JP5169877B2 - Method for producing bisphenols - Google Patents

Description

  The present invention relates to a method for producing bisphenols by reacting a carbonyl compound and a phenol compound in the presence of a solid acid catalyst. Specifically, the present invention relates to a method for producing industrially useful bisphenols with high selectivity and high yield by using a catalyst obtained by modifying a cation exchange clay mineral with a nitrogen-containing compound having a mercapto group. is there.

Bisphenols such as 2,2-bis (4′-hydroxyphenyl) propane (hereinafter sometimes referred to as “bisphenol A”) are intermediate raw materials for polycarbonate, polyester, epoxy resin and color developer for thermal paper. As such, it is an extremely industrially useful compound.
Bisphenol A is usually synthesized by reacting phenol and acetone in the presence of an acidic catalyst, and a sulfur compound such as methyl mercaptan may be added as a co-catalyst during the reaction. As an acidic catalyst, hydrogen chloride or an acidic ion exchange resin is usually used. However, a method using hydrogen chloride as a catalyst is a reactor using an expensive corrosion-resistant material in terms of corrosiveness due to hydrogen chloride. And a purification step for removing hydrogen chloride from the reaction mixture or a neutralization step is required.

In addition, the method using an acidic ion exchange resin as a catalyst has a drawback in that the reaction between phenol and acetone is inhibited by water produced by the reaction and the apparent activity of the catalyst is lowered, and the reaction is carried out while removing water. Although a method has been studied, improvement is desired in terms of the lifetime and cost of the acidic ion exchange resin.
There has also been proposed a method in which a strongly acidic sulfonic acid type ion exchange resin is used as the acidic ion exchange resin and a modified ion exchange resin in which mercaptoamines are ion-bonded is used. However, acidic ion exchange resins, including the above-mentioned modified ion exchange resins, are generally stored in water, and the water contained in the ion exchange resin is replaced with phenol by treatment with phenol before use. And then need to be used for the reaction. Further, when the modified ion exchange resin is used, trisphenol or the like may be by-produced. Furthermore, acidic ion exchange resins are limited in the amount of acid sites introduced per unit volume, making it difficult to reduce the size of the reactor, and further improvements in the heat resistance of the ion exchange resins themselves are desired. .

  On the other hand, as an example of using montmorillonite, which is an inorganic compound, as a catalyst, a neutralized montmorillonite is treated with sulfuric acid or trifluoromethanesulfonic acid to form a proton type, or a proton type montmorillonite is further treated with hydrofluoric acid. A fluorinated catalyst has been proposed (Patent Document 1). However, these montmorillonite catalysts have a low yield of bisphenol A, and the isomer 2- (2'-hydroxyphenyl) -2- (4 "-hydroxyphenyl) propane (hereinafter referred to as 2,4-bisphenol A 2,4- In other words, the selectivity is low and the purification process becomes complicated.

  In addition, coexistence of a cation-exchangeable montmorillonite and a mercapto group-containing compound improves the activity when synthesizing bisphenol A from phenol and acetone, and is a secondary bisphenol A secondary component of bisphenol A. A method for improving the selectivity of bisphenol A by reducing the amount of raw material is known (Patent Document 2). However, according to our study, the conversion rate and the yield of bisphenol A are still insufficient.

JP-A-6-9470 Japanese Patent Laid-Open No. 10-17509

  The present invention solves the above-mentioned problems of the prior art, suppresses the formation of by-products typified by trisphenol by the reaction of a carbonyl compound such as acetone and a phenol compound such as phenol, and bisphenols such as bisphenol A It is an object of the present invention to provide a method for producing bisphenol A with high selectivity and high yield, and particularly preferably to provide a method for producing bisphenol A with high selectivity and high yield.

As a result of studies conducted by the present inventors in view of the present situation, the conversion rate of the raw material can be obtained by using, as a catalyst, a cation-exchangeable clay mineral modified with a nitrogen-containing compound in which at least a part of the acid sites has a mercapto group. The present invention was completed by finding a method for producing bisphenols with high selectivity and high yield.
That is, the gist of the present invention is a method for producing a bisphenol by reacting a carbonyl compound and a phenol compound in the presence of a solid acid catalyst, wherein the solid acid catalyst has a mercapto group having at least a part of acid sites. The present invention resides in a method for producing bisphenols, which is a cation-exchangeable clay mineral modified with a nitrogen-containing compound having the following.

