JP6834756B2 - Method for producing bisphenol compound - Google Patents

Description

The present invention relates to a method for producing a bisphenol compound. More specifically, the present invention relates to a method for producing a bisphenol compound having excellent purification efficiency.

The bisphenol compound is a useful compound widely used as a raw material for a thermoplastic resin such as a polycarbonate resin and a thermosetting resin such as an epoxy resin. In particular, a bisphenol compound having a flexible long-chain alkyl group is expected to have a low melting point and excellent fluidity, and is expected to exhibit elasticity derived from a flexible alkyl group when used as a resin, which is useful. It is a particularly important compound because it is expected to give physical properties. Resins using such bisphenol compounds as raw materials can be applied to various fields such as automobiles, electric / electronics, housing / building materials, and in recent years, devices required in the field of electrical / electronic equipment parts. It is highly expected because it can provide a resin having excellent flexibility, heat resistance, and water absorption characteristics in response to the demand for miniaturization and high performance.

By the way, the production of such a bisphenol compound is usually characterized by undergoing a crystallization step of dissolving a mixture containing the bisphenol compound in a solvent, precipitating the bisphenol compound, and separating by-products. For example, as a method for producing a bisphenol compound having a long-chain alkyl group, Patent Document 1 describes 1,1-bis (1,1-bis), which is a bisphenol compound having a long-chain alkyl group, by crystallization from methylene chloride, which is a chlorine-containing solvent. Methods for producing 4-hydroxyphenyl) dodecane and 1,1-bis (4-hydroxyphenyl) octadecane are disclosed. Further, Patent Document 2 discloses a method for producing 1,1-bis (4-hydroxyphenyl) hexane, which is a bisphenol compound having a long-chain alkyl group, by crystallization from toluene, which is an aromatic hydrocarbon solvent. ing.

JP-A-59-131623 Publication of Chinese Patent Application No. 15577797

However, as a result of diligent studies by the present inventor, by-products tend to remain in the methods of Patent Documents 1 and 2, and the purification effect of the bisphenol compound is not necessarily high, and a plurality of times are required to obtain a high-purity bisphenol compound. A tendency was found to require purification of. Further, it has been clarified that in the methods of Patent Documents 1 and 2, there is a large loss due to dissolution of the bisphenol compound in the solvent in the process of purifying the bisphenol compound, and the isolation yield tends to decrease. From this, it was found that the conventional method cannot purify the bisphenol compound easily and in a high yield.

In view of the above problems, the present invention is a method for producing a bisphenol compound having excellent purification efficiency, that is, a bisphenol compound capable of easily obtaining a high-purity bisphenol compound in a crystalline form having excellent handleability in a high yield. It is an object of the present invention to provide the manufacturing method of.

As a result of diligent studies, the present inventor has found that a high-purity bisphenol compound can be easily produced by undergoing a step of precipitating a specific bisphenol compound from a solvent containing a specific solvent, and completes the present invention. It came to.
That is, the gist of the present invention lies in the following [1] to [6].

[1] A method for producing a bisphenol compound, which comprises a step of precipitating a bisphenol compound represented by the following formula (1) from a solution of a solvent containing at least one fatty alcohol solvent.

[In formula (1), R ¹ represents an alkyl group having 7 to 19 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 19 carbon atoms, and R ^{3 to} R ⁶ are independent of each other. Represents a hydrogen atom or a methyl group. ]

[2] The method for producing a bisphenol compound according to [1], wherein the aliphatic alcohol solvent is a branched alcohol solvent having 3 to 10 carbon atoms.

[3] The solvent according to [1] or [2], wherein the solvent containing at least one type of the aliphatic alcohol solvent is a solvent containing at least one type each of the aliphatic alcohol solvent and the hydrocarbon solvent. Method for producing bisphenol compound.

[4] The method for producing a bisphenol compound according to any one of [1] to [3], ^{wherein R 2} in the formula (1) is a hydrogen atom.

[5] The method for producing a bisphenol compound according to [4], wherein ^{R 3 to} R ⁶ in the formula (1) are hydrogen atoms.

[6] Having at least one X-ray diffraction peak within the range of diffraction angles 2θ = 4.25 ± 0.15 ° and 2θ = 8.45 ± 0.20 ° in the powder X-ray diffraction method using CuKα rays. A crystal of 1,1-bis (4-hydroxyphenyl) dodecane, which is characterized by.

According to the present invention, there is provided a method for producing a bisphenol compound having excellent purification efficiency. That is, according to the present invention, a high-purity bisphenol compound can be easily obtained in a high yield in a crystalline form having excellent handleability.

It is an XRD crystal diffraction pattern of the compound (P-1) obtained in Example 1. It is an XRD crystal diffraction pattern of the compound (P-1) obtained in Example 2. It is an XRD crystal diffraction pattern of the compound (P-1) obtained in Example 3. It is an XRD crystal diffraction pattern of the compound (P-1) obtained in Example 4. It is an XRD crystal diffraction pattern of the compound (P-1) obtained in Comparative Example 1. It is an XRD crystal diffraction pattern of the compound (P-1) obtained in Comparative Example 2.

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 numerical values or physical property values before and after the expression.

