JP2020176109A - Method for producing bisphenol compound - Google Patents

Abstract

To provide a method for producing an aldehyde bisphenol compound, which makes it possible to produce a 4,4'-substituted body with significantly high regioselectivity in an efficient and easy manner.SOLUTION: A production method includes producing a bisphenol compound represented by the formula (1) in a state in which at least phenol, heteropoly acid, and a trioxane compound such as paraldehyde coexist. [In formula (1), R1 is a hydrogen atom or a C1-29 monovalent organic group. R2 and R3 each denote a halogen atom or a C1-29 monovalent organic group. a and b each denote an integer of 0-4].SELECTED DRAWING: None

Description

The present invention relates to a method for producing a bisphenol compound. More specifically, the present invention relates to a method for efficiently producing a 4,4'-substituted product in a process for producing a specific bisphenol compound.

Bisphenol compounds in which two phenol structures are crosslinked with a methylene structure include raw materials for thermoplastic resins such as polycarbonate resins, polyester resins, acrylate resins and polyarylate resins, and epoxy resins, polyimide resins, phenol resins, cyanate resins and the like. Addition of heat-curable resin raw materials, hardeners, natural rubbers, antioxidants such as synthetic rubbers and lubricating oils, color-developing agents for heat-sensitive recorders, as well as bactericides, antioxidants, fungicides, flame retardants, etc. Widely used as an agent, it is an important compound in the chemical industry. The bisphenol compound is a group of compounds having two substituents at the methylene cross-linked portion such as bisphenol A (hereinafter, may be referred to as "ketone type bisphenol compound"), and bisphenol F and bisphenol F, depending on the difference in structure derived from the manufacturing raw material. It can be classified into a group of compounds having a substituent of 0 or 1 in a methylene bridge such as bisphenol E (hereinafter, may be referred to as "aldehyde type bisphenol compound"). Among these, aldehyde-type bisphenol compounds are ketone-type, such as antioxidant properties due to having a hydrogen atom in the methylene bridge, improvement in melting point due to improvement of compound symmetry, and improvement in crystal properties when made into a resin. It is a compound that is expected to be applied industrially because it is expected to exhibit various peculiar properties that bisphenol compounds do not have.

The bisphenol compound is generally produced by condensing a carbonyl group such as a ketone or an aldehyde or a derivative thereof with a phenol or a derivative thereof in the presence of an acid catalyst. It is known that the reaction mixture obtained at the time of production usually contains an oligophenol compound in which isomers having different substitution positions of hydroxy groups and phenols are condensed at 3 or more, and the bisphenol compound can be reduced in viscosity and crystallized. Since it is advantageous in various aspects such as production stability when it is made into a resin, it is generally used by extracting only a bisphenol compound in which a hydroxy group is substituted at a specific substitution position from the mixture by a purification treatment or the like. It has been done. Therefore, from the viewpoint of improving production efficiency and reducing costs by reducing the load in the purification process, bisphenol compounds in which a hydroxy group is substituted at a specific substitution position during production, particularly 4,4'-dihydroxy substitution having wide industrial applicability. There is a strong demand for a method capable of efficiently producing a body (hereinafter, may be referred to as a 4,4'-substituted product).

As the aldehydes for producing the aldehyde-type bisphenol, in addition to the aldehyde itself, a compound that decomposes during the reaction to produce an aldehyde can also be used. Examples of such compounds include 1,3,5-trioxane compounds, which are trimers of aldehydes. When the 1,3,5-trioxane compound is used as a raw material instead of an aldehyde, the expected points are the improvement in the handleability of the raw material due to the decrease in volatility and the decrease in toxicity, and the reaction handleability due to the decrease in the total calorific value during the reaction. Improvements can be mentioned. From this point of view, a method for producing an aldehyde-type bisphenol compound using a trioxane compound as a raw material is expected to be industrially superior.

As a method for producing bisphenol by reacting a trioxane compound and phenols, for example, Patent Document 1 describes paraaldehyde (2,4,6-trimethyl-1,3,5-trioxane) and 2,6-di-tert. A method for producing 1,1-bis (3,5-di-tert-butyl-4-hydroxyphenyl) ethane by condensing −butylphenol in the presence of a base such as sodium methoxydo has been described. Further, Patent Document 2 describes a method for producing 1,1-bis (4-methyl-3-hydroxyphenyl) ethane by condensing paraldehyde and o-cresol in the presence of an aqueous phosphoric acid solution. ..

Chinese Patent Application Publication No. 103193602 Japanese Patent No. 4585251

However, as a result of the examination by the present inventor, it has been found that there is a problem in industrial application in any of the methods of Patent Documents 1 and 2. First, with respect to Patent Document 1, when phenols having no substituent at the ortho position of the hydroxyl group such as o-cresol were used, the selectivity of the 4,4'-substituted product was extremely low and very limited. It turned out that it can only be applied to aldehyde-type bisphenol. On the other hand, Patent Document 2 uses a large excess amount of phosphoric acid as a catalyst, and cannot be said to be a method suitable for industrialization in that the load on catalyst removal in the purification step is large, and further solves the above-mentioned problems. Therefore, when the amount of catalyst is reduced, both the reaction rate and the selectivity of 4,4'-substituted products tend to decrease, and it has been found that there is a problem from the viewpoint of industrialization.

Based on the above, the production of aldehyde-type bisphenol compounds using trioxane as a raw material is expected to have industrial applications as described above, but 4,4'-substituted products can be easily produced in a highly selective and small amount. Since there is no method to obtain it in the reaction process using a catalyst, the problem that its application is hindered has been found.

In view of the above problems, the present inventor can efficiently and efficiently produce 4,4'-substituted products with extremely high regioselectivity by combining a trioxane compound and a specific catalyst species in a method for producing a specific aldehyde-type bisphenol compound. We have found that it can be easily obtained, and have completed the present invention.

That is, the gist of the present invention lies in the following [1] to [4].

[1] A method for producing a bisphenol compound represented by the following formula (1).
A bisphenol comprising a step of producing a bisphenol compound represented by the following formula (1) from a state in which at least phenols, a heteropolyacid, and a trioxane compound represented by the following formula (2) coexist. Method for producing compound.

[In the formula (1), R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 29 carbon atoms, and R ² and R ³ independently represent a halogen atom or a monovalent organic group having 1 to 29 carbon atoms. It represents an organic group, and a and b each independently represent an integer of 0 to 4. When a or b is 2 or more, ^two or more R ² or R ³ on the same benzene ring may be bonded to each other to form a ring condensed with the benzene ring. ]

[In equation (2), R ¹ is synonymous with that in equation (1). ]

[2] The method for producing a bisphenol compound according to [1], wherein the total amount of the heteropolyacid is 0.01 mol% or more and 1.5 mol% or less with respect to the total amount of the trioxane compound. ..