  According to the method for producing bisphenols of the present invention, it is possible to produce bisphenols, particularly preferably bisphenol A, with a high selectivity and a high yield, since the raw material has a high conversion rate. Moreover, since the production amount of impurities is remarkably small, the purification process in the bisphenol production process can be simplified.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of constituent elements described below is an example (representative example) of an embodiment of the present invention, and is not specified by these contents.
<Carbonyl compound>
Examples of carbonyl compounds used in the present invention include ketones having about 3 to 10 carbon atoms such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, and formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and the like. Examples include aldehydes having about 1 to 10 carbon atoms. Among these, formaldehyde and acetone are preferable, and acetone is particularly preferable.

<Phenol compound>
Specific examples of the phenol compound include unsubstituted phenol; o-cresol, m-cresol, 2,5-xylenol, 2,6-xylenol, 2,3,6-trimethylphenol, 2,6- Phenol substituted with an alkyl group having 1 to 4 carbon atoms such as di-tert-butylphenol; substituted with halogen such as o-chlorophenol, m-chlorophenol, 2,5-dichlorophenol, 2,6-dichlorophenol And phenol. Here, when the phenol compound is substituted with a substituent or a halogen, the substituted site may be one site or a plurality of sites. Of these, phenol is particularly preferred. When phenol is used as the phenol compound and acetone is used as the carbonyl compound, bisphenol A useful as a raw material for polycarbonate resin and the like can be obtained, which is particularly preferable.

<Ratio of raw materials>
The molar ratio of the phenol compound and the carbonyl compound used in the reaction is usually 2 mol or more, preferably 4 mol or more, and usually 40 mol or less, preferably 30 mol or less, with respect to 1 mol of the carbonyl compound. If the amount of phenolic compound used is too small, there is a tendency for by-products to increase. On the other hand, if the amount of phenolic compound used is too large, there will be little change in the effect of reducing by-products. There is a tendency to become unfocused.

<Cation-exchangeable clay minerals>
The solid acid catalyst used in the method for producing bisphenols of the present invention is a cation exchangeable clay mineral modified with a nitrogen-containing compound having at least a part of acid sites having a mercapto group. Cation-exchangeable clay minerals are usually layered and have a cation between layers. When the cation (X) existing between the layers is a proton, that portion becomes a Bronsted acid point, and the cation (X ) Is a metal cation, the coordinated water of the exchange ion is polarized to generate protons (H ⁺⁾ , which is preferable because it is strongly solid acidic. Examples of the metal cation include a cation of titanium, aluminum, niobium, tin, iron, and zirconium. Among them, a cation of titanium, aluminum, and niobium is preferable from the viewpoint of acid strength.

  Typical examples of cation exchange clay minerals include tetrahedrons formed by coordination of oxygen ions to silicon and aluminum ions, and oxygen or hydroxide ions to cations such as aluminum, magnesium or iron. An inorganic polymer composed of coordinated octahedrons is a clay mineral that is negatively charged by isomorphous substitution and adsorbs cations, and the cations are exchanged with protons or metal cations The thing which was done is mentioned. Specifically, the cations of clay minerals such as smectite group, vermiculite group, mica group, brittle mica group, etc., which are cation exchanged with protons or metal cations are mentioned, among others, cation exchange capacity From this viewpoint, it is preferable that the cations of the smectite group clay minerals are cation exchanged with protons or metal cations.

As the smectite group clay minerals, those represented by the general formula (1) are preferable.
X _m (Y ²⁺ , Y ³⁺ ) ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (1)
(Wherein, X is a cation between layers selected from the group consisting of K ⁺ , Na ⁺ , 1 / 2Ca ²⁺ and 1 / 2Mg ²⁺ , Y ²⁺ is Mg ²⁺ , Fe ²⁺ , Mn ²⁺ , An octahedral cation selected from the group consisting of Ni ²⁺ and Zn ²⁺ , Y ³⁺ is an octahedral cation selected from the group consisting of Al ³⁺ , Fe ³⁺ and Cr ³⁺ , Z is Si and A tetrahedral cation selected from Al, m is a positive number greater than 0 and less than or equal to 0.6, and n is 0 or a positive number greater than 0.)

