JP2000319216A - Production of bisphenol a - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce high quality bisphenol A at a low cost without causing deterioration of a catalyst by contacting phenol and acetone with a specific sulfonic acid-type cation exchange resin, and further contacting the resultant product with a specified organic high molecular siloxane catalyst. SOLUTION: Phenol is reacted with acetone in a reactor packed with an ion exchange resin (a modified ion exchange resin) in which a part of sulfonic acid group of the sulfonic acid-type cation exchange resin is bonded to a mercapto group-containing compound by an ionic bond, at 40-120 deg.C, and the product is further reacted in a reactor packed with an organic high molecular siloxane catalyst having both of a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group, at 40-140 deg.C to provide the objective bisphenol A. The contamination of the product bisphenol A with the mercapto group-containing hydrocarbon dropping off from the modified ion exchange resin can be also prevented. The reaction is preferably regulated so that 10-80% of the whole amount of the fed acetone may be consumed at the contact with the modified ion exchange resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bisphenol A
And a method for producing the same. More specifically, the present invention relates to a method for producing bisphenol A by reacting acetone and phenol in the presence of a solid acid catalyst.

[0002]

2. Description of the Related Art Bisphenol A [2,2-bis (4-
[Hydroxyphenyl) propane] is usually produced by reacting phenol and acetone in the presence of a homogeneous acid or a solid acid catalyst. The reaction mixture was bisphenol A, unreacted acetone, unreacted phenol,
Contains reaction water and other reaction by-products. The main component of the by-product is 2- (2-hydroxyphenyl) -2- (4-
Hydroxyphenyl) propane (hereinafter o, p'-BP)
A), which also includes trisphenol, polyphenol compounds, chroman compounds, coloring impurities and the like.

[0003] Examples of the homogeneous acid used as a catalyst include hydrochloric acid, sulfuric acid and the like. When a homogeneous acid is used, it is possible to react while precipitating phenol and bisphenol A adduct crystals by reacting at a low temperature, so that the acetone and the isomers o and p ′ are obtained together with a high conversion rate. -It is possible to produce bisphenol A with high selectivity by reducing the amount of by-products of BPA. However, a homogeneous acid catalyst such as hydrochloric acid removes the catalyst from the reaction mixture,
Alternatively, a step of neutralizing is required, and the operation becomes complicated.
In addition, since the acid is uniformly dissolved in the reaction solution, corrosion of the apparatus and the like is caused, and therefore, an expensive corrosion-resistant material must be used for the reaction apparatus, which is not economical.

As a solid acid catalyst, a sulfonic acid type cation exchange resin is mainly used, and a compound containing a mercapto group is allowed to coexist in a reaction system to improve catalyst activity and selectivity. It is known that can be. Specifically, a method of flowing a free mercapto group-containing compound such as an alkyl mercaptan together with phenol and acetone as raw materials into a fixed bed reactor filled with a sulfonic acid type cation exchange resin (Japanese Patent Publication No.
No. 10337), a method of covalently bonding a part of a sulfonic acid group of a sulfonic acid type cation exchange resin to a mercapto group-containing compound, a method of combining a part of a sulfonic acid group of a sulfonic acid type cation exchange resin with a mercapto group-containing compound Are bonded by an ionic bond (Japanese Patent Publication No. 46-19553). A method of flowing a free mercapto group-containing compound such as alkyl mercaptan together with phenol and acetone as raw materials into a fixed bed reactor filled with a sulfonic acid type cation exchange resin is always a fixed amount of the mercapto group-containing compound in the reaction system. Is present, so that there is an advantage that catalyst deterioration is small, but there is a possibility that the mercapto group-containing compound may cause coloring of bisphenol A, and it is necessary to remove and recover the mercapto group-containing compound. On the other hand, the method of bonding a mercapto group-containing compound to a part of the sulfonic acid groups of the sulfonic acid type cation exchange resin is compared with a method of allowing a free mercapto group-containing compound to be present in the reaction system, There are advantages such as low loss and no need to recover the mercapto group-containing compound. However, among the methods of bonding a mercapto group-containing compound to a part of the sulfonic acid group of the sulfonic acid type cation exchange resin, the method of bonding a part of the sulfonic acid group to the mercapto group-containing compound by a covalent bond is called sulfonic acid. The step of bonding the mercapto group-containing compound to a part of the groups is complicated, and a decrease in activity due to poisoning of the mercapto group is observed. The method of bonding a part of the sulfonic acid group of the sulfonic acid type cation exchange resin to the mercapto group-containing compound by an ionic bond is simple, although the step of bonding the mercapto group-containing compound to a part of the sulfonic acid group is simple. There is a deterioration of the catalytic activity due to poisoning of the mercapto group and elimination of the mercapto group-containing compound.
The eliminated mercapto group-containing compound may be mixed into the product bisphenol A and deteriorate the product quality. Also, in any of the methods using a sulfonic acid type cation exchange resin as a catalyst, a large reactor is required because the catalytic activity is reduced by water generated by the reaction.