[3] The method for producing a bisphenol compound according to [1] or [2], wherein the heteropolyacid is at least one selected from silicotungstic acid, phosphotungstic acid, and salts thereof.

[4] The method for producing a bisphenol compound according to any one of [1] to [3], which comprises further coexisting a mercapto compound.

According to the present invention, among aldehyde-type bisphenol compounds, 4,4'-substituted products having wide industrial applicability can be produced on an industrial scale with high selectivity and efficiency.

The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example of the embodiments of the present invention, and the following description contents do not exceed the gist of the present invention. It is not limited to.
In addition, when the expression "~" is used in this specification, it shall be used as an expression including numbers or physical property values before and after the expression.

[mechanism]
The reason why the bisphenol compound of the present invention can be efficiently produced by the production method of the present invention will be described below.
When producing a bisphenol compound, it is usually obtained as a mixture of isomers having different hydroxyl group substitution positions, but it is generally known that each isomer passes through a specific cation as an intermediate in the production process of each isomer. By using the production method of the present invention, it is possible to specifically and strongly stabilize only the cation that is an intermediate of the target 4,4'-substituted product by the heteropolyacid, and as a result, the bisphenol compound of the present invention can be stabilized. It is considered that was able to be obtained with high selectivity. Furthermore, since the heteropolyacid is an acid having excellent activity, a sufficiently high reaction activity can be obtained with a very small amount of catalyst. This means that the amount of catalyst used can be reduced and the reaction time can be shortened at the same time, which is extremely useful for industrial applications from the viewpoint of reducing the load in the manufacturing process. These effects are more pronounced when the heteropolyacid and the mercapto compound are combined.

[Bisphenol compound]
The bisphenol compound produced by the production method of the present invention (hereinafter referred to as the bisphenol compound of the present invention) is characterized by being represented by the following formula (1).

[In formula (1), R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 29 carbon atoms, and R ² and R ³ independently represent a hydrogen atom, a halogen atom and 1 to 29 carbon atoms. It represents a monovalent organic group, and a and b each independently represent an integer of 0 to 4. When a or b is 2 or more, ^two or more R ² or R ³ on the same benzene ring may be bonded to each other to form a ring condensed with the benzene ring. ]

[R ¹ ]
In the formula (1), R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 29 carbon atoms. Here, examples of the monovalent organic group include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a hydrocarbon group containing an aromatic hydrocarbon group, a group containing a hetero atom, and the like. Of these, R ¹ is a hydrocarbon containing a hydrogen atom, a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, and an aromatic hydrocarbon group in that the bisphenol compound of the present invention can be easily produced more efficiently. It is preferably any of the groups, particularly preferably any of a hydrocarbon group containing a hydrogen atom, a saturated aliphatic hydrocarbon group, and an aromatic hydrocarbon group, and preferably a saturated aliphatic hydrocarbon group. More preferred.

When R ¹ is a saturated aliphatic hydrocarbon group having ¹ to 29 carbon atoms, linear or branched alkyl groups, alkyl groups having a partially cyclic structure, and the like can be mentioned. Among them, the bisphenol compound of the present invention is used. A linear or branched alkyl group is preferable, and a linear alkyl group is more preferable, because it is easy to generate more efficiently.

Specific examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-. Decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecil group, n- Examples thereof include an icosyl group, an n-henicosyl group, an n-docosyl group, an n-tricosyl group, an n-tetracosyl group, and among these, a methyl group, an ethyl group, an n-propyl group, an n-butyl group and an n-hexyl group. Group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-heptadecyl group, n-octadecyl group, etc. A linear alkyl group is preferred. The alkyl group preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms, from the viewpoint of improving the crystallinity of the bisphenol of the present invention and easily reducing the load in the purification step.

Specific examples of the branched alkyl group include methyl ethyl group, methyl butyl group, methyl pentyl group, methyl hexyl group, methyl heptyl group, methyl octyl group, methyl nonyl group, methyl decyl group, methyl undecyl group, methyl dodecyl group, and methyl. Tridecyl group, methyltetradecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl group, methyloctadecyl group, methylnonadecil group, methylicosyl group, methylicosyl group, methylhenicosyl group, methyldocosyl group, methyltricosyl group ;
Dimethylethyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl Group, dimethylpentadecyl group, dimethylhexadecyl group, dimethylheptadecyl group, dimethyloctadecyl group, dimethylnonadecil group, dimethylicosyl group, dimethylicosyl group, dimethylhenicosyl group, dimethyldocosyl group;
Trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, Trimethylheptadecyl group, trimethyloctadecyl group, trimethylnonadecil group, trimethylicosyl group, trimethylicosyl group, trimethylhenicosyl group;

Ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group , Ethylheptadecyl group, ethyl octadecyl group, ethyl nonadecyl group, ethyl icosyl group, ethyl icosyl group, ethyl hen icosyl group, ethyl docosyl group;
Propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, Propylheptadecyl group, propyloctadecyl group, propylnonadesyl group, propylicosyl group, propylicosyl group, propylhenicosyl group;
Butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group, butylhepta Decyl group, butyl octadecyl group, butyl nonadecyl group, butyl icosyl group, butyl henicosyl group;
Can be mentioned.

Among these, branched alkyl groups having 7 to 17 carbon atoms such as ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylundecyl group and ethylpentadecyl group are preferable, and ethylpentyl group and ethylhexyl group are preferable. More preferably, an ethylpentyl group is particularly preferable.
In the example of the branched alkyl group, the branching position is arbitrary.

Specific examples of the alkyl group having a partially cyclic structure include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group;
Cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclodecylmethyl group, cycloundecylmethyl group, cyclododecylmethyl group;
Cyclohexyl ethyl group, cycloheptyl ethyl group, cyclooctyl ethyl group, cyclononyl ethyl group, cyclodecyl ethyl group, cycloundecyl ethyl group, cyclododecyl ethyl group;
Cyclohexylpropyl group, cycloheptylpropyl group, cyclooctylpropyl group, cyclononylpropyl group, cyclodecylpropyl group, cycloundecylpropyl group, cyclododecylpropyl group;

Methylcyclohexyl group, methylcycloheptyl group, methylcyclooctyl group, methylcyclononyl group, methylcyclodecyl group, methylcycloundecyl group, methylcyclododecyl group;
Dimethylcyclohexyl group, dimethylcycloheptyl group, dimethylcyclooctyl group, dimethylcyclononyl group, dimethylcyclodecyl group, dimethylcycloundecyl group, dimethylcyclododecyl group;
Ethylcyclohexyl group, ethylcycloheptyl group, ethylcyclooctyl group, ethylcyclononyl group, ethylcyclodecyl group, ethylcycloundecyl group, ethylcyclododecyl group;
Propylcyclohexyl group, propylcycloheptyl group, propylcyclooctyl group, propylcyclononyl group, propylcyclodecyl group, propylcycloundecyl group, propylcyclododecyl group;
Hexylcyclohexyl group, hexylcycloheptyl group, hexylcyclooctyl group, hexylcyclononyl group, hexylcyclodecyl group, hexylcycloundecyl group, hexylcyclododecyl group;

