JP2008214248A - Method for producing bisphenol compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an efficient method for producing a bisphenol compound at high conversion and high selectivity. <P>SOLUTION: The method for producing a bisphenol compound [2,2-bis(4-hydroxy-3-methylphenyl)propane, for example] comprises adding an organic solvent to at least either one of a first mixture containing an acidic catalyst and a second mixture containing a phenol compound (o-cresol, for example) and a ketone compound or an aldehyde compound (acetone, for example), and adding the second mixture to the first mixture to subject them to a condensation reaction. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a bisphenol compound, and more particularly to a method for producing a bisphenol compound by a condensation reaction between a phenol compound and a ketone compound or an aldehyde compound.

  Bisphenol compounds are important compounds as raw materials for polymer materials such as polycarbonates, epoxy resins, and aromatic polyesters. Examples of the bisphenol compound include 4,4-isopropylidene bisphenol compounds represented by 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3-methylphenyl) propane. Are known. As a manufacturing method thereof, for example, Patent Document 1 discloses a method in which o-cresol, which is a phenol compound, and acetone are charged, and hydrogen chloride gas is blown into this to perform dehydration condensation. A large excess of o-cresol, a double mole, is used.

  In the above condensation reaction, the molar ratio between the phenol compound and acetone is theoretically 2. However, when reacted at this ratio, the carbonium ions generated from acetone attack not only the p-position but also the o-position of phenol. As a result, an o, p-positional isomer is by-produced, and a reaction product of an acetone condensate and a phenol compound is by-produced to lower the reaction selectivity, and further, 2- ( Due to the by-product such as trinuclear or tetranuclear further substituted with a hydroxyphenyl) propyl group, there arises a problem that the yield is greatly reduced. Further, according to the knowledge of the inventors of the present application, the following problems arise due to the use of a strongly acidic substance such as concentrated hydrochloric acid as a catalyst. The reaction solution is remarkably colored, and the target 4,4'-isopropylidenebisphenol compound is also colored to deteriorate the hue. Furthermore, the reaction solution is solidified and cannot be agitated. As a result, the reaction cannot be completed, and the catalyst is deactivated by the water produced in the condensation reaction, and the reaction rate is significantly reduced. These problems become more apparent as the ratio decreases. Therefore, it is difficult to produce a bisphenol compound by using a phenol compound at a ratio equal to or less than the stoichiometric amount and applying a conventionally known method as it is.

If a phenol compound is used in a large excess, the problem of reaction selectivity is improved, but prevention of coloring of the target product is still insufficient. In addition, since a large amount of unreacted phenolic compound remains, a recovery step of the raw material compound is required in addition to the purification step of the target product. As a result, the operation becomes complicated and more colored by heating during the operation. It raises a new problem of becoming easier to do. Therefore, the above production method is inefficient as an industrial production method, and is not an economically advantageous method.
In recent years, the demand for bisphenol compounds tends to increase more and more. Therefore, if a bisphenol compound can be efficiently produced with a high reaction rate and selectivity, its technical significance is great.
Japanese Patent Laid-Open No. 62-138443

  This invention is made | formed in view of such a situation, The subject which it is going to solve is providing the manufacturing method of the bisphenol compound with high reaction rate and selectivity and high efficiency.

  As a result of intensive studies on the reaction conditions in the condensation reaction between a phenol compound and a ketone compound or an aldehyde compound in order to solve the above-mentioned problems, the present inventors have determined that, depending on the catalyst composition, the ratio of the reaction substrate, the order of its preparation, etc. The knowledge that reaction rate and reaction selectivity fluctuate greatly was obtained. Furthermore, the present inventors have scrutinized the conditions for the condensation reaction, and as a result, avoiding contact between the acidic catalyst and the reaction substrate before the condensation reaction, dissolving the reaction substrate in the reaction system, and generating the bisphenol compound by the condensation reaction. The present invention has been completed by finding that the above-mentioned problems can be solved by producing the material under the condition that it can be agglomerated and precipitated in the form of granules.