[mechanism]
The method for producing a bisphenol compound of the present invention includes a step of precipitating a specific bisphenol compound described below from a solution of a solvent containing at least one aliphatic alcohol solvent.
As described above, the mechanism by which the method for producing a bisphenol compound of the present invention for precipitating a target bisphenol compound from a solution of a solvent containing at least one fatty alcohol solvent is considered to be excellent in purification efficiency of the bisphenol compound is as follows. ..

The bisphenol compound represented by the formula (1) shown below has a polar phenol structure and a non-polar long-chain alkyl moiety. Therefore, the phenol structure and the aliphatic alcohol solvent easily interact with each other, and the interacted portion and the non-polar long-chain alkyl moiety repel each other and aggregate with each other to precipitate as a powder, thereby precipitating in another solvent. It is considered that it is easy to form a peculiar crystal body different from the case where it is allowed to be formed. Therefore, it is considered that the purification efficiency is improved because the solubility of the bisphenol compound alone in the aliphatic alcohol solvent can be specifically reduced with respect to other by-products.

[Phenol compound]
<Structure>
The bisphenol compound produced by the method for producing a bisphenol compound of the present invention (hereinafter referred to as the phenol compound of the present invention) is characterized by being represented by the following formula (1).

[In formula (1), R ¹ represents an alkyl group having 7 to 19 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 19 carbon atoms, and R ^{3 to} R ⁶ are independent of each other. Represents a hydrogen atom or a methyl group. ]

In the above formula, R ¹ represents an alkyl group having 7 to 19 carbon atoms. When ^{the phenol compound of the present invention is used as a resin raw material when the carbon number of R 1} is equal to or higher than the above lower limit value, the obtained resin tends to exhibit excellent properties such as flexibility and low water absorption. Preferably, when the phenol compound of the present invention is used as a resin raw material, it is preferable that the value is not more than the above upper limit value, because the obtained resin tends to exhibit excellent properties such as mechanical strength and heat resistance. Further, when ^{the carbon number of R 1} is within the range of the lower limit value and the upper limit value, the phenol compound of the present invention easily develops a low melting point, and can be suitably used as a specific color developer. become.

Examples of the alkyl group having 7 to 19 carbon atoms of R ¹ include a linear or branched alkyl group and an alkyl group having a partially cyclic structure. Among them, the raw material is easily available and the present invention is used. Linear or branched alkyl in that the phenol compound is easily available and that when the phenol compound of the present invention is used as a resin raw material, the obtained resin is more likely to exhibit excellent properties such as flexibility. It is preferably a group, more preferably a linear alkyl group.

Specific examples of the linear alkyl group of R ¹ include n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, and the like. Examples thereof include n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecil group, and n-heptyl group, n-octyl group and n-nonyl group. , N-decyl group, n-undecyl group, n-dodecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group and other linear alkyl groups having 7 to 18 carbon atoms are preferable, and n-octyl groups are preferable. , N-nonyl group, n-decyl group, n-undecyl group, linear alkyl group having 8 to 11 carbon atoms is more preferable, and n-undecyl group is particularly preferable.

Specific examples of the branched alkyl group of R ¹ include a methylhexyl group, a methylheptyl group, a methyloctyl group, a methylnonyl group, a methyldecyl group, a methylundecyl group, a methyldodecyl group, a methyltridecyl group, and a methyltetradecyl group. , Methyl pentadecyl group, methyl hexadecyl group, methyl heptadecyl group, methyl octadecyl group;
Dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethyl Hexadecyl group, dimethylheptadecyl group;
Trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl 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 , Ethyl heptadecyl group;
Propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, ;
Butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group;
And so on.

Of these, branched alkyl groups having 7 to 18 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 above example of the branched alkyl group, the branching position is arbitrary.

Specific examples of the alkyl group having a partially cyclic structure of R ¹ include 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, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclohexylethyl group, cycloheptylethyl group, cyclooctylethyl group , Cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group and other alkyl groups having a partially cyclic structure having 7 to 10 carbon atoms are preferable, and cycloheptyl group and cyclooctyl group are more preferable.

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

In the above formula, R ² represents a hydrogen atom or an alkyl group having 1 to 19 carbon atoms. When R ² is an alkyl group, the number of carbon atoms is not more than the above upper limit value, so that when the phenol compound of the present invention is used as a resin raw material, the obtained resin is excellent in terms of mechanical strength and heat resistance. It is preferable because it easily develops its characteristics. Further, when the number of carbon atoms is not more than the above upper limit value, low melting point property is easily exhibited, and it can be suitably used as a specific color developer. R ² is easy to obtain as a raw material and the phenol compound of the present invention is easily available, and when the phenol compound of the present invention is used as a resin raw material, the obtained resin is excellent in terms of mechanical strength and heat resistance. It is preferably a hydrogen atom or an alkyl group having 12 or less carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms, and it is a hydrogen atom or a methyl group, from the viewpoint of easily exhibiting the above characteristics. Is more preferable, and a hydrogen atom is more preferable.

The alkyl group of 1 to 19 carbon atoms R ^2, preferably a linear or branched alkyl group, and an alkyl group having a partially cyclic structure. Among these raw material is easily present invention obtained Linear or branched alkyl in that the phenol compound is easily available and that when the phenol compound of the present invention is used as a resin raw material, the obtained resin is more likely to exhibit excellent properties such as flexibility. It is preferably a group, more preferably a linear alkyl group.