Methylcyclohexylmethyl group, Methylcycloheptylmethyl group, Methylcyclooctylmethyl group, Methylcyclononylmethyl group, Methylcyclodecylmethyl group, Methylcycloundecylmethyl group, Methylcyclododecylmethyl group;
Methylcyclohexylethyl group, methylcycloheptylethyl group, methylcyclooctylethyl group, methylcyclononylethyl group, methylcyclodecylethyl group, methylcycloundecylethyl group, methylcyclododecylethyl group;
Methylcyclohexylpropyl group, methylcycloheptylpropyl group, methylcyclooctylpropyl group, methylcyclononylpropyl group, methylcyclodecylpropyl group, methylcycloundecylpropyl group, methylcyclododecylpropyl group;
Dimethylcyclohexylmethyl group, dimethylcycloheptylmethyl group, dimethylcyclooctylmethyl group, dimethylcyclononylmethyl group, dimethylcyclodecylmethyl group, dimethylcycloundecylmethyl group, dimethylcyclododecylmethyl group;
Dimethylcyclohexylethyl group, dimethylcycloheptylethyl group, dimethylcyclooctylethyl group, dimethylcyclononylethyl group, dimethylcyclodecylethyl group, dimethylcycloundecylethyl group, dimethylcyclododecylethyl group;
Dimethylcyclohexylpropyl group, dimethylcycloheptylpropyl group, dimethylcyclooctylpropyl group, dimethylcyclononylpropyl group, dimethylcyclodecylpropyl group, dimethylcycloundecylpropyl group, dimethylcyclododecylpropyl group, cyclohexylcyclohexyl group;
And so on.

Of these, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclohexylethyl group, cycloheptylethyl group, cyclo A cyclic alkyl group having 6 to 10 carbon atoms such as an octylethyl group or an alkyl group having a cyclic alkyl group as a substituent is preferable, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group are more preferable, and a cyclohexyl group is particularly preferable.

In the alkyl group having a partially cyclic structure, the substitution position of the substituent is arbitrary.

Specific examples of the case where R ¹ is an unsaturated aliphatic hydrocarbon group having ¹ to 29 carbon atoms include the linear alkyl group, the branched alkyl group, and the alkyl group having a partially cyclic structure in the structure. The structure is not particularly limited as long as it has a structure having one or more carbon-carbon double bonds or triple bonds, but specific examples thereof include an ethenyl group, an ethynyl group, a propenyl group, a propynyl group, a butynyl group, and a butenyl group. Pentynyl group, pentenyl group, hexenyl group, heptenyl group, heptynyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nodecenyl group. , Icosenyl group, henicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group, 4,8,12-trimethyltridecyl group, bicyclo [2,2,1] hepta-5-en-2-yl group and the like.

Of these, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group It is preferably an unsaturated aliphatic hydrocarbon group having 18 or less carbon atoms such as a group and an octadecenyl group, and an ethenyl group is more preferable.

Specific examples of the case where R ¹ is a hydrocarbon group containing an aromatic hydrocarbon group having ¹ to 29 carbon atoms include a phenyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, and a 1-naphthyl group. 3-Methylphenyl group, 2-Methylphenyl group, 2,5-dimethylphenyl group, 9-anthrasenyl group, 4-tert-butylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 2 , 3-Dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 2,4,5-trimethylphenyl group, 3,5-di-tert-butylphenyl group , 4-Ethynylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-phenylethenylphenyl group, 4-phenylphenyl group, 1-azurenyl group, 1-methyl-2- (4-isopropyl) Examples thereof include a phenyl) ethyl group, a 1-methyl-2- (4-tert-butylphenyl) ethyl group, and a 1-n-hexyl-2-phenylethenyl group.

Of these, phenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 1-naphthyl group, 3-methylphenyl group, 2-methylphenyl group, 2,5-dimethylphenyl group, 9-anthrasenyl group , 4-tert-butylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 2,3-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4 -Isopropylphenyl group, 2,4,5-trimethylphenyl group, 3,5-di-tert-butylphenyl group, 4-ethynylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-phenyl An aromatic hydrocarbon group which may have a substituent such as an ethenylphenyl group or a 4-phenylphenyl group is preferable, and a phenyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, or a 3-methylphenyl group is preferable. Group, 2-methylphenyl group, 2,5-dimethylphenyl group, 4-tert-butylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 2,3-dimethylphenyl group, 2, 4,6-trimethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 2,4,5-trimethylphenyl group, 3,5-di-tert-butylphenyl group, 4-ethynylphenyl group, 4- A phenyl group which may have a substituent such as n-butylphenyl group, 4-isobutylphenyl group, 4-phenylethenylphenyl group, 4-phenylphenyl group is more preferable, and a phenyl group and 4-methylphenyl group. , 3,5-dimethylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,5-dimethylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 2,3-dimethyl A phenyl group such as a phenyl group, a 2,4,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group or a phenyl group substituted with a methyl group is more preferable, and a phenyl group is particularly preferable.

Specific examples of the case where R ¹ is a group containing a hetero atom having ¹ to 29 carbon atoms include a group containing a cyano group such as a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group;
Tribromomethyl group, 2-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, Contains halogen atoms such as 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 4-iodophenyl group. Group;

2-Hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,4-dihydroxyphenyl group, 4-hydroxy-3,5-dimethylphenyl group, 2-hydroxynaphthyl group, 3,4-dihydroxyphenyl Groups containing hydroxyl groups such as 4-hydroxy-3,5-di-tert-butylphenyl group, 4- (2-hydroxyethyl) phenyl group;
3- (Methylthio) propyl group, 2- (Methylthio) butyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 4-n-butoxyphenyl group, 4-tert-butoxyphenyl group, 4-hexyloxyphenyl group , 3-Phenyloxyphenyl group, 4-Phenyloxyphenyl group, 2,3-Dimethoxyphenyl group, 2,5-Dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-Dimethoxyphenyl group, 3,5-Dimethoxy Phenyl group, 3,4,5-trimethoxyphenyl group, 4-methylthiophenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 2-methoxynaphthyl group, 4-methoxynaphthyl group, 3,4-methylenedi A group containing an ether or thioether structure such as an oxyphenyl group or a 4-octadecyloxyphenyl group;