That is, the present invention has the following features.
[1] Of a first mixture containing an acidic catalyst and a second mixture containing a phenol compound represented by the following general formula (I) and a ketone compound or an aldehyde compound represented by the following general formula (II) A method for producing a bisphenol compound represented by the following general formula (III), wherein an organic solvent is added to at least one, and the second mixture is added to the first mixture to cause a condensation reaction.

In the above formula, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, and R ⁵ and R ⁶ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

[2] The production method of the above-mentioned [1], wherein the ratio of the phenol compound to the ketone compound or the aldehyde compound is 2.5 or less in terms of molar ratio (I / II).
[3] The production method according to the above [1] or [2], wherein the bisphenol compound produced by the condensation reaction is aggregated and precipitated in a granular form.
[4] The production method according to any one of [1] to [3], wherein the addition amount of the organic solvent is 0.1 to 25% by weight based on the phenol compound.
[5] The production method according to any one of [1] to [4], wherein the organic solvent is an aromatic hydrocarbon, an aliphatic carboxylic acid, or an alcohol.
[6] The production method according to any one of [1] to [5], wherein the first mixture contains a thiol compound.
[7] The production method of the above-mentioned [6], wherein the thiol compound is 3-mercaptopropionic acid.
[8] The production method according to any one of [1] to [7], wherein the first mixture contains a hypophosphite compound.
[9] The production method of the above-mentioned [8], wherein the hypophosphorous acid compound is hypophosphorous acid or sodium hypophosphite.
[10] The production method according to any one of [1] to [9], wherein the acidic catalyst is an inorganic acid.
[11] The production method of the above-mentioned [10], wherein the inorganic acid is hydrochloric acid.
[12] The production method according to any one of [1] to [11], wherein the phenol compound is an o-substituted phenol compound.
[13] The production method of the above-mentioned [12], wherein the o-substituted phenol compound is o-cresol.

  According to the present invention, since the reactivity and selectivity are high and the production of by-products is suppressed, the bisphenol compound can be efficiently obtained with high purity by a simple purification means such as recrystallization. In addition, by using a phenol compound equal to or less than the stoichiometric amount with respect to the ketone compound or aldehyde compound, recovery of the phenol compound becomes unnecessary, and coloration of the bisphenol compound is suppressed, so It is possible to economically produce good high quality bisphenol compounds. Therefore, the production method of the present invention is technically significant in that it overcomes the problems in the conventional production methods such as reduction in reaction rate and selectivity, coloring, and economy.

  Hereinafter, a method for producing a bisphenol compound (hereinafter, also referred to as “bisphenol compound (III)”) represented by the general formula (III) according to the present invention will be described in detail according to the preferred embodiment.

First, definitions of symbols in each formula used in this specification will be described.
Examples of the alkyl group having 1 to 6 carbon atoms in R ^{1 to} R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples thereof include linear, branched or cyclic alkyl groups such as a group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexane Examples are a propyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group. Among these, a linear or branched alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) is preferable.

As the alkyl group in R ^{5 to} R ⁶ , the above-described alkyl group is preferable, and specifically, a linear or branched alkyl group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms) is preferable. Used for. Moreover, as an aryl group, a C6-C14 (preferably 6-8) aryl group is suitable. Specific examples include a phenyl group, a tolyl group, a xylyl group, a biphenylyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like, and among them, a phenyl group is preferable.

The substituted alkyl group in R ^{1 to} R ⁶ is one or more substituted with a halogen atom (particularly a fluorine atom), a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms (as defined above), an aryl group (as defined above) or the like. For example, a benzyl group, an ethylphenyl group (for example, an aralkyl group having 7 to 10 carbon atoms), a trifluoromethyl group, and a methoxymethyl group are exemplified.