As a solid acid catalyst other than a sulfonic acid type cation exchange resin, an organic high molecular siloxane catalyst having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group has been reported (JP-A-8-208545). JP-A-9-110767, JP-A-9-110989, and JP-A-10-225638. This catalyst has high activity and high selectivity as compared with the modified ion exchange resin, and is excellent as a catalyst for producing bisphenol A because the decrease in catalytic activity due to water produced by the reaction is small. It has not been put to practical use because it is more expensive than the above and has a reduced activity due to poisoning of the mercapto group.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a method for producing bisphenol A by reacting phenol and acetone, comprising an organic polymer siloxane catalyst having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group. It is intended to provide a low-cost and high-quality method for producing high-quality bisphenol A, which is less deteriorated and has less mercapto group-containing compounds in the product.

[0007]

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, at least a part of phenol and acetone was replaced with a part of sulfonic acid groups of a sulfonic acid type cation exchange resin. After the mercapto group-containing compound is brought into contact with an ion-exchange resin (hereinafter, referred to as a modified ion-exchange resin) bound by an ionic bond and reacted, an organic compound having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group is obtained. By further performing the reaction in the presence of a molecular siloxane catalyst (hereinafter, referred to as an organic polymer siloxane catalyst), it is possible to prevent a decrease in the activity of the organic polymer siloxane catalyst having the characteristics of high activity and high selectivity. It is possible to prevent the mercapto group-containing compound desorbed from the modified ion exchange resin from being mixed into the product, and to obtain high-quality bisphenol A. It found Rukoto. In addition, the organic polymer siloxane catalyst is less susceptible to poisoning by the water produced by the reaction, and even in the presence of water produced by the reaction in the presence of the modified ion exchange resin catalyst, high acetone conversion can be achieved in a small reactor. The present inventors have found that the reaction can be carried out with the present invention, and have completed the present invention.

That is, the present invention relates to a method for producing bisphenol A by reacting phenol with acetone, wherein a sulfonic acid type cation exchange resin comprising phenol and acetone combined with a compound containing a mercapto group at a part of sulfonic groups. And then contacting with an organic polymer siloxane having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As the phenol used as a raw material in the present invention, commercially available industrial phenol can be used. Industrial phenols include those produced by the cumene method or the toluene oxidation method, and those produced by either method may be used. Generally 98% pure
The above phenols are commercially available. Such an industrial phenol may be used as it is in the bisphenol A synthesis reaction, but preferably, before the reaction is carried out, the phenol is previously treated with a strong acid type cation exchange resin in a continuous or batch manner at a treatment temperature of 50. ~ 120 ° C, contact time 5min ~ 10
Use the one processed in time. More preferably, after the industrial phenol is subjected to the contact treatment with the strong acid type cation exchange resin as described above, the phenol is subjected to a distillation treatment at a temperature of 70 to 200 ° C. under a reduced pressure of normal pressure to 10 mmHg.

There is no particular limitation on the acetone used in the present invention, and commercially available commercially available acetone may be used. Generally, those having a purity of 99% or more are available.