A group containing an amino group such as 2-dimethylamino-1-methylethenyl group, 4-dimethylaminophenyl group, 4-diethylaminophenyl group;
A group containing a carboxy group such as a 2-hydroxycarbonylphenyl group, a 4-hydroxycarbonylphenyl group, and a 3-hydroxycarbonyl-4-hydroxyphenyl group;
1- (ethoxycarbonyl) ethyl group, 8-methoxycarbonyloctyl group, 4-acetoxy-3-methoxyphenyl group, 3,4-diacetoxyphenyl group, 3-methoxycarbonylphenyl group, 4-methoxycarbonylphenyl group, 3 A group containing a carbonyl or ester structure such as a −acetylphenyl group, 3-methoxy-4-hydroxyphenyl group, 4-tert-butoxycarbonylphenyl group;

Groups containing amide structures such as 4-acetamidophenyl group, 4-methoxycarbonylaminophenyl group, phthalimidemethyl group;
2- (Diphenylphosphino) A group containing a phosphorus atom such as a phenyl group;
Groups containing nitro groups such as 3-nitroisobutyl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2-hydroxy-4-nitrophenyl group, 4-chloro-2-nitrophenyl group ;
Groups containing silicon atoms such as trimethylsilylethynyl groups;
2-Frill Group, 5-Methyl-2-Frill Group, 3-Pyrazolyl Group, 2-Imidazolyl Group, 4-Imidazolyl Group, 2-Thiophenyl Group, 3-Methyl-2-thiophenyl Group, 2-Thiazolyl Group, 2- Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolyl group, 5-nitro-2-furyl group, 2- (5-methyl-2-furyl) ethyl group, N-ethyl-3-carbazolyl group, A group containing a heterocycle such as (5-thiophenyl) -2-thiophenyl group;
And so on.

Of these, 2-furyl group, 5-methyl-2-furyl group, 3-pyrazolyl group, 2-imidazolyl group, 4-imidazolyl group, 2-thiophenyl group, 3-methyl-2-thiophenyl group, 2-thiazolyl Group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolyl group, 5-nitro-2-furyl group, 2- (5-methyl-2-furyl) ethyl group, N-ethyl-3 Groups containing heterocycles such as −carbazolyl group, (5-thiophenyl) -2-thiophenyl group are preferable, 2-furyl group, 5-methyl-2-furyl group, 2-thiophenyl group, 3-methyl-2-thiophenyl. A group containing a 5-membered ring such as a group, a 2-thiazolyl group, a (5-methyl-2-furyl) ethyl group, an N-ethyl-3-carbazolyl group, and a (5-thiophenyl) -2-thiophenyl group. More preferably, it is a 2-furyl group or a 2-thiophenyl group.

[R ² and R ³ ]
R ² and R ³ in the formula (1) independently represent a halogen atom and a monovalent organic group having 1 to 29 carbon atoms. Wherein the carbon Examples of the halogen atom, fluorine atom, chlorine atom, bromine atom, an iodine atom, and specific examples of the monovalent organic group of 1 to 29 carbon atoms, represented by R ¹ Specific examples mentioned as monovalent organic groups of Nos. 1-29 can be mentioned. Of these, a hydrocarbon group having 1 to 29 carbon atoms is preferable because it is easy to improve the handleability of the bisphenol compound of the present invention, and a hydrocarbon group having 1 to 15 carbon atoms is more preferable. It is more preferably a hydrocarbon group having a number of 1 to 6, and more preferably a substituent having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an allyl group. Groups are most preferred.

It is preferable that R ² and R ³ are the same because the bisphenol compound of the present invention can be easily produced.
The bond positions of R ² and R ³ in the formula (1) are not particularly specified, but the fact that they are bonded to the ortho position with respect to the hydroxyl group makes it easier to generate the bisphenol compound of the present invention more efficiently. preferable.

[A and b]
a and b each independently represent an integer of 0 to 4. When a or b is 2 or more, ^two or more R ² or R ³ on the same benzene ring may be bonded to each other to form a ring condensed with the benzene ring.
Here, when a or b is 2 or more, the 2 or more R ² or R ³ may be the same or different. Further, two or more of ^two or more R ² or R ³ may be bonded to each other to form a ring that condenses with the benzene ring. It is preferable that a and b are the same because the bisphenol compound of the present invention can be easily produced efficiently, and 0 or 1 is preferable because the handleability of the bisphenol compound of the present invention can be easily improved. It is particularly preferably 0.

[Example of bisphenol compound]
Specific examples of the bisphenol compound of the present invention are illustrated below. The bisphenol compound of the present invention is not limited to the following specific examples.

Among them, the bisphenol compound of the present invention is
1,1-bis (4-hydroxyphenyl) methane (Compound (p-1))
1,1-bis (4-hydroxyphenyl) ethane (Compound (p-2))
1,1-bis (4-hydroxyphenyl) propane (Compound (p-3))
1,1-bis (4-hydroxyphenyl) butane (Compound (p-4))
1,1-bis (4-hydroxyphenyl) -2-methylbutane (Compound (p-19))
1,1-bis (4-hydroxyphenyl) -2,2-dimethylpropane (Compound (p-21))
Bis (4-hydroxyphenyl) methylcyclohexane (Compound (p-29))
1,1-bis (3-methyl-4-hydroxyphenyl) butane (Compound (p-96))
Bis (3-methyl-4-hydroxyphenyl) methane (Compound (p-119))
1,1-bis (3-methyl-4-hydroxyphenyl) ethane (Compound (p-120))
Bis (3,5-dimethyl-4-hydroxyphenyl) methane (Compound (p-124))
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane (Compound (p-125))
1,1-bis (5-isopropyl-4-hydroxy-2-methylphenyl) ethane (Compound (p-134))
Is even more preferable
1,1-bis (4-hydroxyphenyl) methane (Compound (p-1))
1,1-bis (4-hydroxyphenyl) ethane (Compound (p-2))
Bis (3-methyl-4-hydroxyphenyl) methane (Compound (p-119))
1,1-bis (3-methyl-4-hydroxyphenyl) ethane (Compound (p-120))
Bis (3,5-dimethyl-4-hydroxyphenyl) methane (Compound (p-124))
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane (Compound (p-125))
1,1-bis (5-isopropyl-4-hydroxy-2-methylphenyl) ethane (Compound (p-134))
Is particularly preferable. Such a bisphenol compound can be particularly preferably used as a raw material for a resin or a color developer.

[Trioxane compound]
The bisphenol compound of the present invention is characterized by being produced using the phenols described below and the trioxane compound represented by the following formula (2) as raw materials.

（式（２）中、Ｒ^１は式（１）におけると同義である。）

(In equation (2), R ¹ is synonymous with that in equation (1).)

In the formula (2), R ¹ has the same meaning as in the formula (1), and specific examples and preferred examples thereof include those listed as specific examples and preferred examples of R ¹ in the formula (1).

