled with a modified resin that has undergone the above-described treatment to carry out the reaction. It is done in a manner. The supply of the raw material mixture is performed in the range of LHSV 0.1 to 20 hr ^-1 , preferably 0.5 to 10 hr ^-1 . The reaction temperature ranges from 40 to 120C, preferably from 60 to 100C. If the reaction temperature is lower than 40 ° C., the reaction rate is low.
If the temperature exceeds 20 ° C., the denaturation of the denatured resin is remarkably deteriorated, and the by-products increase, which is not preferable.

The molar ratio of phenol to acetone used in the reaction is in the range of 3 to 30 moles, preferably 5 to 20 moles of phenol per mole of acetone. If the amount of phenol is less than 3 moles, the amount of by-products increases. 3
The use of more than 0 moles has little effect on the reaction performance, and is not economical because the amount of phenol from the reaction mixture is unnecessarily increased. In order to separate and purify bisphenol A as a target substance from the reaction mixture, for example, unreacted phenol is recovered, an adduct of bisphenol A and phenol is separated as crystals, and then phenol is recovered from the adduct by an operation such as distillation. Can be performed by a known method.

[0018]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples unless it exceeds the gist thereof. Note that the embodiment,
The conversion rate of acetone, the selectivity of 4,4'-bisphenol A (abbreviated as 4,4'-BPA), the modification rate and the residual rate of sulfonic acid in the comparative examples were calculated by the following formulas (all units are%).

[0019]

(Equation 1)

Example 1 4- (2-mercaptoethyl) quinoline-modified ion-exchange resin In a 100 ml autoclave, 4-methylquinoline was added.
2 g and 24.4 g of 37% formaldehyde were charged.
The mixture was stirred at 110 ° C. for 9 hours under a pressure of 0 kg / cm ² nitrogen. The reaction product was separated and purified by silica gel column chromatography to obtain 6.8 g of 4- (2-hydroxyethyl) quinoline. 5.14 g of 4- (2-hydroxyethyl) quinoline was dissolved in 72 ml of chloroform in a 200 ml three-necked flask, and thionyl chloride was dissolved in a nitrogen stream.
4 g were added dropwise. After stirring at 60 ° C for 1 hour, chloroform and unreacted thionyl chloride were distilled off under reduced pressure.
7.8 g of crude 4- (2-chloroethyl) quinoline hydrochloride were obtained.

4.0 g of this hydrochloride was dissolved in 40 ml of water in a 200 ml eggplant-shaped flask, and potassium thioacetate was dissolved in 2.0 ml of water.
4 g was added, and the mixture was heated under reflux for 1.5 hours. Under ice-cooling, 38 ml of 1N aqueous sodium hydroxide solution was added, and ethyl acetate 15 ml was added.
Extracted with 0 ml. After drying the ethyl acetate layer over anhydrous magnesium sulfate, the solvent was distilled off to give crude 4- (2-
2.94 g of (acetylthioethyl) quinoline were obtained.

In a 100 ml three-necked flask, 15 ml of anhydrous diethyl ether and 0.3 ml of lithium aluminum hydride were added.
2 g was charged under a nitrogen stream, and a solution of 1.62 g of the above thioacetate in 35 ml of anhydrous diethyl ether was added dropwise with stirring at room temperature. After heating and refluxing for 1.5 hours, the mixture was ice-cooled, and 0.17 g of distilled water and 0.55 g of acetic acid were added. The inorganic salt was separated by filtration, the organic layer washed with ethyl acetate was dried over anhydrous magnesium sulfate, the solvent was distilled off, and then the residue was separated and purified by silica gel column chromatography to obtain 605 mg of 4- (2-mercaptoethyl) quinoline. Obtained. (Purity by gas chromatography 93.0%)

4- (2-mercaptoethyl) quinoline 6
05 mg was dissolved in 10 ml of methanol.
11.2 g of ion exchange resin Diaion (registered trademark) SK104 (H type) suspended in 0 ml (manufactured by Mitsubishi Chemical Corporation,
(Exchange capacity: 1.63 meq / g) and stirred at room temperature for 5 hours. The ion exchange resin was filtered and washed with ion exchange water to obtain a modified ion exchange resin. When the residual amounts of the mercapto group and the sulfonic acid were analyzed, the modification rate was 14.4%.
And the residual ratio of sulfonic acid was 86.0%.