A mixture of phenol and acetone as described above is supplied to a reactor (first reactor) filled with a modified ion exchange resin, and the reaction mixture obtained in the first reactor is converted into an organic polymer. Reactor filled with siloxane catalyst (second
Reactor). In the present invention, the reactors filled with these catalysts will be referred to as a first reactor and a second reactor, respectively, for convenience. The modified ion exchange resin is provided at the inlet side where phenol and acetone as raw materials are supplied. , And one reactor filled with an organic polymer siloxane catalyst on the outlet side may be used. It is preferable that the entire amount of phenol supplied as a raw material be supplied to the first reactor. Acetone may be supplied separately to the first reactor and the second reactor. If you supply acetone in divided parts,
More than 50%, preferably more than 70% of the total feed is fed to the first reactor. The molar ratio of phenol to acetone fed to the first reactor is 4-30, preferably 6-2.
0. In the reaction in the first reactor, usually, 10 to 80%, preferably 20 to 70%, more preferably 20 to 70% of the total amount of acetone supplied to the combined reaction system of the first reactor and the second reactor. The reaction takes place such that 50% is consumed. When the consumption of acetone in the first reactor is 10% or more, the deterioration of the organic polymer siloxane catalyst having both the sulfonic acid group-containing hydrocarbon group and the mercapto group-containing hydrocarbon group in the second reactor is small. If the consumption of acetone in the first reactor is 80% or less, the size of the first reactor does not increase, and the characteristics of the organic polymer siloxane catalyst having high activity and high selectivity can be utilized. The reaction temperature in the first reactor is generally 40 to 120 ° C., preferably 5 to 120 ° C.
0-90 ° C.

Modified ion exchange resins are generally available sulfonic acid type cation exchange resins, for example,
It can be prepared by bonding a mercapto group-containing compound by a method disclosed in 199553 or the like. The ratio at which the mercapto group-containing compound is bonded to the sulfonic acid groups is 2 to 50%, preferably 5 to 30% of the total sulfonic acid groups of the sulfonic acid type cation exchange resin. When the proportion of the mercapto group-containing compound is within the above range, the reaction can be carried out efficiently, so that the size of the first reactor is reduced, and the effect of extending the life of the organic polymer siloxane catalyst is also increased.

The sulfonic acid type cation exchange resin before binding the mercapto group-containing compound may be any of those generally available, such as Diaion manufactured by Mitsubishi Chemical Corporation, Amberlite and Amberlyst manufactured by Rohm and Haas Company,
Bayer's Levatit etc. are mentioned. As the strong acid type cation exchange resin, any of a gel type and a macroporous type can be used, but the use of a gel type having a degree of crosslinking of 2 to 8% provides higher conversion and bisphenol A selectivity, and It is preferable because it can be used stably for a long period of time.

There is no particular limitation on the mercapto group-containing compound to be bonded to a part of the sulfonic acid group of the sulfonic acid type cation exchange resin, and it is a compound which forms an ionic bond with the sulfonic acid group of the sulfonic acid type cation exchange resin. I just want it. Examples of such compounds include 2-mercaptoethylamine (cysteamine), 3-mercaptopropylamine, mercaptoalkylamines such as N, N-dimethyl-3-mercaptopropylamine, 3-mercaptomethylpyridine, 3-mercaptoethylpyridine , 4-mercaptoethylpyridine and other mercaptoalkylpyridines, thiazolidine, 2,2-dimethylthiazolidine,
And thiazolidines such as -methyl-2-phenylthiazolidine and 3-methylthiazolidine. As a method for bonding the mercapto group-containing compound to the sulfonic acid type cation exchange resin, a conventionally known method as shown in JP-B-46-19953 can be used.

The reaction mixture obtained in the first reactor is supplied to a second reactor filled with an organic high molecular siloxane. When acetone is divided and fed to the reactor, the first
The remaining acetone supplied to the first reactor together with the reaction mixture obtained in the reactor is supplied to the second reactor. The amount of unreacted acetone at the outlet of the second reactor is preferably
The reaction is performed so that the amount of acetone supplied to the reaction system is 20% or less of the total amount. When the amount of unreacted acetone is 20% or less, the energy for recovering unreacted acetone is small, and the amount of liquid flowing through the reaction system is small, which is more economical. The reaction temperature of the second reactor is usually 40 to 140
° C, preferably 50 to 100 ° C.