Specific examples of the trioxane compound include 1,3,5-trioxane, paraldehyde (2,4,6-trimethyl-1,3,5-trioxane), and 2,4,6-triethyl-1,3. 5-trioxane, 2,4,6-tri-n-propyl-1,3,5-trioxane, 2,4,6-triisopropyl-1,3,5-trioxane, 2,4,6-tri-n -Butyl-1,3,5-trioxane, 2,4,6-triphenyl-1,3,5-trioxane and the like can be mentioned, but the present invention is not limited thereto.

These trioxane compounds may be used alone or in combination of two or more.

[Phenols]
In the method for producing a bisphenol compound of the present invention, the raw material phenols are preferably monophenol compounds represented by the following formulas (3) and (3') (hereinafter, referred to as "monophenol compounds of the present invention". There is.) Is used. The monophenol compounds of the formulas (3) and (3') may be the same or different, but it is preferable that they are the same because the bisphenol compound of the present invention can be easily produced.

[Equation (3), (3 ') ^in, R ^{2, R} 3, a and b have the same meanings as in the formula (1). ]

Specific examples of the monophenol compound represented by the formulas (3) and (3') include phenol, o-cresol, m-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, and 2,6. -Dimethylphenol, 2-ethylphenol, 2-ethyl-6-methylphenol, 2-allylphenol, 2-isopropylphenol, 2-propylphenol, 2,3,6-trimethylphenol, 5,6,7,8- Tetrahydro-1-naphthol, 2-sec-butylphenol, 2-tert-butylphenol, carbachlor, timol, 2-tert-amylphenol, 6-tert-butyl-o-cresol, 2-phenylphenol, 2-cyclohexylphenol, 2-Amil-5-methylphenol, 2,6-diisopropylphenol, 2-benzylphenol, 2-cyclohexyl-5-methylphenol, 2-allylphenol, 1-naphthol, 3-pentadecylphenol, cardanol, guayacol, 2 -Chlorophenol, 2-bromophenol, 3-methoxyphenol, 2-fluorophenol, 3-ethoxyphenol, 2-hydroxymethylphenol, 2-acetylphenol, 3-hydroxycarbonylphenol, 2-nitrophenol, 3-nitrophenol , 2-Aminocarbonylphenol, 2,6-dimethoxyphenol, 3-acetoxyphenol, 2-methoxycarbonylphenol, 3-methoxycarbonylphenol, 5-nitroguayacol, 3-hydroxyacetanilide, 2,2-dimethyl-7-hydroxy Examples thereof include kumaran, benzyl salicylate, phenyl salicylate, butyl salicylate, isoamyl salicylate, salicylic acid (2-hydroxyethyl) and salicylic acid (2-ethylhexyl), among which phenol, o-cresol, 2,3-dimethylphenol, etc. 2,5-dimethylphenol, 2,6-dimethylphenol, 2-ethylphenol, 2-ethyl-6-methylphenol, 2-isopropylphenol, 2-propylphenol, 2-allylphenol, 2,3,6-trimethyl Monophenol compounds having a hydrocarbon group having 3 or less carbon atoms such as phenol and timol are preferable, phenol, o-cresol and timol are more preferable, and o-cresol or timol is particularly preferable.
These monophenol compounds may be used alone or in combination of two or more.

[Ratio of trioxane compounds and phenols used]
The ratio of the trioxane compound to the monophenol compound which is a phenol during the production of the bisphenol compound of the present invention is not particularly specified as long as the bisphenol compound of the present invention is efficiently produced, but the monophenol compound with respect to 1 mol of the trioxane compound. The amount of the compound used is usually 3 mol times or more, preferably 6 mol times or more, and particularly preferably 9 mol times or more. When the amount of the phenol compound is at least the above lower limit value, the bisphenol compound of the present invention tends to be efficiently produced, which is preferable. On the other hand, the amount of the monophenol compound used with respect to 1 mol of the trioxane compound is usually 60 mol times or less, preferably 45 mol times or less, and particularly preferably 30 mol times or less. When the amount of the monophenol compound used is not more than the above upper limit value, the load in the step of separating the unreacted monophenol compound tends to be reduced in the production of the bisphenol compound of the present invention, which is preferable.

When producing the bisphenol compound of the present invention, the trioxane compound and the phenol compound may be produced in a state where all the amounts are mixed, or either one or both may be continuously or intermittently added. .. In particular, it is preferable to produce the trioxane compound while continuously or intermittently adding it, because the bisphenol compound of the present invention can be produced more efficiently and easily.

[Heteropoly acid]
The production method of the present invention is characterized in that the bisphenol compound of the present invention is produced in the presence of a heteropolyacid as an acid catalyst.

Specific examples of heteropolyacids include phosphotungstic acid, phosphomolybdic acid, phosphoribdate tungstic acid, phosphotungstic acid, phosphoribdate tungstic acid, phosphotungstic acid, phosphotungstic acid, silicotungstic acid, Examples thereof include heteromolybdic acid, molybdate tungstic acid, molybdate tongue tungstic acid, germanium tungstic acid, arsenic molybdic acid, and arsenic tungstic acid. Of these, it is preferable to include tungsten as a constituent atom in that the effect of producing the bisphenol compound of the present invention is more easily exhibited in the manufacturing process, and phosphotungstic acid or silicate-tungstic acid is more preferable, and silicate-tungstic acid is more preferable. Is particularly preferable.

Heteropolyacids may be mixed with other bases and used in the form of salts. Specific examples thereof include alkali metal salts such as lithium salts, sodium salts, and cesium salts;
Alkaline earth metal salts such as magnesium salt, calcium salt, barium salt;
Transition metal salts such as palladium salts;
Salts of Group 15 atoms such as ammonium salts, tetramethylammonium salts, tetraethylammonium salts, tetraphenylammonium salts;
And so on. These salts are variously selected depending on the ease of dissolution in the reaction solution, the effect of efficiently producing the bisphenol compound of the present invention, the ease of separation in the purification step, and the like.

These heteropolyacids and salts thereof may be used alone or in combination of two or more.

The amount of the heteropolyacid catalyst used in producing the bisphenol compound of the present invention is not particularly specified as long as the bisphenol compound of the present invention can be efficiently produced, but the total amount of the heteropolyacid catalyst with respect to the trioxane compound used in the present invention is It is usually 0.001 mol% or more, preferably 0.005 mol% or more, more preferably 0.01 mol% or more, and particularly preferably 0.05 mol% or more. When this amount is at least the above lower limit value, the bisphenol compound of the present invention tends to be efficiently produced, which is preferable. The total amount of the heteropolyacid catalyst with respect to the trioxane compound is usually 10 mol% or less, preferably 3 mol% or less, more preferably 1.5 mol% or less, and particularly preferably 0.5 mol% or less. Is. When this amount is not more than the above upper limit value, the load of separating the acid catalyst in the purification step tends to be reduced in the production of the bisphenol compound of the present invention, which is preferable.