The substituted alkoxy group in R ¹ to R ^4, the alkyl moiety (defined above) Number 6 alkoxy group having a carbon refers to one or more substituted with and alkoxy group such as a trifluoromethyl group.
The substituted aryl group in R ^{5 to} R ⁶ is an aryl group substituted with one or more halogen atoms (as defined above), C 1-6 alkoxy groups (as defined above), trifluoromethyl groups and the like. For example, o-, m- or p-methoxyphenyl group, o-, m- or p-trifluoromethylphenyl group is exemplified.

R ^{1 to} R ⁶ can be arbitrarily combined with the above substituents. For example, any one of (iv) to (vii) is combined with one of the following (i) to (iii): Those are preferred.
(I) All of R ^{1 to} R ⁴ are hydrogen atoms.
(Ii) R ¹ is an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms, and R ^{2 to} R ⁴ are hydrogen atoms.
(Iii) R ¹ is an aryl group having 6 to 8 carbon atoms, and R ^{2 to} R ⁴ are hydrogen atoms.
(Iv) R ⁵ and R ⁶ are alkyl groups having 1 to 6 (preferably 1 to 4) carbon atoms.
(V) R ⁵ is an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms, and R ⁶ is an aryl group having 6 to 8 carbon atoms.
(Vi) R ⁵ is a hydrogen atom, and R ⁶ is an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms.
(Vii) R ⁵ is a hydrogen atom, and R ⁶ is an aryl group having 6 to 8 carbon atoms.

Next, the manufacturing method according to the present invention will be described.
The method for producing the bisphenol compound (III) is characterized in that the second mixture is added to the first mixture to cause a condensation reaction. The first mixture includes an acidic catalyst, the second mixture includes a phenol compound and a ketone compound or an aldehyde compound, and at least one of the first and second mixtures is added with an organic solvent. ing.

Examples of the acidic catalyst include inorganic acids (for example, hydrochloric acid, sulfuric acid, hydrogen bromide, perchloric acid), organic acids (for example, p-toluenesulfonic acid), solid acids (for example, acidic cation having a sulfonic acid group and the like). Ion exchange resin, zeolite, clay). These can be used alone or in combination of two or more, and are preferably used in the form of an aqueous solution. Of these, inorganic acids are preferable, hydrochloric acid is more preferable, and concentrated hydrochloric acid is still more preferable. The acidic catalyst may be in the form of a gas such as hydrogen chloride.
The usage-amount of an acidic catalyst becomes like this. Preferably it is 15-150 weight% with respect to a phenol compound, More preferably, it is 25-110 weight%, More preferably, it is 30-70 weight%. If the amount is less than 15% by weight, stirring tends to be impossible or the reactivity tends to decrease. In addition, when the acidic catalyst is in the form of an aqueous solution such as hydrochloric acid, it is the weight of the acid component in the aqueous solution.

Moreover, the first mixture may contain a thiol compound. Thereby, reaction can be promoted further.
Examples of the thiol compound include mercaptoacetic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, and alkyl mercaptans such as nonyl mercaptan. The above can be used in combination. Of these, 3-mercaptopropionic acid is preferable.
The amount of the thiol compound used is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the phenol compound. If the amount is less than 0.1% by weight, the selectivity tends to decrease. On the other hand, if the amount exceeds 10% by weight, an effect commensurate with the added amount cannot be obtained in selectivity and reactivity, which is not economical.

Furthermore, the first mixture may contain a hypophosphorous acid compound. Thereby, coloring of the target bisphenol compound can be significantly prevented.
Examples of hypophosphorous acid compounds include hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, and calcium hypophosphite. These may be in the form of hydrates and can be used alone or in combination of two or more. Of these, hypophosphorous acid and sodium hypophosphite are preferably used.
The amount of the hypophosphorous acid compound used is preferably 0.1 to 3.0% by weight, more preferably 0.5 to 2% by weight, based on the phenol compound. In addition, when preparing a 1st mixture, a hypophosphorous acid compound can be used in addition to an acidic catalyst with the form of powder or aqueous solution.