As the organic high molecular siloxane, for example,
JP-A-8-208545, JP-A-9-110989 and JP-A-10-225638, a hydrocarbon group having a sulfonic acid group partially and a mercapto group in a silica matrix composed of a siloxane bond. And an organic polymer siloxane having a structure in which a hydrocarbon group having a structure is directly bonded to a silicon atom in a silica matrix by a carbon-silicon bond. As a method for preparing such an organic polymer siloxane, for example, (1)
A preparation method in which an alkoxysilane having a sulfonic acid group-containing hydrocarbon group, an alkoxysilane having a mercapto group-containing hydrocarbon group, and tetraalkoxysilane are mixed at an arbitrary ratio, and synthesized by hydrolysis and polycondensation, (2) A hydrolyzate of a water-soluble alkoxysilane having a sulfonic acid group-containing hydrocarbon group, an alkoxysilane having a mercapto group-containing hydrocarbon group, and tetraalkoxysilane are mixed at an arbitrary ratio and synthesized by hydrolysis and polycondensation. So-called alkoxysilane sol-
Preparation methods (1) and (2) by a gel method, and (3) silylation of an alkoxysilane having a mercapto group-containing hydrocarbon group to a silanol group present in an organic polymer siloxane having a sulfonic acid group-containing hydrocarbon group; A preparation method by immobilizing a mercapto group, that is, a so-called silylation is known.

The hydrocarbon group having a sulfonic acid group is less
At least one sulfonic acid group (—SO _ThreeH) having carbonization
Any hydrocarbon group as long as it is a hydrogen group is included in the present invention.
It is possible to use, but preferably a sulfonic acid group
Having at least one and having 1 to 20 carbon atoms
Elementary group. Preferably it has 6 to 20 carbon atoms, more preferably
Preferably at least one sulfo having 6 to 15 carbon atoms
Substituted or unsubstituted aromatic hydrocarbons having a phonic acid group
Groups (even groups in which aromatic groups are directly substituted with sulfonic acid groups,
Sulfonic acid group replaces hydrocarbon group substituted by aromatic group
Any of the following groups); or, preferably,
1 to 15 carbon atoms with at least one sulfonic acid group
Under, more preferably, substitution of 1 to 10 carbon atoms or less
Is from the group consisting of unsubstituted aliphatic and alicyclic hydrocarbon groups
At least one selected hydrocarbon group. like this
Examples of hydrocarbon groups having various sulfonic acid groups include:
Phenyl nucleus substituted by at least one sulfonic acid group
, Tolyl, naphthyl, methylnaphthyl, etc.
Aromatic groups such as aromatic groups, benzyl groups, and naphthylmethyl groups.
Substituted with at least one sulfonic acid group, such as
Methyl, ethyl, n-propyl, i-propyl
Group, n-butyl group, i-butyl group, t-butyl group,
Chain or branched pentyl group, straight or branched hexyl
Group, straight-chain or branched heptyl group, straight-chain or branched
Octyl group, cyclohexyl group, methylcyclohexyl
And an ethylcyclohexyl group. More
Their aromatic or saturated aliphatic or cycloaliphatic hydrocarbons
In addition to sulfonic acid groups, halogen groups, alkoxy groups
Group, nitro group, amino group, hydroxy group, etc.
Hydrocarbon group.

The hydrocarbon group having a mercapto group has at least one mercapto group represented by the formula -SH.
At least one selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms, wherein aliphatic or alicyclic saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon is -SH
A hydrocarbon group to which the group is attached. Preferably, an aliphatic or alicyclic saturated hydrocarbon group or an aromatic hydrocarbon group has S
It is a hydrocarbon group having at least one H group bonded thereto. Examples of the hydrocarbon group having such a mercapto group include:
Mercaptoalkyl groups such as mercaptomethyl group, 2-mercaptoethyl group and 3-mercapto-n-propyl group; alicyclic hydrocarbon groups such as 4-mercaptocyclohexyl group and 4-mercaptomethylcyclohexyl group; p-
And mercapto aromatic groups such as a mercaptophenyl group and a p-mercaptomethylphenyl group. Further, these aromatic or aliphatic or alicyclic hydrocarbon groups may be hydrocarbon groups having a substituent such as a halogen atom, an alkoxy group, a nitro group, an amino group or a hydroxy group in addition to a mercapto group. .

The molar ratio of acetone to phenol supplied to the whole reaction system is 4 to 20, preferably 5 to 16.
When the molar ratio of phenol to acetone is 4 or more, generation of impurities such as mesityl oxide by-produced from acetone is reduced. Further, when the molar ratio is 20 or less, the amount of unreacted phenol circulated is reduced, so that equipment such as a reactor and a crystallizer are reduced, and power required for circulation, energy required for heating and cooling, and the like are reduced. Economic and economical.