[Other acid catalysts]
In the production method of the present invention, another acid may be used in combination as a diacid catalyst for the purpose of more efficiently producing the bisphenol compound of the present invention. Specific examples thereof include inorganic acid catalysts such as phosphoric acid, oxalic acid, hydrochloric acid, and sulfuric acid; acetic acid, trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid, hydroxybenzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, and the like. Organic acid catalysts; examples include heterogeneous acid catalysts such as solid acids and cation exchange resins.
The type and amount of these diacid catalysts are variously selected depending on the ease of dissolution in the reaction solution, the effect of efficiently producing the bisphenol compound of the present invention, the ease of separation in the purification step, and the like.
These diacid catalysts may be used alone or in combination of two or more.

[Mercapt compound]
In the method for producing a bisphenol compound of the present invention, it is preferable to further produce the bisphenol compound of the present invention in a state where the mercapto compound coexists as a co-catalyst.

Specific examples of the mercapto compound include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, 2-propanethiol, n-butyl mercaptan, sec-butyl mercaptan, t-butyl mercaptan, n-pentyl mercaptan, 3-methyl-2-. Butan thiol, isoamyl mercaptan, n-hexyl mercaptan, cyclohexanethiol, n-heptyl mercaptan, n-octyl mercaptan, 2-ethyl-1-hexanethiol, n-nonyl mercaptan, n-decyl mercaptan, n-undecyl mercaptan, n -Dodecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecanethiol, n-hexadecyl mercaptan, n-octadecyl mercaptan, n-docosyl mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3- Propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,10-decandithiol, 3,6-dioxa-1,8-octanedithiol, methyl thioglycolate, thio Ethyl glycolate, butyl thioglycolate, octyl thioglycolate, 2-ethylhexyl thioglycolate, methyl 2-mercaptopropionate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octadecyl 3-mercaptopropionate, thio Ethyl lactate, pentaerythritol tetrakis (mercaptoacetic acid), 1,4-butanediolbis (thioglycolic acid), 2-ethylhexyl (thioglycolic acid), mercaptoacetic acid, 3-mercaptopropionic acid, sodium 3-mercaptopropionate, thioapple Acid, 3-mercaptopropane sulfonate sodium, 2-mercaptoethanol, 1-thioglycerol, 2-aminoethanethiol, L-cysteine, N-acetyl-L-cysteine, thioacetic acid, thiobutyric acid, thiobenzoic acid, benzenethiol , Furfuryl mercaptan, 2-mercaptothiazolin, 4-6-dimethyl-2-mercaptopyrimidine, 2-thiobarbituric acid, thiocianuric acid and the like.

In particular, in the present invention, since the synergistic effect of the combined use with the heteropolyacid of the present invention is excellent, it is preferable to use the mercapto compound represented by the following formula (4), and the combined use of this mercapto compound is aimed at 4, The selectivity of the 4'-substituted product can be further increased.
_{^{R 4 - (SH) n (}} 4)
[In the formula (4), R ⁴ represents an n-valent aliphatic hydrocarbon group having 1 to 30 carbon atoms, and n represents an integer of 1 to 6. Incidentally, the carbon of R ⁴ - carbon bond may be interrupted 1-6 times with ester structure. ]

Specific examples of the mercapto compound represented by the formula (4) include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, 2-propanethiol, n-butyl mercaptan, sec-butyl mercaptan, t-butyl mercaptan, and n-pentyl. Mercaptan, 3-methyl-2-butane thiol, isoamyl mercaptan, n-hexyl mercaptan, cyclohexanethiol, n-heptyl mercaptan, n-octyl mercaptan, 2-ethyl-1-hexanethiol, n-nonyl mercaptan, n-decyl mercaptan From hydrocarbon groups such as n-undecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecanethiol, n-hexadecyl mercaptan, n-octadecyl mercaptan, n-docosyl mercaptan and one mercapto group. Compound;

Hydrocarbon groups such as 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,10-decandithiol and two or more Compound consisting of mercapto groups;
Methyl thioglycolate, ethyl thioglycolate, butyl thioglycolate, octyl thioglycolate, 2-ethylhexyl thioglycolate, methyl 2-mercaptopropionate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 3- A compound consisting of a hydrocarbon group interrupted by an ester structure such as octadecyl mercaptopropionate and a single mercapto group;

Ethylene glycol bis (3-mercaptopropionate), pentaerythritol tetra (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimethylpropanthris (3-mercaptopropionate) A compound consisting of a hydrocarbon group interrupted by an ester structure such as and two or more mercapto groups;
And so on.

Of these, from the viewpoint removed in the purification process it is easy, it is preferable to use an n-mercapto compound is 1, R ⁴ bisphenol compound of the present invention in that easily secure the effect of producing in the manufacturing process It is more preferable that the alkyl group is an ester structure having 1 to 30 carbon atoms and is not interrupted. Among them, the number of carbon atoms is preferably 6 to 16, more preferably 8 to 14, and the number of carbon atoms is 10 to 12 in terms of low volatility and odor and easy application to the manufacturing process. Is particularly preferable. On the other hand, from the viewpoint that it can be easily removed together with the solvent in the concentration step described later, the number of carbon atoms is preferably 1 to 5, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 2 carbon atoms. preferable.

The amount of the mercapto compound used in producing the bisphenol compound of the present invention is not particularly specified as long as the bisphenol compound of the present invention can be efficiently produced, but the amount of the mercapto compound is usually 0.1 with respect to the above-mentioned heteropolyacid catalyst. It is mol times or more, preferably 1 mol times or more, and particularly preferably 10 mol times or more. Further, it is usually 2000 mol times or less, preferably 1000 mol times or less, and more preferably 400 mol times or less.
The total amount of the mercapto compound is usually 0.001 mol% or more, preferably 0.005 mol% or more, still more preferably 0.1 mol% or more, and particularly preferably 0.1 mol% or more, based on the total amount of the trioxane compound. Is 1 mol% or more. Further, it is usually 150 mol% or less, preferably 100 mol% or less, further preferably 50 mol% or less, and particularly preferably 30 mol% or less.
When the amount of the mercapto compound is at least the above lower limit value, the bisphenol compound of the present invention tends to be produced efficiently and with high selectivity, which is preferable. On the other hand, when the amount of the mercapto compound is not more than the above upper limit value, the load of separating the mercapto compound after use tends to be reduced in the production of the bisphenol compound of the present invention, which is preferable.
The mercapto compound may be used alone or in combination of two or more.