  When preparing the first mixture, there is no particular limitation on the mixing order of the blending components, and all the blending components may be charged simultaneously, or the components may be sequentially charged into a container to form a mixture. When hydrochloric acid is used as the acidic catalyst, for example, hydrogen chloride gas may be blown into water or an organic solvent to prepare the first mixture. Of the hypophosphorous acid compound and the thiol compound, When at least one of them is contained, hydrogen chloride gas may be blown into them, or these may be added to hydrochloric acid to prepare the first mixture.

  The phenol compound contained in the second mixture is a compound represented by the above general formula (I), specifically, phenol, o-cresol, m-cresol, o-ethylphenol, o-isopropylphenol. , O-t-butylphenol (above, monosubstituted phenol compound) and the like are preferably used. Of these, phenol and o-substituted phenol compounds are preferable, and o-cresol and ot-butylphenol are more preferable.

  The ketone compound or aldehyde compound is a compound represented by the above general formula (II). Specifically, acetone, methyl ethyl ketone, cyclohexanone, acetophenone, etc. (above, ketone compound); formaldehyde, acetaldehyde, benzaldehyde, etc. (above) And aldehyde compounds). Among these, ketone compounds are preferable, and acetone is more preferable.

  Although a phenol compound and a ketone compound or an aldehyde compound can be combined arbitrarily, the combination of Table 1 is especially suitable.

The compounding ratio (I / II, molar ratio) of the phenol compound and the ketone compound or aldehyde compound can be used in large excess with respect to the ketone compound or aldehyde compound, but from an economic viewpoint. , Preferably 2.5 or less, more preferably 2 or less, still more preferably 1.8 or less. The lower limit of the molar ratio is preferably 0.5 or more and more preferably 1 or more from the economical viewpoint.
In the present invention, even when the ratio of (I) / (II) is equal to or less than the stoichiometric amount, production of by-products is suppressed and production is efficiently performed with high reaction rate and selectivity. It is possible. Therefore, it is economically advantageous as compared with the conventional production method using a phenol compound in a large excess.

  In the present invention, the acidic catalyst and the reaction substrate are each separated into two mixtures to avoid contact between the acidic catalyst and the reaction substrate before the condensation reaction, and these are contacted for the first time during the condensation reaction. Thereby, the side reaction before a condensation reaction can be suppressed effectively. Further, in the condensation reaction, the reaction substrate is dissolved and an organic solvent in an amount that does not completely dissolve the bisphenol compound is used, so that the bisphenol compound produced by the condensation reaction is aggregated and precipitated as a granular bisphenol compound. Thereby, the inside of a reaction system will be in a suspended state, the side reaction after a condensation reaction can be suppressed effectively, and also the raise of the viscosity of a reaction liquid will be suppressed and stirring will be achieved easily. If the phenolic compound is used at or below the stoichiometric amount, in addition to the above effects, a high reaction rate and high selectivity can be achieved more reliably, and a good hue can be realized. Therefore, the above-described method according to the present invention should be a new technical means that is completely different from a conventionally known production method.

  The method for preparing the second mixture is not particularly limited, and the phenol compound and the ketone compound or the aldehyde compound may be simultaneously added or each compound may be put into a container in order and mixed.

As long as at least one of the first and second mixtures contains an organic solvent, both may contain them.
Any organic solvent can be used without particular limitation as long as it does not inhibit the condensation reaction. For example, aliphatic hydrocarbons (eg, hexane, heptane), aromatic hydrocarbons (eg, toluene, xylene, mesitylene), halogenated hydrocarbons (eg, dichloroethane, chloroform, chlorobenzene), aliphatic carboxylic acids (eg, formic acid) , Acetic acid, propionic acid) and alcohol (for example, C1-C4 alcohols such as methanol, ethanol, propanol, isopropanol, etc.), and these can be used alone or in combination of two or more. Of these, aromatic hydrocarbons, aliphatic carboxylic acids, and alcohols are preferable, and toluene, acetic acid, and methanol are particularly preferable.