Specific examples of the linear alkyl group of R ² is a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl group, n- hexyl group, heptyl group n-, n- octyl group , N-nonyl group, 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-Nonadecyl group and the like, but a linear alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a butyl group and an undecyl group is preferable, and a methyl group is particularly preferable.

Specific examples of the branched alkyl group R ² is an isopropyl group, methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, heptyl group, methyl octyl group, methylnonyl group, methyldecyl group, a methyl undecyl group , Methyl dodecyl group, methyl tridecyl group, methyl tetradecyl group, methyl pentadecyl group, methyl hexadecyl group, methyl heptadecyl group, methyl octadecyl group;
t-butyl group, dimethylethyl group, methylpropyl 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;
Trimethylpropyl group, trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group Group, trimethylpentadecyl group, trimethylhexadecyl group;
Ethylpropyl group, ethylbutyl group, ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpenta Decyl group, ethyl hexadecyl group, ethyl heptadecyl group;
Propylbutyl group, propylpentyl group, propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpenta Decyl group, propylhexadecyl group ,;
Butylpentyl group, butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group;
And so on.

Of these, branched alkyl groups having 7 to 18 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 above example of the branched alkyl group, the branching position is arbitrary.

Specific examples of the alkyl group having a part-annular structure of R ² include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, a cycloalkyl Dodecyl group;
Cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclodecylmethyl group, cycloundecylmethyl group, cyclododecylmethyl group;
Cyclopropylethyl group, cyclobutylethyl group, cyclopentylethyl group, cyclohexylethyl group, cycloheptylethyl group, cyclooctylethyl group, cyclononylethyl group, cyclodecylethyl group, cycloundecylethyl group, cyclododecylethyl group;
Cyclopropylpropyl group, cyclobutylpropyl group, cyclopentylpropyl group, cyclohexylpropyl group, cycloheptylpropyl group, cyclooctylpropyl group, cyclononylpropyl group, cyclodecylpropyl group, cycloundecylpropyl group, cyclododecylpropyl group;
Methylcyclopropyl group, methylcyclobutyl group, methylcyclopentyl group, methylcyclohexyl group, methylcycloheptyl group, methylcyclooctyl group, methylcyclononyl group, methylcyclodecyl group, methylcycloundecyl group, methylcyclododecyl group;
Dimethylcyclopropyl group, dimethylcyclobutyl group, dimethylcyclopentyl group, dimethylcyclohexyl group, dimethylcycloheptyl group, dimethylcyclooctyl group, dimethylcyclononyl group, dimethylcyclodecyl group, dimethylcycloundecyl group, dimethylcyclododecyl group;
Ethylcyclopropyl group, ethylcyclobutyl group, ethylcyclopentyl group, ethylcyclohexyl group, ethylcycloheptyl group, ethylcyclooctyl group, ethylcyclononyl group, ethylcyclodecyl group, ethylcycloundecyl group, ethylcyclododecyl group;
Propylcyclopropyl group, propylcyclobutyl group, propylcyclopentyl group, propylcyclopropyl group, propylcyclobutyl group, propylcyclopentyl 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 An alkyl group having a partially cyclic structure having 6 to 10 carbon atoms such as an octylethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, and a cyclooctylmethyl group is preferable, and a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are more preferable.

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

In the above formula, R ^{3 to} R ⁶ each independently represent a hydrogen atom or a methyl group. Since R ^{3 to} R ⁶ are these substituents, it is preferable that the obtained resin easily exhibits excellent properties such as mechanical strength and heat resistance when the phenol compound of the present invention is used as a resin raw material. .. Of these, the fact that R ³ and R ⁵ and R ⁴ and R ⁶ are the same makes it easy to obtain raw materials and the phenol compound of the present invention, and purifies the phenol compound of the present invention. In this case, it is preferable that the purification efficiency can be further improved, R ⁴ and R ⁶ are more preferably ^{hydrogen atoms, and all R 3 to} R ⁶ are particularly preferably hydrogen atoms.

<Melting point>
The phenolic compounds of the present invention are usually solid at room temperature. The melting point is not particularly specified, but is usually 30 ° C. or higher, preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher. On the other hand, it is usually 180 ° C. or lower, preferably 170 ° C. or lower, more preferably 160 ° C. or lower, and particularly preferably 150 ° C. or lower. When the melting point is at least the above lower limit value, the phenol compound of the present invention can be easily handled as a powder at room temperature, which is preferable. On the other hand, when the melting point is not more than the upper limit value, when the phenol compound of the present invention is handled as a resin raw material, it tends to be easy to handle such as easy melting treatment, which is preferable. Here, the melting point represents the temperature at which the start of melting of the phenol compound of the present invention is observed in the measurement of raising the temperature at a rate of 2 ° C./min using a melting point measuring device.