[solvent]
When producing the bisphenol compound of the present invention, a solvent may be used for the reaction. Specific examples of the solvent include linear hydrocarbon solvents having 5 to 18 carbon atoms such as n-pentane, n-hexane, n-heptane, n-octane and petroleum ether; and branches having 5 to 18 carbon atoms such as isooctane. Chain hydrocarbon solvent; cyclic hydrocarbon solvent having 5 to 18 carbon atoms such as cyclohexane, cyclooctane and methylcyclohexane; water; alcohol solvent such as methanol, ethanol, isopropanol and butanol; nitrile solvent such as acetonitrile; dibutyl ether and dimethoxy Ether solvent such as ethane; Ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone; Ester solvent such as ethyl acetate and butyl acetate; Nitrogen-containing solvent such as dimethylformamide and dimethylacetamide; Sulfur-containing solvent such as dimethyl sulfoxide and sulfolane; Methylene chloride, Chlorine-containing solvents such as chloroform and dichloroethane; aromatic hydrocarbon solvents such as benzene, toluene and xylene can be mentioned. It should be noted that it is preferable to use these solvents because the operability of the reaction can be improved, such as suppressing the solidification of the raw material during the reaction and suppressing an unexpected side reaction due to internal heat generation. On the other hand, it is preferable not to use these solvents because the separation between the bisphenol compound of the present invention and the solvent becomes unnecessary and the purification step can be simplified.

The amount of the solvent used in producing the bisphenol compound of the present invention is not particularly specified as long as the bisphenol compound can be efficiently produced, but the amount of the solvent with respect to the trioxane compound is usually 0.1% by mass or more, preferably 0. It is 2 mass times or more, and particularly preferably 0.5 mass times or more. When the amount of the solvent is at least the above lower limit value, the effect of the solvent tends to be exhibited more efficiently during the production of the bisphenol compound, which is preferable. The amount of the solvent with respect to the trioxane compound is usually 30 times by mass or less, preferably 20 times by mass or less, and particularly preferably 10 times by mass or less. When the amount of the solvent is not more than the above upper limit value, the bisphenol compound tends to be efficiently produced, which is preferable.

[Reaction temperature]
The reaction temperature at the time of producing the bisphenol compound of the present invention is usually 0 ° C. or higher, preferably 15 ° C. or higher, and particularly preferably 30 ° C. or higher. When the reaction temperature is at least the above lower limit value, it tends to be easy to prevent the reaction mixture from solidifying, which is preferable. On the other hand, it is usually 150 ° C. or lower, preferably 120 ° C. or lower, and particularly preferably 90 ° C. or lower. When the reaction temperature is not more than the above upper limit value, the bisphenol compound of the present invention tends to be efficiently produced, which is preferable.

[Reaction pressure]
The reaction pressure at the time of producing the bisphenol compound of the present invention is not particularly specified as long as the conditions can efficiently produce the bisphenol compound, but the normal pressure among them is that the raw material is intermittent when the bisphenol compound is produced. It is preferable because it can be easily added to the compound, and as a result, the risk of causing an unexpected reaction runaway due to the heat of reaction can be suppressed.

[Reaction time]
The reaction time for producing the bisphenol compound of the present invention is not particularly specified as long as the conditions can efficiently produce the bisphenol compound, but it is usually 30 minutes or more, preferably 1 hour or more, preferably 2 hours or more. It is more preferable to have. When the reaction time is at least the above lower limit value, the bisphenol compound tends to be efficiently produced, which is preferable.
On the other hand, the reaction time for producing the bisphenol compound of the present invention is usually 24 hours or less, preferably 20 hours or less, and particularly preferably 16 hours or less. When the reaction time is not more than the above upper limit value, the process load in producing the bisphenol compound tends to be reduced, which is preferable.

[Use]
The bisphenol compound of the present invention is a polyether resin, polyester resin, polyarylate resin, polycarbonate resin, polyurethane resin used for various purposes such as optical materials, recording materials, insulating materials, transparent materials, electronic materials, adhesive materials, and heat-resistant materials. , Acrylic resin and other thermoplastic resins, epoxy resin, unsaturated polyester resin, phenolic resin, polybenzoxazine resin, cyanate resin and other thermosetting resins, curing agents, additives or precursors thereof It can be used as a body or the like. It is also useful as an additive for a color developer such as a heat-sensitive recording material, a fading inhibitor, a bactericidal agent, and an antibacterial and antifungal agent.
Of these, it is preferable to use it as a raw material (monomer) for a thermoplastic resin or a thermosetting resin, and it is more preferable to use it as a raw material for a polycarbonate resin or an epoxy resin, because it can impart good mechanical properties. It is also preferable to use it as a color developer, and it is more preferable to use it in combination with a leuco dye and a discoloration temperature adjusting agent.

Examples of the present invention are shown below, but the present invention is not limited thereto.
In the following, the following reagents were used.
・ Paraaldehyde, 2,6-xylenol, timol, methylisobutylketone: manufactured by Tokyo Kasei Kogyo Co., Ltd. ・ Phenol: manufactured by Nakaraitesk Co., Ltd. ・ o-cresol: manufactured by Genuine Chemical Co., Ltd. Chemical Industry Co., Ltd. H ₄ (SiW ₁₂ O ₄₀ ), 24 hydrate, phosphotungstic acid: Nippon Inorganic Chemical Industry Co., Ltd. H ₃ (PW ₁₂ O ₄₀ ), 30 hydrate, 85% phosphoric acid Aqueous solution, n-octyl mercaptan, n-dodecyl mercaptan, sodium methoxyd: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

In addition, various analysis methods in the following examples and comparative examples are as follows.

<High Performance Liquid Chromatography (HPLC) Analysis>
After dissolving 20 mg of the sample in 100 ml of acetonitrile, a mixed solution of acetonitrile / 0.1% by mass ammonium acetate aqueous solution was used as an eluent for 5 μl of the sample, and measurement and analysis were performed under the following conditions. The reaction formation rate and the isolation yield were determined by the absolute calibration curve method using a calibration curve prepared in advance using the standard, and the selectivity when the raw material trioxane compound was added to the 100% 4,4'-substituted product. Was obtained as mol% when 100%.

(Measurement condition)
Controller: SCL-10AVP manufactured by Shimadzu Corporation
Column: GL Sciences inertsil ODS3V (4.6 x 150 mm, 5 μm)
Column oven: CTO-10AVP manufactured by Shimadzu Corporation, 40 ° C.
Pump: LC-10ADVP manufactured by Shimadzu Corporation, flow rate 1.0 ml / min Elution condition: K1-acetonitrile, K2-0.1 mass% ammonium acetate aqueous solution K1 / K2 = 60/40 (0-5 minutes)
K1 / K2 = 60/40 → 95/5 (linear concentration change, 5-30 minutes)
K1 / K2 = 95/5 (30-80 minutes)
(Ratio is volume ratio)
Detector: SPD-10AVP UV254nm manufactured by Shimadzu Corporation

(Analysis conditions)
Software: LC-solution ver. Made by Shimadzu Corporation. 1.22SP1
Settings: Slope = 5, Slope = 200, Drift = 0, T.I. DBL = 1000, Min. Area = 500

<GC analysis>
After dissolving 20 mg of the sample and 10 mg of n-undecane (manufactured by Kanto Chemical Co., Inc.) as an internal standard in 100 ml of acetonitrile, 0.1 μl of the sample was measured and analyzed under the following conditions. The trioxane (paraldehyde) conversion rate was obtained as mol% with respect to the raw material trioxane compound after quantifying the residual rate of the trioxane compound by a relative calibration curve method using n-undecane as an internal standard.