The organic solvent may be added to at least one of the first and second mixtures before the condensation reaction, or may be added to both.
The amount of the organic solvent used is not particularly limited as long as it is less than the amount capable of dissolving the reaction substrate and capable of completely dissolving the target bisphenol compound. , Preferably 0.1 to 25% by weight, more preferably 0.1 to 15% by weight. Thereby, since it becomes possible to aggregate the bisphenol compound produced | generated by the condensation reaction within a reaction system, and to precipitate with a granular form, the side reaction after a condensation reaction can be suppressed more reliably. If the amount is less than 0.1% by weight, the reaction solution tends to solidify and cannot be stirred. On the other hand, if it exceeds 25% by weight, the condensation reaction may be significantly reduced.

The condensation reaction is preferably carried out under the following conditions.
The reaction temperature is preferably 20 to 70 ° C., more preferably 30 to 60 ° C., and further preferably 35 ° C. to 50 ° C., and the temperature may be raised stepwise depending on the progress of the reaction. Moreover, when adding a 2nd mixture to a 1st mixture, it is preferable to add by dripping, Preferably dripping time is 1 to 5 hours, More preferably, it is 2-3. The reaction time is preferably 3 to 12 hours, more preferably 3 to 8 hours. The progress of the reaction may be checked by high performance liquid chromatography, and when a predetermined reaction rate is reached, the condensation reaction may be stopped by adding water to the reaction solution.

  Isolation and purification of the bisphenol compound (III) after the condensation reaction can be performed by a conventional method. Since the production method of the present invention has a high reaction rate and selectivity and suppresses the formation of by-products, it can be purified by simple means such as recrystallization or column chromatography. Specifically, after the condensation reaction, the organic layer obtained by separating the reaction solution is washed with water or a saline solution, and further neutralized and washed with an aqueous sodium bicarbonate solution as necessary. Next, the washed organic layer is cooled and crystallized. Moreover, since a purification means such as distillation for recovering the phenol compound is unnecessary, a high-quality bisphenol compound (III) having a good hue can be obtained.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.
In addition, the composition and purity of the reaction product in the reaction liquid were measured as area% under the following conditions by high performance liquid chromatography (HPLC, model LC-10A, manufactured by Shimadzu Corporation).
Column: ODS-2 (6 mm × 150 mm) manufactured by Gaskuro Industry Co., Ltd.
Moving layer: CH ₃ CN / 0.05% phosphoric acid water (65/35 (v / v%))
Detection wavelength: 280 nm
Flow rate: 0.8ml / min
Column temperature: 40 ° C
The hue (APHA) was measured according to JISK 1545 after melting a bisphenol compound at 150 ° C./1 h.
Based on the measurement results, the reaction selectivity was obtained from the following formula.
Reaction selectivity = area% of target product / (total area% of target product and by-product) × 100
Reaction rate = area% of target

  Further, the by-product 1 identified in the above measurement is an o, p-position isomer represented by the following formula (IV), and the by-product 2 is an isopropylidenebisphenol represented by the following formula (V). It is a trinuclear body in which the aromatic ring of the compound is further substituted with 2- (hydroxymethylphenyl) propyl group.

(Example 1)
A 200 ml four-necked flask was charged with 47 g of concentrated hydrochloric acid, 2 g of 3-mercaptopropionic acid and 0.5 g of sodium diphosphite monohydrate and stirred to prepare a first mixture. After this was heated and the internal temperature reached 35 ° C., a second mixture of 45 g of o-cresol, 18 g of acetone and 6 g of toluene was added dropwise over 2 hours, and the reaction was further carried out at 40 ° C. for 6 hours. Crystals were precipitated during the reaction, but when the stirring was continued, the precipitate became granular and the reaction could be continued. The reaction was stopped by adding 40 g of water and 60 g of toluene to the reaction solution.