<Moisture content>
The phenolic compound of the present invention may contain water. The water content is usually 0.001% by mass or more, preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, it is usually 10% by mass or less, preferably 5% by mass or less, and particularly preferably 1.5% by mass or less. When the phenol compound of the present invention is used as a resin raw material such as a polycarbonate resin or an epoxy resin, when the water content is at least the above lower limit value, it tends to be handled safely in terms of handling such as suppressing the generation of static electricity, which is preferable. On the other hand, when the phenol compound of the present invention is used as a resin raw material such as a polycarbonate resin or an epoxy resin, the water content is not more than the above upper limit value, so that foaming or bumping of the resin raw material due to water vapor generation is suppressed. It is preferable because it tends to be handled safely.

<Solvent content>
The phenolic compound of the present invention may contain an organic solvent. The solvent content is usually 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and 5% by mass or less. Is particularly preferable, and in particular, it is preferably 1% by mass or less. When the solvent content is not more than the above upper limit, when the phenol compound of the present invention is used as a resin raw material such as a polycarbonate resin or an epoxy resin, it is safe in terms of handling such as suppressing poisoning and ignition risk due to volatilization of the organic solvent. It tends to be handled in a plastic manner, which is preferable. Although the lower limit of the solvent content is not particularly specified, it is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, in terms of making the phenol compound of the present invention easily available. preferable.

<Example>
The structure of the bisphenol compound represented by the formula (1) will be illustrated below by showing the combination ^{of each of the substituents R 1 to} R ^{6 in the formula (1).} The phenolic compound of the present invention is not limited to the following examples.

Among them, the phenolic compound of the present invention is
1,1-bis (4-hydroxyphenyl) dodecane (Compound (P-1))
1,1-bis (4-hydroxyphenyl) undecane (Compound (P-2))
1,1-bis (4-hydroxyphenyl) decane (Compound (P-3))
1,1-bis (4-hydroxyphenyl) nonane (Compound (P-4))
1,1-bis (4-hydroxyphenyl) tetradecane (Compound (P-5))
1,1-bis (4-hydroxyphenyl) octadecane (Compound (P-6))
1,1-bis (4-hydroxy-3-methylphenyl) dodecane (Compound (P-7))
1,1-bis (4-hydroxy-3-methylphenyl) undecane (Compound (P-9))
1,1-bis (4-hydroxy-3-methylphenyl) decane (Compound (P-11))
1,1-bis (4-hydroxy-3-methylphenyl) nonane (Compound (P-13))
1,1-bis (4-hydroxyphenyl) -2-ethylhexane (Compound (P-15))
2,2-Bis (4-hydroxyphenyl) nonane (Compound (P-19))
2,2-Bis (4-hydroxyphenyl) undecane (Compound (P-23))
12,12-Bis (4-hydroxyphenyl) tricosane (Compound (P-29))
Is preferable
1,1-bis (4-hydroxyphenyl) dodecane 1,1-bis (4-hydroxyphenyl) undecane 1,1-bis (4-hydroxyphenyl) decane 1,1-bis (4-hydroxyphenyl) nonane 1, 1-bis (4-hydroxyphenyl) octadecane 1,1-bis (4-hydroxyphenyl) -2-ethylhexane 2,2-bis (4-hydroxyphenyl) undecane 12,12-bis (4-hydroxyphenyl) tricosane Is more preferable
1,1-bis (4-hydroxyphenyl) dodecane 1,1-bis (4-hydroxyphenyl) undecane 1,1-bis (4-hydroxyphenyl) decane 1,1-bis (4-hydroxyphenyl) nonane in particular preferable. Such a bisphenol compound can be particularly preferably used as a raw material for a resin or a color developer.

[Manufacturing of phenolic compounds]
The phenolic compound of the present invention can be easily produced by a known method, for example, by condensing a corresponding aldehyde, ketone, acetal, thioacetal, trioxane or other aldehyde or ketone with a monophenol under an acid catalyst. Can be done. As an example, a method of reacting an aldehyde or ketone compound represented by the following formula (2) with a monophenol compound represented by the following formula (3) can be mentioned.

[In the formula (2), R ¹ and R ² are synonymous with ^{R 1} and R ² in the formula (1). ]

[In the formula (3), R ³ and R ⁴ are synonymous with ^{R 3} and R ⁴ in the formula (1). ]

<Aldehydes or ketones>
The aldehydes and ketones used in the production of the phenol compound of the present invention represent at least one selected from the group consisting of aldehyde compounds or ketone compounds, and corresponding acetal compounds, thioacetal compounds, trioxane compounds and the like. However, an aldehyde compound or a ketone compound is preferable because the amount of by-products produced is small and the purification process can be simplified and the amount of waste is small because the main by-product is water. When a phenol compound is used as a resin raw material, it is particularly preferable that the aldehyde compound is an aldehyde compound in that characteristics such as mechanical strength of the obtained resin are easily exhibited.

The aldehyde compound refers to a compound in which ^{R 2} is a hydrogen atom in the above formula (2). Specific examples thereof include linear alkyl aldehydes, branched alkyl aldehydes, and alkyl aldehydes having a partially cyclic structure. Of these, when the phenol compound of the present invention is used as a resin raw material, a linear alkyl aldehyde or a branched alkyl aldehyde is preferable in that characteristics such as mechanical strength of the obtained resin are easily exhibited. It is particularly preferably a linear alkyl aldehyde.