[0024] The modified ion exchange resin 14ml inner diameter 7.6 mm, was packed into a stainless column of full length 320 mm, the ion-exchanged water 200ml flushed with LHSV2hr ^-1, thereafter LHSV2hr ^-1 phenol at 70 ° C. 2
Run for 4 hours. Next, phenol / acetone = 10/1
The mixture (molar ratio) was passed at 70 ° C. and an LHSV of 1.0 hr ⁻¹ to carry out a continuous reaction. After 24 hours, the conversion of acetone was 92.4%, and the selectivity of 4,4'-BPA was 94.9.
%, And the conversion of acetone after 300 hours was 94.9.
%, The selectivity of 4,4'-BPA is 94.9%, and
The conversion of acetone after 00 hours was 94.7%, 4,4 '.
The selectivity for -BPA was 94.7%.

Example 2 2- (2-mercaptoethyl) quinoline-modified ion-exchange resin In a 100 ml autoclave, 2-methylquinoline was added.
2 g and 24.4 g of 37% formaldehyde were charged.
The mixture was stirred at 110 ° C. for 9 hours under a pressure of 0 kg / cm ² nitrogen. The reaction product was separated and purified by silica gel column chromatography to obtain 10.2 g of 2- (2-hydroxyethyl) quinoline. 5.14 g of 2- (2-hydroxyethyl) quinoline was dissolved in 72 ml of chloroform in a 200 ml three-necked flask, and thionyl chloride was dissolved in a nitrogen stream.
g was added dropwise. After stirring at 60 ° C. for 1 hour, chloroform and unreacted thionyl chloride were distilled off under reduced pressure to obtain 6.9 g of crude 2- (2-chloroethyl) quinoline hydrochloride.

4.0 g of this hydrochloride was dissolved in 40 ml of water in a 200 ml eggplant type flask, and potassium thioacetate was dissolved in 2.0 ml of water.
4 g was added, and the mixture was heated under reflux for 1.5 hours. Under ice-cooling, 38 ml of 1N aqueous sodium hydroxide solution was added, and ethyl acetate 15 ml was added.
Extracted with 0 ml. After drying the ethyl acetate layer over anhydrous magnesium sulfate, the solvent was distilled off to give crude 2- (2-
2.94 g of (acetylthioethyl) quinoline were obtained.

In a 100 ml three-necked flask, 20 ml of anhydrous diethyl ether and 0.4 ml of lithium aluminum hydride were placed.
0 g was charged under a nitrogen stream, and a solution of 2.03 g of the above thioacetate in 40 ml of anhydrous diethyl ether was added dropwise with stirring at room temperature. After heating under reflux for 1.5 hours, the mixture was ice-cooled, and 0.21 g of distilled water and 0.69 g of acetic acid were added. The inorganic salt was separated by filtration, the organic layer washed with ethyl acetate was dried over anhydrous magnesium sulfate, the solvent was distilled off, and then 756 mg of 2- (2-mercaptoethyl) quinoline was separated and purified by silica gel column chromatography. Obtained. (Purity by gas chromatography: 95.0%)

2- (2-mercaptoethyl) quinoline 7
56 mg was dissolved in 15 ml of methanol.
Diaion SK104 (H type) 1 suspended in 5 ml
5.0 g and stirred at room temperature for 5 hours. The ion exchange resin was filtered and washed with ion exchange water to obtain a modified ion exchange resin. When the residual amounts of the mercapto group and the sulfonic acid were analyzed, the modification ratio was 12.5% and the residual ratio of the sulfonic acid was 88.0%. Using this modified resin, the reaction was evaluated under the same conditions as in Example 1. Tables 1 and 2 show the reaction results for 24 hours, 300 hours, and 500 hours after the start of the reaction.

COMPARATIVE EXAMPLE 1 4- (Mercaptomethyl) quinoline-modified ion-exchange resin In a 1000 ml three-necked flask, 4-methylquinoline 2 was added.
4.0 g, 44.8 g of N-bromosuccinimide and 700 ml of chloroform were charged and heated under reflux with an infrared lamp for 3 hours. Chloroform was distilled off, and the crude reaction product was separated and purified by silica gel column chromatography to obtain 4.30 g of 4- (2-bromomethyl) quinoline. 4.3 g of this bromide was added to THF 330 in a 500 ml eggplant-shaped flask.
dissolved in potassium hydroxide, and added with 2.44 g of potassium thioacetate.
Stirred at 0 ° C. for 2 hours. Under ice-cooling, 44 ml of a 1N aqueous sodium hydroxide solution and 66 ml of water were added, and 300 ml of ethyl acetate was added.
Extracted in ml. After the ethyl acetate layer was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was separated by silica gel column chromatography to obtain 1.68 g of crude 4- (2-acetylthiomethyl) quinoline.