  When the reaction product composition in the reaction solution was measured by HPLC, o-cresol: 6.4 area%, 2,2-bis (4-hydroxy-3-methylphenyl) propane: 88.9 area%, by-product Product 1: 1.8 area%, by-product 2: 2.0 area%, other products total: 0.9 area%. Therefore, the reaction selectivity was 95%, and the reaction rate was 88.9%.

  The reaction solution was heated to 75 ° C., the hydrochloric acid aqueous phase was separated, and the toluene phase was washed with 30 g of water and then washed with neutralized water with sodium bicarbonate water. When the toluene phase was cooled, crystals crystallized out and 45 g of 2,2-bis (4-hydroxy-3-methylphenyl) propane crystals having a melting point of 140 ° C. were obtained. The HPLC purity of the crystals was 99.8 area%, and the hue (APHA) was APHA10. From this result, it was confirmed that the obtained crystal was a white crystal having high purity and good hue.

(Example 2)
The reaction was performed in the same manner as in Example 1 except that 6 g of toluene was added to the first mixture before starting the reaction instead of the second mixture. The reaction solution became granular and the reaction could be continued. The reaction product composition in the reaction solution was as follows: o-cresol: 8.3 area%, 2,2-bis (4-hydroxy-3-methylphenyl) propane: 86.7 area%, and by-product 1: 1. 6 area%, by-product 2: 2.1 area%, other products total: 1.3 area%. Therefore, the reaction selectivity was 94.5%, and the reaction rate was 86.7%.
The same operation as in Example 1 was performed to obtain 44 g of white crystals. The HPLC purity of the obtained crystal was 99.9 area%, and the hue (APHA) was APHA10. From this result, it was confirmed that the obtained crystal was a crystal having high purity and good hue.

(Example 3)
The reaction was performed in the same manner as in Example 1 except that 13.2 g of acetone was used instead of 18 g of acetone, and 4 g of acetic acid was used instead of 6 g of toluene. The reaction proceeded in the granular state. The reaction product composition of the reaction solution was: o-cresol: 2.6 area%, 2,2-bis (4-hydroxy-3-methylphenyl) propane: 91.6 area%, by-product 1: 2.3. Area%, by-product 2: 2.6 area%, and other products total: 0.9 area%. Therefore, the reaction selectivity was 94% and the reaction rate was 91.6%.
Next, the same operation as in Example 1 was performed to obtain 46 g of white crystals. The HPLC purity of the obtained crystal was 99.9 area%, and the hue (APHA) was APHA10. From this result, it was confirmed that the obtained crystal was a crystal having high purity and good hue.

Example 4
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 50 ° C. The reaction could be carried out in the granular state. The reaction product composition in the reaction solution was: o-cresol: 4.3 area%, 2,2-bis (4-hydroxy-3-methylphenyl) propane: 91.6 area%, and by-product 1: 1. 5% by area, by-product 2: 1.7% by area, and other products total: 0.9% by area. Therefore, the reaction selectivity was 95.7%, and the reaction rate was 91.6%.
Next, the same operation as in Example 1 was performed to obtain 46 g of white crystals. The HPLC purity of the obtained crystal was 99.9 area%, and the hue (APHA) was APHA10. From this result, it was confirmed that the obtained crystal was a crystal having high purity and good hue.

(Comparative Example 1)
A 200 ml flask was charged with 47 g of concentrated hydrochloric acid, 45 g of o-cresol and 2 g of 3-mercaptopropionic acid and heated to an internal temperature of 30 ° C., and 13.2 g of acetone was added dropwise over 1 hour. After stirring for 2 hours after the completion of dropping, crystals were precipitated and the reaction solution was solidified and could not be stirred.