Specific examples of the linear alkyl aldehyde include n-octanal, n-nonanal, n-decanal, n-undecanal, n-dodecanal, n-tridecanal, n-tetradecanal, n-pentadecaneal, n. -Hexadecanal, n-heptadecanal, n-octadecanal, n-nonadecanal, n-nonadesylaldehyde, n-icosylaldehyde and the like, but n-octanal, n-nonanal, n-decalaldehyde, etc. Linear alkylaldehydes having 8 to 19 carbon atoms such as n-undecanal, n-dodecanal, n-tridecanal, n-heptadecanal, n-octadecanal, and n-nonadecanal are preferable, and n-nonanal and n -Decanal, n-undecanal, n-dodecanal are more preferable, and n-dodecanal is particularly preferable.

Specific examples of the branched alkyl aldehyde include methyl hexyl aldehyde, methyl heptyl aldehyde, methyl octyl aldehyde, methyl nonyl aldehyde, methyl decyl aldehyde, methyl undecyl aldehyde, methyl dodecyl aldehyde, methyl tridecyl aldehyde, and methyl tetradecyl aldehyde. Methylpentadecylaldehyde, methylhexadecylaldehyde, methylheptadecylaldehyde, methyloctadecylaldehyde, methylnonadecilaldehyde;
Dimethylpentylaldehyde, dimethylhexylaldehyde, dimethylheptylaldehyde, dimethyloctylaldehyde, dimethylnonylaldehyde, dimethyldecylaldehyde, dimethylundecylaldehyde, dimethyldodecylaldehyde, dimethyltridecylaldehyde, dimethyltetradecylaldehyde, dimethylpentadecylaldehyde, dimethyl Hexadecylaldehyde, dimethylheptadecylaldehyde, dimethyloctadecylaldehyde;
Trimethylhexyl aldehyde, trimethyl heptyl aldehyde, trimethyl octyl aldehyde, trimethyl nonyl aldehyde, trimethyl decyl aldehyde, trimethyl undecyl aldehyde, trimethyl dodecyl aldehyde, trimethyl tridecyl aldehyde, trimethyl tetradecyl aldehyde, trimethyl pentadecyl aldehyde, trimethyl hexadecyl aldehyde, Trimethylheptadecylaldehyde;
Ethylpentylaldehyde, ethylhexylaldehyde, ethylheptylaldehyde, ethyloctylaldehyde, ethylnonylaldehyde, ethyldecylaldehyde, ethylundecylaldehyde, ethyldodecylaldehyde, ethyltridecylaldehyde, ethyltetradecylaldehyde, ethylpentadecylaldehyde, ethylhexa Decylaldehyde, ethylheptadecylaldehyde, ethyloctadecylaldehyde;
Propylhexyl aldehyde, propyl heptyl aldehyde, propyl octyl aldehyde, propyl nonyl aldehyde, propyl decyl aldehyde, propyl undecyl aldehyde, propyl dodecyl aldehyde, propyl tridecyl aldehyde, propyl tetradecyl aldehyde, propyl pentadecyl aldehyde, propyl hexadecyl aldehyde, Propylheptadecylaldehyde;
Butylhexyl aldehyde, butyl heptyl aldehyde, butyl octyl aldehyde, butyl nonyl aldehyde, butyl decyl aldehyde, butyl undecyl aldehyde, butyl dodecyl aldehyde, butyl tridecyl aldehyde, butyl tetradecyl aldehyde, butyl pentadecyl aldehyde, butyl hexadecyl aldehyde;
And so on.

Of these, branched alkyl aldehydes having 8 to 19 carbon atoms such as ethyl hexyl aldehyde, ethyl heptyl aldehyde, ethyl octyl aldehyde, ethyl undecyl aldehyde, and ethyl pentadecyl aldehyde are preferable, and ethyl pentyl aldehyde and ethyl hexyl aldehyde are more preferable. Ethylhexyl aldehyde is particularly preferred.

In the above example of the branched alkylaldehyde, the branching position is arbitrary.

Specific examples of alkylaldehydes having a partially cyclic structure include formylcycloheptane, formylcyclooctane, formylcyclononane, formylcyclodecane, formylcycloundecane, formylcyclododecane;
Formylmethylcyclohexane, formylmethylcycloheptane, formylmethylcyclooctane, formylmethylcyclononane, formylmethylcyclodecane, formylmethylcycloundecane, formylmethylcyclododecane;
Formyldimethylcyclohexane, formyldimethylcycloheptane, formyldimethylcyclooctane, formyldimethylcyclononane, formyldimethylcyclodecane, formyldimethylcycloundecane, formyldimethylcyclododecane;
Formylethylcyclohexane, formylethylcycloheptane, formylethylcyclooctane, formylethylcyclononane, formylethylcyclodecane, formylethylcycloundecane, formylethylcyclododecane;
Formyl diethylcyclohexane, formyldiethylcycloheptane, formyldiethylcyclooctane, formyldiethylcyclononane, formyldiethylcyclodecane, formyldiethylcycloundecane, formyldiethylcyclododecane;
Formylpropylcyclohexane, formylpropylcycloheptane, formylpropylcyclooctane, formylpropylcyclononane, formylpropylcyclodecane, formylpropylcycloundecane, formylpropylcyclododecane, formylcyclohexylcyclohexane;
And so on.