(Measurement condition)
Equipment: GC-2010 manufactured by Shimadzu Corporation
Column: Agilent DB-1 (non-polar)
Temperature rise conditions: 50-250 ° C, 10 ° C / min temperature rise, 7 min hold at 250 ° C

(Analysis conditions)
Software: GCsolution ver. Made by Shimadzu Corporation. 2.43

<Example 1> Synthesis of 1,1-bis (3-methyl-4-hydroxyphenyl) ethane (p-120) After o-cresol (10.8 g, 100 mmol) was heated to 40 ° C. and melted. Tungstic acid (33.1 mg, 0.0100 mmol) and n-dodecyl mercaptan (0.202 g, 1.00 mmol) were added. Then, paraldehyde (0.880 g, 6.67 mmol) was added dropwise over 4 hours while maintaining the internal temperature at 50 ° C. After the dropping, the mixture was heated and stirred for 2 hours for aging. A part of the obtained reaction solution was taken and subjected to LC and GC analysis. The paraldehyde conversion was 100% and the 4,4'-substituent selectivity was 92%.

<Example 2> Synthesis of 1,1-bis (3-methyl-4-hydroxyphenyl) ethane (p-120) The same operation as in Example 1 was performed except that the n-dodecyl mercaptan in Example 1 was not used. went. The paraldehyde conversion rate was 100% and the 4,4'-substituted product selectivity was 78% 2 hours after the dropping.

<Example 3> Synthesis of 1,1-bis (4-hydroxyphenyl) ethane (p-2) Except for changing the o-cresol in Example 1 to phenol (9.40 g, 100 mmol), the same as in Example 1. The same operation was performed. The paraldehyde conversion rate was 100% and the 4,4'-substituted product selectivity was 77% 2 hours after the dropping.

<Example 4> Synthesis of 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane (p-125) The o-cresol in Example 2 was divided into 2,6-xylenol (6.10 g, 50. The same operation as in Example 2 was performed except that the value was changed to 0 mmol). The paraldehyde conversion rate was 100% and the 4,4'-substituted product selectivity was 99% 2 hours after the dropping.

<Example 5> Synthesis of 1,1-bis (5-isopropyl-4-hydroxy-2-methylphenyl) ethane (compound (p-134)) Timol (204 g, 1.36 mol) and methyl isobutyl ketone (150 ml) The mixture was heated to 40 ° C. to thaw, and then phosphotungstic acid (1.47 g, 0.453 mmol) and n-octyl mercaptan (2.94 g, 22.6 mmol) were added. Then, paraldehyde (20.0 g, 151 mmol) was added dropwise over 1 hour while maintaining the internal temperature at 80 ° C. After the dropping, the mixture was heated and stirred for 2 hours for aging. A part of the obtained reaction solution was taken and subjected to LC and GC analysis. The paraldehyde conversion rate after aging was 99%, and the 4,4'-substituent selectivity was 94%.

<Comparative Example 1> Synthesis of 1,1-bis (3-methyl-4-hydroxyphenyl) ethane (p-120) After o-cresol (10.8 g, 100 mmol) was heated to 40 ° C. and melted. , Sodium methoxide (0.40 g, 7.4 mmol), paraldehyde (2.64 g, 20.0 mmol) and toluene (30.0 g) were added and aged at 110 ° C. for 6 hours. The paraldehyde conversion rate after aging was 100%, and the 4,4'-substituent selectivity was 23%.

<Comparative Example 2> Synthesis of 1,1-bis (3-methyl-4-hydroxyphenyl) ethane (p-120) After o-cresol (10.8 g, 100 mmol) was heated to 40 ° C. and melted. 85% phosphoric acid (2.83 g, 24.6 mmol) and paraldehyde (0.880 g, 6.67 mmol) were added and aged at 50 ° C. for 6 hours. The paraldehyde conversion rate after aging was 100%, and the 4,4'-substituted product selectivity was 78%.

<Comparative Example 3> Synthesis of 1,1-bis (3-methyl-4-hydroxyphenyl) ethane (p-120) After o-cresol (10.8 g, 100 mmol) was heated to 40 ° C. and melted. 85% phosphoric acid (0.540 g, 4.69 mmol) and paraldehyde (0.880 g, 6.67 mmol) were added and aged at 50 ° C. for 6 hours. The paraldehyde conversion rate after aging was 72%, and the 4,4'-substituted product selectivity was 54%.

The results of Examples 1 to 5 and Comparative Examples 1 to 3 are summarized in Table 1 below.
From Examples 1 to 5, according to the present invention, 4,4'-substituted products can be obtained in a short time and with high selectivity, regardless of the raw materials used, even if a very small amount of catalyst is used. it is obvious.
Under basic conditions such as Comparative Example 1, a sufficient 4,4'-substituent selectivity cannot be obtained.
Although a high 4,4'-substituted product selectivity can be obtained under the reaction conditions as in Comparative Example 2, the amount of acid used is 3 mol times or more that of the trioxane compound, and the load on catalyst removal during purification is large.
When the amount of the acid catalyst is reduced to 1 mol times or less as in Comparative Example 3, the reaction rate and the 4,4'-substituent selectivity tend to decrease, which is not preferable.
From the above results, it is clear that the method for producing bisphenol using the heteropolyacid catalyst of the present invention is an industrially excellent method.

Claims (4)

A method for producing a bisphenol compound represented by the following formula (1).
A bisphenol comprising a step of producing a bisphenol compound represented by the following formula (1) from a state in which at least phenols, a heteropolyacid, and a trioxane compound represented by the following formula (2) coexist. Method for producing compound.

[In the formula (1), R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 29 carbon atoms, and R ² and R ³ independently represent a halogen atom or a monovalent organic group having 1 to 29 carbon atoms. It represents an organic group, and a and b each independently represent an integer of 0 to 4. When a or b is 2 or more, ^two or more R ² or R ³ on the same benzene ring may be bonded to each other to form a ring condensed with the benzene ring. ]

[In equation (2), R ¹ is synonymous with that in equation (1). ] The method for producing a bisphenol compound according to claim 1, wherein the total amount of the heteropolyacid is 0.01 mol% or more and 1.5 mol% or less with respect to the total amount of the trioxane compound. The method for producing a bisphenol compound according to claim 1 or 2, wherein the heteropolyacid is at least one selected from silicotungstic acid, phosphotungstic acid, or salts thereof. The method for producing a bisphenol compound according to any one of claims 1 to 3, wherein a mercapto compound is further coexisted.