In the clay layer, a tetrahedron surrounded by four O ²⁻ layers of Si ⁴⁺ or Al ³⁺ shares three of the four vertices with the adjacent tetrahedron, and the remaining one vertex points in the same direction. A tetrahedral sheet having a composition of (Si, Al) ₂ O ₅ , Al ³⁺ , Mg ²⁺ , Fe ²⁺ , Fe ³⁺ , Cr ³⁺ , Mn ²⁺ , An octahedron surrounded by six (OH) ⁻ or O ²⁻ ions having the same ionic radius as a metal cation represented by Ni ²⁺ , Zn ^2+, etc. shares a two-dimensional shape. It is basically composed of an octahedral sheet having a composition of Al ₂ · (OH) ₆ or Mg ₃ (OH) ₆ .

  Natural smectites usually have cations such as sodium and calcium between the layers. As a method for cation exchange of these cations with protons or another metal cation, a known method can be adopted and is not particularly limited, but usually a compound of smectite and a metal cation in the presence of a solvent. It is performed by the method of mixing. Examples of the metal cation compound include chlorides, nitrates, carbonates, sulfates, acetates, and phosphates of the metal cation compounds as described above. In addition, when cation exchange is performed in the presence of a solvent, in order to shorten the cation exchange time, the temperature of the solvent is heated within the range of room temperature to the boiling point of the solvent and stirred for about 30 minutes to 30 hours. Also good. The solvent used in the ion exchange is not particularly limited as long as it dissolves the compound containing the metal element used in the ion exchange. Water is usually used, an organic solvent is used, or an organic solvent and water are used. And may be used in combination.

  Examples of the smectite group clay mineral represented by the general formula (1) include montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, soconite, and stevensite. Among these, montmorillonite is preferable from the viewpoint of availability. Therefore, in the present invention, a cation-exchangeable montmorillonite that has been converted to an acidic form by subjecting the montmorillonite to an acid treatment or a cation exchange treatment is preferable.

In addition, as a montmorillonite, the thing of following formula (2) is mentioned.
X _m (Al _2-l Mg _l ) Si ₄ O ₁₀ (OH) ₂ .nH ₂ O (2)
(Wherein, X is a cation between layers selected from the group consisting of K ⁺ , Na ⁺ , 1 / 2Ca ²⁺ and 1 / 2Mg ²⁺ , l is a positive number greater than 0 and less than 2, and m is 0. A positive number exceeding 0.6 and below, n is 0 or a positive number exceeding 0.)
Examples of the montmorillonite include sodium-type montmorillonite represented by Kunipia F and Kunigel V1 (manufactured by Kunimine Industries), Benclay SL (manufactured by Mizusawa Chemical Industry), montmorillonite K10 (manufactured by Aldrich), and the like.

<Nitrogen-containing compound having a mercapto group>
The nitrogen-containing compound having a mercapto group is not particularly limited as long as it is a compound having basic nitrogen and mercapto group in the same molecule, and examples thereof include mercaptoalkylpyridines and mercaptoalkylamines. Examples of mercaptoalkylpyridines include 3-mercaptomethylpyridine, 3- (2-mercaptoethyl) pyridine, 4- (2-mercaptoethyl) pyridine (hereinafter sometimes abbreviated as “4PET”), 2- ( 2-mercaptoethyl) mercaptoalkylpyridine having 6 to 8 carbon atoms such as pyridine, and examples of mercaptoalkylamines include 2-mercaptoethylamine, 3-mercaptopropylamine, N, N-dimethyl-3- Examples thereof include mercaptoalkylamines having 2 to 8 carbon atoms in total such as mercaptopropylamine. Of these, 2- (2-mercaptoethyl) pyridine, 4PET, and 2-mercaptoethylamine are preferable, 2- (2-mercaptoethyl) pyridine, and 4PET are more preferable, and 4PET is particularly preferable.

  As the nitrogen-containing compound having a mercapto group, mercaptoalkylpyridines and mercaptoalkylamines may be used alone or in combination. Further, in the present application, a compound that functions in the same manner as a mercapto group when the mercapto group of the nitrogen-containing compound having a mercapto group is protected by a protecting group and these protecting groups are removed in the reaction system. It is contained in the nitrogen compound and can be used similarly.

<Modification by a nitrogen-containing compound having a mercapto group>
The method for modifying a cation-exchangeable clay mineral with a nitrogen-containing compound having a mercapto group is usually performed in a liquid phase using a solvent under a nitrogen atmosphere, and typically, a proton or a metal cation according to the above method. The clay minerals subjected to the ion exchange treatment in (1) are modified using, for example, cation exchangeable clay minerals obtained by vacuum drying at room temperature to about 130 ° C.