Of these, formylcycloheptane, formylcyclooctane, formylcyclononane, formylcyclodecane, formylmethylcyclohexane, formylmethylcycloheptane, formylmethylcyclooctane, formyldimethylcyclohexane, formyldimethylcycloheptane, formylethylcyclohexane, formylethylcyclo Alkylaldehyde having a partially cyclic structure having 8 to 11 carbon atoms such as heptane is preferable, and formylcycloheptane and formylcyclooctane are more preferable.

In the example of the alkylaldehyde having a partially cyclic structure, the substitution position of the formyl group is arbitrary.

^{The ketone compound refers to a compound in which R 2} is an alkyl group having 1 to 19 carbon atoms in the above formula (2). Specific examples thereof include 2-nonanone, 2-decanone, 3-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 2-dodecanone, 5-dodecanone, 2-tridecanone, 2-methyl-4-undecanone, 2-Tetradecanone, 3-Tetradecanone, 2-Pentadecanone, 6-Pentadecanone, 3-Hexadecanone, 9-Heptadecanone, 10-Nonadecanone, 11-Heneikosanone, 12-Tricosanone, 14-Heptacosanone, 16-Hentria Contanone, 18-Penta Tria-Contanone and the like. Of these, 2-nonanone, 2-decanone, 2-undecanone, 2-dodecanone, 2-Toridekanon, 2 Tetoradekanon those ^{R 2,} such as 2-pentadecanone is a methyl group, or 9-Heputadekanon, 11- ^{It is preferable that R 1} and R ² are the same, such as henei cosanone, 10-nonadecanone, 12-tricosanone, 16-hentria contanone, and 18-pentatria contanone, 2-nonanone, 2-decanone, 2-undecanone, etc. 2-Dodecanone, 2-Tridecanone and 12-Tricosanone are more preferred, 2-Undecanone, 2-Dodecanone, 2-Tridecanone and 12-Tricosanone are particularly preferred, and 2-Undecanone, 2-Dodecanone and 2-Tridecanone are more preferred.

These aldehydes or ketones may be used alone or in combination of two or more. In the process for producing the phenol compound of the present invention, it is preferable to use these aldehydes or ketones alone from the viewpoint of improving the purification efficiency of the phenol compound of the present invention.

<Monophenols>
Specific examples of the monophenols represented by the formula (3) used in the production of the phenol compound of the present invention include phenol, o-cresol, and 2,6-dimethylphenol. Of these, when the phenolic compound of the present invention is used as a resin raw material, it is preferable to use phenol or o-cresol because it is easy to exhibit excellent properties such as mechanical strength of the obtained resin, and phenol is used. Is particularly preferred. These monophenols may be used alone or in combination of two or more. In the process for producing the phenol compound of the present invention, it is preferable to use these phenols alone from the viewpoint of improving the purification efficiency of the phenol compound of the present invention.

<Ratio of monophenols / aldehydes or ketones>
The ratio of aldehydes or ketones to monophenols in producing the phenolic compound of the present invention is not particularly specified as long as the conditions for producing the phenolic compound of the present invention are not specified, but monophenols to aldehydes or ketones are not specified. The class is usually 1 mol times or more, preferably 2 mol times or more, and particularly preferably 3 mol times or more. When the amount of monophenols is at least the above lower limit value, the phenol compound of the present invention tends to be efficiently produced, which is preferable. On the other hand, the ratio of monophenols to aldehydes or ketones is usually 20 mol times or less, preferably 15 mol times or less, and particularly preferably 10 mol times or less. When the amount of the monophenols is not more than the above upper limit value, the load of the step of separating the unreacted monophenols tends to be reduced in the production of the phenol compound of the present invention, which is preferable.

<Acid catalyst>
Examples of the acid catalyst used for producing the phenol compound of the present invention include inorganic acid catalysts such as phosphoric acid, oxalic acid, hydrochloric acid and sulfuric acid; acetic acid, trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid and trifluoromethanesulfonic acid. Organic acid catalysts such as solid acid, heterogeneous acid catalysts such as cation exchange resin, and the like. The type and amount of these acid catalysts are selected in consideration of various points such as ease of handling when producing the phenol compound of the present invention, reaction selectivity at the time of production, and cost. These acid catalysts may be used alone or in combination of two or more.

<Third component>
When producing the phenolic compound of the present invention, the reaction system may contain a third component for the purpose of shortening the reaction time. Specifically, the third component includes quaternary ammonium salts such as tetraethylammonium bromide, tetrabutylammonium hydrosulfate, and tetrabutylammonium chloride; methanethiol, ethanethiol, butanethiol, octanethiol, dodecanethiol, and mercaptoacetic acid. , 3-Mercaptopropionic acid, 2-Mercaptoethanol, 2-aminoethanethiol, ethyl thiolactic acid, thiobutyric acid, pentaerythritol tetrakis (mercaptoacetic acid), 1,4-butanediolbis (thioglycolic acid), 2-ethylhexyl ( Examples thereof include sulfur-containing compounds such as thioglycolic acid). Of these, it is preferable to use a sulfur-containing compound as the third component because the phenol compound of the present invention can be easily produced. On the other hand, it is preferable not to include these third components because the separation of the phenol compound of the present invention and the third component becomes unnecessary and the purification step of the phenol compound of the present invention can be simplified. In addition, these third components may be used in a state of being supported on a resin or the like.