An organic polymer siloxane catalyst having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group is a catalyst having higher activity and higher selectivity than a modified ion exchange resin. When used alone, the catalyst activity is greatly reduced. According to the method of the present invention, the degradation of the catalyst can be prevented by using the organic high molecular siloxane catalyst after first reacting at least a part of phenol and acetone with the modified ion exchange resin catalyst. When the modified ion exchange resin alone is used, the modified ion exchange resin catalyst is poisoned by the generated water, so a large reactor is required.However, the organic polymer siloxane catalyst is hardly poisoned by water, And since it is highly active, the size of the reactor can be reduced. Therefore, by using a high selectivity organic polymer siloxane catalyst after the modified ion exchange resin, the yield of bisphenol A is improved and it is economical. Furthermore, since the modified ion exchange resin catalyst binds the mercapto group-containing hydrocarbon group with an ionic bond,
It is considered that a part of the bisphenol A is desorbed in a small amount and mixed into the product, thereby coloring the product bisphenol A. However, according to the method of the present invention, the amount of the modified ion exchange resin used can be significantly reduced. The amount of the mercapto group-containing hydrocarbon group to be eliminated can be reduced, and since the eliminated mercapto group-containing hydrocarbon group is captured by the sulfonic acid group of the organic polymer siloxane catalyst, the mercapto group-containing hydrocarbon is substantially reduced. No groups are incorporated into the product bisphenol A.

The reaction solution obtained as described above is cooled after the reaction product water, unreacted acetone and a part of unreacted phenol are removed, if necessary, and then an equimolar adduct of bisphenol A and phenol is added. Bisphenol A is separated in the form of crystals. Further, phenol is removed from this equimolar adduct and bisphenol A is isolated.

[0022]

Next, the present invention will be described in more detail with reference to examples. The organic polymer siloxane catalyst and modified ion exchange resin catalyst used were each prepared by the following methods.

[Preparation of organic polymer siloxane catalyst] An organic polymer siloxane having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group was prepared according to the following procedures (a) and (b).

(A) Synthesis of sulfonic acid group-containing alkoxysilane 200 ml of methylene chloride was placed in a two-necked 500 ml round bottom flask equipped with a dropping funnel, and 123.0 g (0.580 mol) of phenyltrichlorosilane was added thereto. Ice cooled. 46.4 g of sulfuric anhydride (0.580 g)
(mol) in 100 ml of methylene chloride was added dropwise over 30 minutes under a nitrogen stream, and the ice bath was removed, followed by stirring at room temperature for 5 hours to perform sulfonation. The dropping funnel was removed, and the mixture was heated to 100 ° C. using an oil bath under a nitrogen stream to distill off methylene chloride and unreacted sulfuric anhydride.
After allowing to cool, 160 g of ethanol was added dropwise at room temperature over 3 hours, followed by refluxing for 2 hours while bubbling with nitrogen to carry out an ethoxylation reaction while removing generated hydrogen chloride. 234.7 g of an ethanol solution of ethoxysilane containing a phenylsulfonic acid group containing impurities obtained was mixed with a sulfone in a sol-gel preparation of an organic polymer siloxane catalyst having the following hydrocarbon group containing a sulfonic acid group and a hydrocarbon group containing a mercapto group. Used as a raw material for the acid component.

(B) Preparation of an organic high molecular siloxane having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group The above-mentioned sulfonic acid group-containing ethoxysilane was placed in a two-necked 500 ml round bottom flask equipped with a stirring bar. 26.0 g of ethanol solution and 35.5 g of tetraethoxysilane (1
70.7 mmol), 6.7 g (34.3 mmol) of mercaptopropyltrimethoxysilane, ethanol 30
ml and mixed. 7.5 g of water (0.42 m
ol) was added dropwise over 30 minutes. Then heat this,
Stirred at 65 ° C. for 4 hours. After cooling, an aqueous solution obtained by mixing 15 ml of 28% aqueous ammonia and 75 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours. The mixture was further stirred at 65 ° C. for a day and aged to mature. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Then, 200 ml of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. After filtration, the operation of washing with 500 ml of ion-exchanged water was repeated 10 times to remove hydrochloric acid. Finally, it was dried at 100 ° C. under reduced pressure for 6 hours. Through the above operations, 30 g of an organic polymer siloxane having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group was obtained.
The solid acid content of the catalyst was measured to be 0.98 meq /
g.