  Any solvent may be used as long as it dissolves and / or disperses a nitrogen-containing compound having a mercapto group, and examples thereof include phenols, alcohols, ketones, ethers, and water. Preferable solvents include phenols, but they may be used in combination with other solvents. The denaturation temperature is appropriately selected depending on the type of solvent used, but is usually 50 to 180 ° C, preferably 80 to 130 ° C, and more preferably 100 to 120 ° C. If the denaturation temperature is too high, a pressure vessel may be required for denaturation, which is not economical, and if it is too low, the viscosity of the solvent increases, especially when phenols are used as the solvent, and stirring is not possible. In some cases, the nitrogen-containing compound having a mercapto group is insufficiently dispersed, and phenols used as a solvent may solidify. Although the modification time depends on the temperature, it is usually 0.1 to 24 hours, preferably 1 to 5 hours, and the modification is usually carried out with heating and stirring. After the modification, the solvent is removed, and then washed with an inert solvent such as toluene and acetone, followed by vacuum drying treatment at room temperature to about 130 ° C. for about 0.5 to 15 hours, whereby cation-exchangeable clay minerals are obtained. It is possible to obtain cation-exchangeable clay minerals in which at least a part of the acid sites is modified with a nitrogen-containing compound having a mercapto group.

In the solid acid catalyst of the present invention, at least a part of the acid sites of the cation exchange clay minerals as described above are modified with a nitrogen-containing compound having a mercapto group. , 0.1 to 50 mol%, preferably 0.5 to 10 mol%, based on all acid points.
As described above, the acid point of the solid acid catalyst is a portion that is derived from protons or metal cations and exhibits solid acidity. For example, the measurement is performed after replacing the inside of the measurement system with helium, and then measuring the solid acid catalyst. Is dried at 115-125 ° C. for 2 hours using a vacuum line, for example, benzeneazodiphenylamine at −5.6 <pKa ≦ + 1.5, and benzene at −8.2 <pKa ≦ −5.6. In the case of salacetophenone and pKa ≦ −8.2, the mixture is mixed in a toluene solvent to which a titration indicator such as anthraquinone is added, and a basic solution such as 2,6-dimethylpyridine having a known concentration is added dropwise as a titrant, and the color changes. Can be measured by using an in-situ reaction analysis UV system (PMA-11 manufactured by Hamamatsu Photonics Co., Ltd., GT1000 manufactured by Dia Instruments Co., Ltd.).

As a method of using a solid acid catalyst and a mercapto group-containing compound during the reaction, a method of simply adding a mercapto group-containing compound to a reaction system using a solid acid catalyst and causing it to coexist without any chemical reaction (see the above-mentioned JP-A 10-17509) is known, but the conversion rate of acetone and the selectivity of bisphenol A are improved as compared with the case where no mercapto group-containing compound is used, but it still remains as compared with the production method of the present invention. The yield of bisphenol A is poor. In addition, a method of intercalating and immobilizing between clay layers (physical adsorption method) is also conceivable, but there is a possibility that interlayer materials may flow out during the reaction. The amount of production increases. In the present invention, for example, when producing bisphenol A from acetone and phenol, by using the modified product as a catalyst, it becomes possible to obtain high conversion of acetone and bisphenol A in high yield.
The modified cation exchange clay minerals may be used, and a mercapto group-containing compound or a nitrogen-containing compound having a mercapto group may be supplied together with the starting phenol compound or carbonyl compound.

<Manufacture of bisphenols>
The production of bisphenols can be carried out according to a known method, and examples of the reaction method include a batch method and a continuous method. For example, as described in JP-A-9-194414, the production by the continuous method is produced through a reaction step, a light boiling point separation step, a concentration step, a crystallization step, a granulation step, and the like.

  When the reaction step is a batch type, the amount of the catalyst is not particularly limited, but is usually 0.05 to 2 g, preferably 0.1 to 1.2 g, with respect to 1 g of acetone. Although there is no restriction | limiting in particular in reaction conditions, Usually, reaction pressure is 30-150 degreeC under the pressure of about 500 kPa by normal pressure or absolute pressure, Preferably it is 50-120 degreeC. When the reaction temperature is too low, the activity of the catalyst is not sufficiently exhibited, and the reaction rate tends to become slow as the reaction proceeds. On the other hand, when the reaction temperature is too high, the amount of by-products generated tends to increase. The reaction time varies depending on the amount of catalyst and reaction temperature, but is usually about 0.1 to 20 hours.