The amount of the third component used in producing the phenol compound of the present invention is not particularly specified as long as the phenol compound of the present invention can be efficiently produced, but the amount of the third component is larger than that of the aldehydes or ketones to be subjected to the reaction. , Usually 0.001 mol times or more, preferably 0.005 mol times or more, and particularly preferably 0.01 mol times or more. When the amount of the third component is at least the above lower limit value, the phenol compound of the present invention tends to be efficiently produced, which is preferable. The amount of the third component with respect to the aldehydes or ketones to be subjected to the reaction is usually 1 mol times or less, preferably 0.5 mol times or less, and particularly preferably 0.2 mol times or less. .. When the amount of the third component is not more than the above upper limit value, the load of the step of separating the third component after the reaction tends to be reduced in the production of the phenol compound of the present invention, which is preferable. These third components may be used alone or in combination of two or more.

<Solvent>
When producing the phenolic compound of the present invention, a solvent may be used. 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; linear alcohol solvent such as ethanol and n-butanol; isopropanol, 2-butanol, isobutanol and the like Branched chain alcohol solvent; nitrile solvent such as acetonitrile; ether solvent such as dibutyl ether; 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 solvents such as dimethyl sulfoxide and sulfolane; chlorine-containing solvents such as methylene chloride, chloroform and dichloroethane; aromatic hydrocarbon solvents such as benzene, toluene and xylene can be mentioned. It should be noted that the use of these solvents is preferable in that the operability of the reaction can be improved, such as suppressing the solidification of the raw material during the reaction and suppressing unexpected side reactions due to internal heat generation, and it is preferable that the solvent and the raw material are unexpectedly used. It is preferable to use a solvent containing at least one of water or a hydrocarbon solvent in that side reactions can be prevented and by-products can be easily removed during the production of the phenolic compound of the present invention. On the other hand, it is preferable not to use these solvents because it is not necessary to separate the phenol compound of the present invention from the solvent and the purification step of the phenol compound of the present invention can be simplified.

The amount of the solvent used in producing the phenol compound of the present invention is not particularly specified as long as the phenol compound of the present invention can be produced efficiently, but the amount of the solvent is usually 0.1 times by mass with respect to aldehydes or ketones. The above is preferably 0.2 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 phenol compound of the present invention, which is preferable. The amount of the solvent is usually 20 times by mass or less, preferably 10 times by mass or less, and particularly preferably 5 times by mass or less with respect to aldehydes or ketones. When the amount of the solvent is not more than the above upper limit value, the phenol compound of the present invention tends to be efficiently produced, which is preferable.

<Reaction temperature>
The reaction temperature at the time of producing the phenol 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 equal to or higher than the lower limit, it tends to be easy to prevent the reaction mixture from solidifying, which is preferable. On the other hand, the reaction temperature 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 upper limit value, the phenol compound of the present invention tends to be efficiently produced, which is preferable.

<Acid catalyst removal process>
The step of producing the phenolic compound of the present invention preferably includes a step of removing the acid catalyst used after the reaction. Specific examples of the acid catalyst removal step include a base neutralization step, a removal step by dissolving in a solvent, a removal step by filtration, and the like. Of these, when an inorganic acid catalyst or an organic acid catalyst is used as the acid catalyst, a neutralization step with a base is included, and when a heterogeneous acid catalyst is used, a removal step by filtration is included. It tends to be able to remove the catalyst, which is preferable. In addition, these acid catalyst removal steps may be used individually or in combination of 2 or more types.

Further, when these removal steps are carried out, it is preferable to carry out the steps in a state where the mixture containing the phenol compound of the present invention is dissolved or suspended in a solvent. Specific examples thereof include a solvent that can be used in producing the phenolic compound of the present invention. Of these solvents, it is preferable to use a solvent selected from at least one of the hydrocarbon solvents because the purification treatment of the phenol compound of the present invention can be facilitated and the cost at the time of production can be reduced. It is particularly preferable to use a solvent containing a hydrocarbon solvent. These solvents may be used alone or in combination of two or more. When a solvent is used in the reaction step of the phenol compound of the present invention, the solvent may be used as it is as the solvent in the removal step.

Specific examples of the base used in the base neutralization step include sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium hydroxide, potassium hydroxide, and phosphorus. Inorganic bases having alkali metal atoms or alkaline earth metal atoms such as sodium monohydrogen acid, potassium monohydrogen phosphate, sodium phosphate, potassium phosphate, magnesium hydroxide, calcium hydroxide, sodium hydride, sodium amide; Organic bases having alkali metal atoms or alkaline earth metal atoms such as sodium acid, potassium citrate, sodium succinate, potassium succinate, calcium slaked, sodium methoxide, potassium methoxide, potassium-tert-butoxide; pyridine, Examples thereof include nitrogen-containing compounds such as aniline, triethylamine, N, N-dimethylaniline, morpholine, 1,4-diazabicyclo [2,2,2] octane, and diazabicycloundecene. Of these, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium hydroxide, potassium hydroxide, sodium monohydrogen phosphate, potassium monohydrogen phosphate, Bases having alkali metal atoms or alkaline earth metal atoms such as sodium phosphate, potassium phosphate, magnesium hydroxide, calcium hydroxide, sodium hydride, sodium citrate, potassium citrate, sodium succinate, potassium succinate, etc. It is preferable to use it because it facilitates removal of the neutralizing salt. In addition, these bases may be used alone or in combination of two or more.