(Comparative Example 2)
The reaction was carried out in the same manner as in Comparative Example 1 except that 68 g of o-cresol was used. The reaction solution could be carried out without solidification, but a large amount of raw material remained. Toluene and water were added to the reaction solution and dissolved by heating, and the same operation as in Example 1 was performed to obtain 45 g of 2,2-bis (4-hydroxy-3-methylphenyl) propane crystals. The APHA of the obtained crystal was 150, and coloring was confirmed. Although the yield based on acetone was good, a large amount of unreacted o-cresol remained in the filtrate and had to be recovered. The reaction product composition in the reaction solution was as follows: o-cresol: 23.8 area%, 2,2-bis (4-hydroxy-3-methylphenyl) propane: 69.1 area%, by-product 1: It was 3.2 area%, by-product 2: 3.2 area%, and other products total: 0.7 area%. Therefore, the reaction selectivity was 90.7%, and the reaction rate was 69.1%.

(Comparative Example 3)
45 g of o-cresol and 5 g of concentrated sulfuric acid were added, and 13.2 g of acetone was added dropwise and reacted at 33 ° C. for 8 hours. The reaction product composition in the reaction solution was as follows: o-cresol: 63.5 area%, 2,2-bis (4-hydroxy-3-methylphenyl) propane: 22.2 area%, by-product 1: 3. 8 area%, by-product 2: 4.7 area%, and other products total: 5.8 area%, and a large amount of isomers and by-products were produced. The reaction selectivity was 60.8%, and the reaction rate was 22.2%.

(Comparative Example 4)
The reaction was performed in the same manner as in Comparative Example 1 except that 20 g of toluene was used and the reaction was performed at 33 ° C. The reaction product composition of the reaction solution was: o-cresol: 25.1 area%, 2,2-bis (4-hydroxy-3-methylphenyl) propane: 71.3 area%, and by-product 1: 1.2. Area%, by-product 2: 1.6 area%, and other products total: 0.8 area%. The same operation as in Example 1 was performed to obtain 36 g of 2,2-bis (4-hydroxy-3-methylphenyl) propane crystals. APHA of the obtained crystal was 120, and coloring was confirmed. The reaction selectivity was 95.2% and the reaction rate was 71.3%.

Claims (13)

A first mixture comprising an acidic catalyst;
The following general formula (I):

[Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms. ]
And the following general formula (II):

[Wherein, R ⁵ and R ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. ]
An organic solvent is added to at least one of the second mixture containing a ketone compound or an aldehyde compound represented by:
The second mixture is added to the first mixture to cause a condensation reaction, and the following general formula (III):

[Wherein, R ^{1 to} R ⁶ have the same meanings as described above. ]
The manufacturing method of the bisphenol compound represented by these.   The manufacturing method of Claim 1 whose ratio of the said phenolic compound and the said ketone compound or an aldehyde compound is 2.5 or less by molar ratio (I / II).   The production method according to claim 1 or 2, wherein the bisphenol compound produced by the condensation reaction is aggregated and precipitated in a granular form.   The manufacturing method as described in any one of Claims 1-3 whose addition amount of the said organic solvent is 0.1-25 weight% with respect to a phenol compound.   The manufacturing method as described in any one of Claims 1-4 whose said organic solvent is aromatic hydrocarbon, aliphatic carboxylic acid, or alcohol.   The manufacturing method as described in any one of Claims 1-5 in which a said 1st mixture contains a thiol compound.   The production method according to claim 6, wherein the thiol compound is 3-mercaptopropionic acid.   The manufacturing method according to any one of claims 1 to 7, wherein the first mixture contains a hypophosphorous acid compound.   The production method according to claim 8, wherein the hypophosphorous acid compound is hypophosphorous acid or sodium hypophosphite.   The manufacturing method as described in any one of Claims 1-9 whose said acidic catalyst is an inorganic acid.   The manufacturing method of Claim 10 whose said inorganic acid is hydrochloric acid.   The production method according to claim 1, wherein the phenol compound is an o-substituted phenol compound.   The production method according to claim 12, wherein the o-substituted phenol compound is o-cresol.