If the reaction step is a reaction in a fixed bed in a continuous manner, the supply of the raw material mixture is a solid acid catalyst based phenolic compounds wet, usually LHSV0.05Hr ^-1 or more, preferably 0.2 hr ^-1 or more. The reaction is usually performed at 20 hr ⁻¹ or less, preferably 10 hr ⁻¹ or less. Although there is no restriction | limiting in particular in reaction conditions, Usually, reaction pressure is 40-150 degreeC under the pressure of about 500 kPa by normal pressure or absolute pressure, Preferably it is 60-130 degreeC. When the reaction temperature is too low, the activity of the catalyst tends to be hardly exhibited. On the other hand, when the reaction temperature is too high, the amount of by-products generated tends to increase.

  From the viewpoint of reaction efficiency, a continuous system with a fixed bed is preferable.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded. In addition, the acetone conversion rate (%), bisphenol A yield (%), and bisphenol A selectivity (%) in the following examples and comparative examples were calculated from the measured values by gas chromatography according to the following formulas.

Acetone conversion rate (%) = [(moles of charged acetone−moles of unreacted acetone) / (moles of charged acetone)] × 100
Bisphenol A yield (%) = (number of moles of bisphenol A produced / number of moles of charged acetone) × 100
Bisphenol A selectivity (%) = (bisphenol A yield (%) / acetone conversion (%)) × 100

The trisphenol data shown in Table 1 is weight% (wt%) in the product solution.
The analysis of acetone and the obtained bisphenol A (2,4-form of bisphenol A and bisphenol A) and trisphenol was conducted under the following conditions.

<Analysis method>
Gas chromatography: “GC-2010” manufactured by Shimadzu Corporation
Column: manufactured by Restek “Rtx-5 (Crossband 5% diphenyl-95% dimethylpolysiloxane) 30 m × 0.32 mm × 0.5 μm”
Detector: FID
Carrier gas: He

<Method for measuring acid point of cation exchange clay minerals>
After replacing the inside of the measurement system with helium, the cation exchangeable clay minerals which are solid acid catalysts were dried at 115 to 125 ° C. for 2 hours using a vacuum line. The cation exchange clay mineral after drying is mixed in a toluene solvent to which a titration indicator is added, a basic solution such as 2,6-dimethylpyridine having a known concentration is added dropwise as a titrant, and the color change is The in-situ reaction analysis UV system (PMA-11 manufactured by Hamamatsu Photonics, GT1000 manufactured by Dia Instruments) was used for measurement.

In addition, as the titration indicator, the following indicators were used according to the pKa of the solid acid catalyst.
−5.6 <pKa ≦ + 1.5: Benzeneazodiphenylamine −8.2 <pKa ≦ −5.6: Benzalacetophenone pKa ≦ −8.2: Anthraquinone The modification rate described below is a cation exchange clay. This is the ratio of the acid point of the mineral to the acid point of pKa ≦ −5.6.

<Production Example 1> Preparation of Titanium Ion Exchanged Montmorillonite (Ti-Mont) 21 g of sodium montmorillonite (Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was added to 700 mL of 1.8 mol / L titanium chloride aqueous solution with stirring, and then the temperature was raised to 50 ° C. Then, the mixture was stirred for 24 hours while maintaining the temperature, and ion exchange was performed. Thereafter, the mixture was allowed to cool to room temperature, and the resulting slurry was subjected to suction filtration and then washed with 1500 mL of ion exchange water to completely remove chloride. It was vacuum-dried at 120 ° C. for 12 hours to obtain grayish white titanium ion-exchanged montmorillonite (hereinafter sometimes abbreviated as “Ti-Mont”) (acid amount: 3.1 mmol / g).