[Preparation of modified ion exchange resin] 500 ml of a sulfonic acid type cation exchange resin (K1221 manufactured by Bayer AG) swollen with water and having an exchange capacity of 1.9 eq / l was added to 500 parts of water.
The mixture was stirred at 85 ° C. 8. Add the cysteamine hydrochloride to 50 ml of water in the slurry of the ion exchange resin.
An aqueous solution in which 4 g was dissolved was added over 1 hour, and the mixture was left at 85 ° C. for 16 hours with stirring. After that, the ion exchange resin is separated by filtration, washed sufficiently with water,
Vacuum drying was performed at 00 ° C. for 20 hours. The modified ion exchange resin obtained here was a modified ion exchange resin in which 15% of the sulfonic acid groups were bonded to cysteamine.

Example 1 A reactor filled with 30 ml of a modified ion exchange resin (modified IER) converted to a state swollen with water and a cylindrical reactor filled with 30 ml of an organic high molecular siloxane catalyst and having an inner diameter of 20 mm were mixed with a modified ion exchange resin. Two units were connected in series in the order of an exchange resin and an organic polymer siloxane catalyst. While keeping these reactors at 75 ° C., a mixture of 95.1 wt% of phenol and 4.9 wt% of acetone was continuously passed at 50 g / h to start the reaction.

At 24 hours and 500 hours after the start of the reaction, the results of analysis of the reaction solution at the outlet of each reactor by high performance liquid chromatography are shown in Table 1. When the nitrogen content in the reaction solution after 24 hours was measured as an index of cysteamine desorbed from the modified ion exchange resin, it was not detected (10 ppb or less).

Example 2 A reaction was carried out in the same manner as in Example 1 except that the amount of the modified ion exchange resin charged was 20 ml. Table 1 shows the results.
The nitrogen content of each reaction solution was measured, but none was detected.

Example 3 A reaction was carried out in the same manner as in Example 1 except that the filling amount of the modified ion exchange resin was changed to 10 ml. Table 1 shows the results.
The nitrogen content of each reaction solution was measured, but none was detected.

Comparative Example 1 The procedure of Example 1 was repeated, except that a modified ion exchange resin was not used, and only a reactor filled with 30 ml of an organic high molecular siloxane catalyst was used. Table 1 shows the results. When only the organic polymer siloxane catalyst was used, after 500 hours, the acetone conversion and bisphenol A (BP
A) It can be seen that both the selectivity is greatly reduced.

COMPARATIVE EXAMPLE 2 In place of the modified ion exchange resin, a reactor filled with 10 ml of an organic polymer siloxane catalyst and two cylindrical reactors filled with 30 ml of an organic polymer siloxane catalyst and having an inner diameter of 20 mm were connected in series. Was performed in the same manner as in Example 1. Table 1 shows the results. After 500 hours, both the acetone conversion and the bisphenol A (BPA) selectivity
It turns out that it has fallen greatly.

Comparative Example 3 Two reactors each containing 30 ml of the modified ion exchange resin were charged.
The reaction was carried out in the same manner as in Example 1 except that the reactors were connected in series. Twenty-four hours after the start of the reaction, the acetone conversion in the total of two reactors was 74.8%, and the acetone conversion was low despite the same reactor capacity as in Example 1. When the nitrogen content of the reaction solution was measured,
ppb.

[0034]

[Table 1]

[0035]

According to the method of the present invention, it is possible to prevent deterioration of an organic polymer siloxane catalyst having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group, which is highly active and has high selectivity. A method for producing bisphenol A with a high conversion rate and a high yield can be provided, and bisphenol A can be produced economically and advantageously.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Kazuyo Matsu 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. F-term (reference) 4H006 AA02 AC25 BA72 BC40 FC52 FE13 4H039 CA19 CA41 CD10 CD40

Claims (3)

[Claims] 1. A method for producing bisphenol A by reacting phenol with acetone, wherein the phenol and acetone are brought into contact with a sulfonic acid type cation exchange resin in which a compound containing a mercapto group is partially bonded to a sulfonic acid group. And then contacting with an organic polymer siloxane having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group. 2. A reaction by contact with a sulfonic acid type cation exchange resin in which a mercapto group-containing compound is partially bonded to a part of sulfonic acid groups, whereby 10 to 80% of the total amount of acetone supplied to the reaction system. A process according to claim 1, wherein an amount of acetone is consumed. 3. The amount of unreacted acetone after contacting with an organic high molecular siloxane having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group is based on the total amount of acetone supplied to the reaction system. 2. The method of claim 1, wherein the weight is less than 20%.