In a 100 ml three-necked flask, 20 ml of anhydrous diethyl ether and 0.3 ml of lithium aluminum hydride were added.
4 g was charged under a nitrogen stream, and a solution of 1.68 g of the above thioacetate in 20 ml of anhydrous diethyl ether was added dropwise with stirring at room temperature. After stirring at room temperature for 3 hours, the mixture was ice-cooled, and 0.18 g of distilled water and 0.6 g of acetic acid were added. Filtration of inorganic salts,
The organic layer washed with ethyl acetate was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was separated and purified by silica gel column chromatography to obtain 869 mg of 4-mercaptomethylquinoline. (Purity by gas chromatography 98.0%)

683 mg of 4-mercaptomethylquinoline
Was dissolved in 20 ml of methanol, added to 20 g of Diaion SK104 (H type) suspended in 10 ml of methanol, and stirred at room temperature for 5 hours. Filter the ion exchange resin,
After washing with ion-exchanged water, a modified ion-exchange resin was obtained. When the residual amounts of mercapto groups and sulfonic acids were analyzed,
The modification ratio was 10.2%, and the residual ratio of sulfonic acid was 87.
It was 0%. Using this modified resin, the reaction was evaluated under the same conditions as in the examples. Tables 1 and 2 show the reaction results for 24 hours and 300 hours after the start of the reaction.

Comparative Example 2 2-aminoethanethiol (cisamine) -modified ion exchange resin 0.58 g of commercially available 2-aminoethanethiol and 0.1% of acetic acid.
46 g of Diaion SK104 (H-type) dissolved in 20 ml of ion-exchanged water and suspended in 30 ml of ion-exchanged water
30.0 g, and the mixture was stirred at room temperature for 1 hour. The ion exchange resin was filtered and washed with ion exchange water to obtain a modified ion exchange resin. When the residual amounts of the mercapto group and the sulfonic acid were analyzed, the modification ratio was 15.2%, and the residual ratio of the sulfonic acid was 84.1%. Using this modified resin, the reaction was evaluated under the same conditions as in the examples. Tables 1 and 2 show the reaction results for 24 hours and 300 hours after the start of the reaction.

[0033]

According to the present invention, the use of the modified strongly acidic sulfonic acid type ion-exchange resin to which the quinoline having a mercapto group is bound according to the present invention allows a high acetone conversion and a high 4,4 Bisphenol A can be efficiently produced with a '-bisphenol A selectivity and with its performance connected for a long time.

[0034]

[Table 1]

[0035]

[Table 2]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Katsufumi Whale 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Inside Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (72) Inventor Hiroshi Iwane 8-Chome, Ami-cho, Inashiki-gun, Ibaraki Prefecture No.3-1 Inside the Tsukuba Research Laboratory, Mitsubishi Chemical Corporation

Claims (5)

[Claims] 1. A modified strongly acidic sulfonic acid type ion exchange resin in which a quinoline having a mercapto group represented by the following general formula (I) is ionically bonded to a strongly acidic sulfonic acid type ion exchange resin. Embedded image (Wherein, X and Y each independently represent a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, a cycloalkyl group or an aryl group having 5 to 10 carbon atoms, and n represents 2 to 4
Represents an integer. Further, the bonding position of the substituent having a mercapto group is any one of positions 2, 3, 4, 6, and 8 of quinoline.) 2. The modified strongly acidic sulfonic acid type ion exchange resin according to claim 1, wherein a quinoline having a mercapto group is bonded to 5 to 30 mol% of the sulfonic acid group. 3. The modified strongly acidic sulfonic acid type ion exchange resin according to claim 1, which has a skeleton composed of a styrene-divinylbenzene copolymer. 4. A method for producing bisphenol, comprising reacting a phenol with a ketone in the presence of the modified strongly acidic sulfonic acid type ion exchange resin according to claim 1. 5. The method for producing bisphenol according to claim 4, wherein the phenol is phenol and the ketone is acetone.