<Production Example 2> Preparation of 4- (2-mercaptoethyl) pyridine-modified titanium ion-exchanged montmorillonite (4PET / Ti-Mont) 40.0 g of phenol and 4- (2-mercaptoethyl) were added to a 100 mL eggplant flask equipped with a condenser. ) 0.0186 g of pyridine hydrochloride and 3.0 g of Ti-Mont prepared in Production Example 1 were added, and the modification reaction was performed by heating and stirring at 110 ° C. for 1 hour. The modification rate (modification ratio of 4- (2-mercaptoethyl) pyridine with respect to the acid point of Ti-Mont) is 1.1 mol%. Thereafter, the mixture was allowed to cool at room temperature, and the phenol was removed by decantation before the phenol solidified. Washing was repeated 5 times by adding 50 mL of acetone and stirring at room temperature for 20 minutes, followed by decantation. The remainder obtained by decantation was dried at 100 ° C. for 12 hours to obtain orange 4- (2-mercaptoethyl) pyridine-modified titanium ion-exchanged montmorillonite (4PET / Ti-Mont).

<Production Example 3> Preparation of 2-mercaptoethylamine-modified titanium ion-exchanged montmorillonite In Production Example 2, instead of 4- (2-mercaptoethyl) pyridine hydrochloride, 0.069 g of 2-mercaptoethylamine hydrochloride (in Production Example 1) 2-mercaptoethylamine-modified titanium ion-exchanged montmorillonite was obtained in the same manner as in Production Example 2 except that the modification was performed using 6.3 mol% of the acid amount of the prepared Ti-Mont.

<Production Example 4> Preparation of aluminum ion-exchanged montmorillonite (Al-Mont) The same as Production Example 1 except that 1400 ml of an aqueous aluminum nitrate solution having a concentration of 0.15 mol / l was used in place of the titanium chloride aqueous solution in Production Example 1. To obtain aluminum ion-exchanged montmorillonite (acid amount 2.4 mmol / g). Hereinafter, the aluminum ion exchange montmorillonite may be abbreviated as “Al-Mont”.

<Production Example 5> Preparation of 4- (2-mercaptoethyl) pyridine-modified aluminum ion-exchanged montmorillonite (4PET / Al-Mont) In Production Example 2, instead of Ti-Mont in Production Example 1, Al- in Production Example 4 Other than using Mont, modification was performed using 0.0186 g of 4- (2-mercaptoethyl) pyridine hydrochloride (corresponding to 1.5 mol% with respect to the acid amount of Al-Mont in Production Example 4). In the same manner as in Production Example 2, 4- (2-mercaptoethyl) pyridine-modified aluminum ion-exchanged montmorillonite was obtained.

<Production Example 6> Preparation of acid-treated montmorillonite (H-Mont) In Production Example 1, 210 g of 2N hydrochloric acid was used instead of an aqueous solution of titanium chloride, and the temperature was raised to 90 ° C instead of 50 ° C. In the same manner as in Production Example 1, acid-treated montmorillonite (acid amount 3.5 mmol / g) was obtained. Hereinafter, the acid-treated montmorillonite may be abbreviated as “H-Mont”.

<Production Example 7> Preparation of 4- (2-mercaptoethyl) pyridine-modified acid-treated montmorillonite (4PET / H-Mont) In Production Example 2, instead of Ti-Mont prepared in Production Example 1, prepared in Production Example 6 The modified H-Mont was used to modify 0.0186 g (corresponding to 1.0 mol% with respect to H-Mont of Production Example 6) of 4- (2-mercaptoethyl) pyridine hydrochloride. In the same manner as in Production Example 2, 4- (2-mercaptoethyl) pyridine-modified acid-treated montmorillonite was obtained.

<Example 1>
A reactor equipped with a nitrogen gas introduction tube, a reflux condenser, and a stirrer was charged with 9.4 g of phenol and 0.50 g of 4PET / Ti-Mont obtained in Production Example 2, and nitrogen was introduced. The reaction was carried out while stirring at 70 ° C. and adding 0.58 g of acetone to reflux. At 60 minutes after the start of the reaction, the reaction solution was collected and analyzed by gas chromatography. The analysis results are shown in Table 1.

<Example 2>
In Example 1, the reaction was performed in the same manner as in Example 1 except that the reaction temperature was 80 ° C. The results are shown in Table 1.
<Example 3>
In Example 1, instead of 4PET / Ti-Mont in Production Example 2, the reaction was performed in the same manner as in Example 1 except that 2-mercaptoethylamine-modified titanium ion-exchanged montmorillonite of Production Example 3 was used. The results are shown in Table 1.

<Example 4>
In Example 1, instead of 4PET / Ti-Mont in Production Example 2, 4PET / Al-Mont in Production Example 5 was used and the reaction temperature was changed to 80 ° C., and the reaction was performed in the same manner as in Example 1. It was. The results are shown in Table 1.
<Example 5>
In Example 1, instead of 4PET / Ti-Mont of Production Example 2, 4PET / H-Mont of Production Example 7 was used and the reaction temperature was changed to 80 ° C. The reaction was performed in the same manner as in Example 1. It was. The results are shown in Table 1.

<Comparative Example 1>
In Example 1, the reaction was performed in the same manner as in Example 1 except that the unmodified Ti-Mont obtained in Production Example 1 was used instead of 4PET / Ti-Mont in Production Example 2. The results are shown in Table 1.
<Comparative example 2>
In Example 1, instead of 4PET / Ti-Mont in Production Example 2, the unmodified Ti-Mont obtained in Production Example 1 was used, and 4- (2-mercaptoethyl) pyridine hydrochloride was further added in 3. The reaction was conducted in the same manner as in Example 1 except that 1 mg was added. The results are shown in Table 1.

<Comparative Example 3>
In Example 1, instead of 4PET / Ti-Mont in Production Example 2, the unmodified Ti-Mont obtained in Production Example 1 was used, and 7.5 mg of 2-mercaptoethylamine hydrochloride was added. The reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.
<Comparative example 4>
In Example 1, instead of 4PET / Ti-Mont obtained in Production Example 2, 20 g of sulfonic acid type cation exchange resin (Diaion SK104H, manufactured by Mitsubishi Chemical Corporation) was 4- (2-mercaptoethyl). The same as in Example 1 except that 0.5 g of 4- (2-mercaptoethyl) pyridine-modified sulfonic acid type cation exchange resin obtained by modification with 0.73 g of pyridine hydrochloride (modification rate: 15%) was used. The reaction was carried out. The results are shown in Table 1.

  From Table 1, by using a catalyst in which at least a part of the acid sites of the cation-exchangeable clay mineral is modified with a nitrogen-containing compound having a mercapto group, the conversion rate of the raw material is high, and bisphenol A is It can be seen that it can be produced with high selectivity and high yield.

Claims (9)

  A method for producing a bisphenol by reacting a carbonyl compound and a phenol compound in the presence of a solid acid catalyst, wherein the solid acid catalyst is modified with a nitrogen-containing compound having at least a part of acid sites having a mercapto group. A method for producing bisphenols, which is a cation exchange clay mineral.   The method for producing bisphenols according to claim 1, wherein the cation exchange clay minerals are layered and have protons or metal cations between the layers.   The method for producing bisphenols according to claim 1 or 2, wherein the cation exchange clay minerals are smectite group clay minerals ion-exchanged with protons or metal cations.   The method for producing bisphenols according to claim 2 or 3, wherein the metal cation is selected from the group consisting of titanium, aluminum, niobium, tin, iron and zirconium. The method for producing bisphenols according to claim 3 or 4, wherein the smectite clay mineral is represented by the following general formula (1).
X _m (Y ²⁺ , Y ³⁺ ) ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (1)
(Wherein, X is a cation between layers selected from the group consisting of K ⁺ , Na ⁺ , 1 / 2Ca ²⁺ and 1 / 2Mg ²⁺ , Y ²⁺ is Mg ²⁺ , Fe ²⁺ , Mn ²⁺ , An octahedral cation selected from the group consisting of Ni ²⁺ and Zn ²⁺ , Y ³⁺ is an octahedral cation selected from the group consisting of Al ³⁺ , Fe ³⁺ and Cr ³⁺ , Z is Si and (A tetrahedral cation selected from Al, m is a positive number greater than 0 and less than or equal to 0.6, and n is a positive number greater than or equal to 0.)   The method for producing bisphenols according to any one of claims 3 to 5, wherein the smectite clay mineral is montmorillonite.   The method for producing bisphenols according to any one of claims 1 to 6, wherein the nitrogen-containing compound having a mercapto group is mercaptoalkylpyridine and / or mercaptoalkylamine.   The method for producing a bisphenol according to any one of claims 1 to 7, wherein the nitrogen-containing compound having a mercapto group is 4- (2-mercaptoethyl) pyridine and / or 2-mercaptoethylamine. .   The method for producing a bisphenol according to any one of claims 1 to 8, wherein the phenol is phenol, the ketone is acetone, and the bisphenol is bisphenol A.