In the neutralization step, a second component may be added for the purpose of adjusting the acidity of the reaction mixture. Specific examples thereof include organic acids such as acetic acid, citric acid, succinic acid, and malic acid; heteroatoms other than oxygen such as phosphoric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium chloride, and monosodium citrate. Examples include acids containing. The type and amount of the second component are variously selected depending on the type and amount of the acid catalyst used in the reaction step and the base used in the neutralization step, and the target value of the acidity of the reaction mixture after neutralization.

It is preferable that the reaction mixture after the neutralization step is weakly acidic or weakly basic because the stability of the phenol compound of the present invention tends to be improved. In addition, when the reaction mixture is weakly acidic or weakly basic, the pH of the aqueous layer is usually 2 or more when water is added to the mixture to adjust the weight ratio of water and other components to 1: 3. It means that it is preferably 3 or more, particularly preferably 4 or more, usually 11 or less, preferably 10 or less, and particularly preferably 9 or less. When the pH of the aqueous layer is within the above range, the stability of the phenol compound of the present invention tends to be improved, which is preferable.

Specific examples of the solvent used in the acid catalyst removal step by dissolving in a solvent include water; organic solvents such as methanol, ethanol, propanol, dimethyl sulfoxide, diethyl ether, and N-methylpyrrolidone. Of these, it is preferable to use water because the purification process can be simplified.
In the above step, a second component may be added in order to increase the removal efficiency. Specific examples thereof include organic salts such as sodium methanesulfonate; and inorganic salts such as sodium chloride and sodium sulfate. The type and amount of the second component are variously selected depending on the removal efficiency of the acid catalyst.

Filter agents used in the acid catalyst removal step by filtration include powdery, crushed or spherical filters such as activated carbon, silica gel, activated clay, and diatomaceous earth; fibrous or cloth-like filters such as filter paper, filter cloth, and thread-wound filter. Examples thereof include a filter agent molded into the above. These filtering agents are variously selected based on the properties of the acid catalyst used, the possibility of reusing the acid catalyst, and the like.
In addition, these removal steps are a part of the phenol compound of the present invention such as unreacted raw materials, by-products, the second and third components used at the time of reaction or in the removal step of the acid catalyst, and components other than the acid catalyst, or It may also serve as a step of removing all of them.

<Concentration process>
The method for producing a phenol compound of the present invention is a step of removing low boiling point components such as a solvent and unreacted raw materials from a mixture containing the phenol compound of the present invention by concentration (hereinafter, may be referred to as a concentration step). It is preferable to include it. By carrying out this step, the efficiency of taking out the phenol compound of the present invention in the precipitation step described later tends to be improved. The concentration step is usually carried out under heating and depressurizing conditions. The heating temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and particularly preferably 80 ° C. or higher. Further, it is usually 200 ° C. or lower, preferably 180 ° C. or lower, and particularly preferably 160 ° C. or lower. When the heating temperature is within the above temperature range, the concentration step can be efficiently carried out, and the decomposition of the phenol compound of the present invention tends to be suppressed. The heating temperature in this concentration step refers to the temperature of the heat medium used for heating. The degree of decompression is usually less than 760 Torr, preferably 200 Torr or less, more preferably 100 Torr or less, and particularly preferably 50 Torr or less. When the degree of decompression is not more than the above upper limit value, the concentration step tends to be carried out efficiently. On the other hand, the lower limit of the degree of decompression is not particularly specified, but is usually 0.1 Torr or more, preferably 1 Torr or more, and more preferably 10 Torr or more from the viewpoint that a widely and generally used decompression device can be used. , Particularly preferably 20 Torr or more.

<Rough purification process>
When producing the phenolic compound of the present invention, a reaction mixture usually obtained through the above-mentioned reaction of aldehydes or ketones with monophenols, a subsequent removal step of an acid catalyst, or a removal step of an acid catalyst and a concentration step. Is a mixture containing the phenolic compound of the present invention as a main component. In the method for producing a bisphenol compound of the present invention, a mixture containing the phenol compound of the present invention as a main component is dissolved in a solvent containing an aliphatic alcohol solvent (hereinafter, may be referred to as a "crystallization solvent") to form a solution. After that, a step of precipitating the phenol compound of the present invention (hereinafter, may be referred to as a “precipitation step”) is included, but prior to this precipitation step, the reaction mixture other than the phenol compound of the present invention is included. It is preferable to include a crude purification step of roughing the components.
In this crude purification step, preferably, the phenol compound of the present invention is extracted from the reaction mixture with an extraction solvent, the extractor layer containing the phenol compound of the present invention is washed with water, and then the extractor layer is subjected to reduced pressure. This is done by removing the extraction solvent with.

The extraction solvent used for this extraction may be a good solvent of the phenol compound of the present invention, and is not particularly limited, but as a specific example thereof, a solvent that can be used for producing the phenol compound of the present invention can be used. Among them, those excluding water and the like can be mentioned. Of these, it is preferable to contain at least one of a solvent selected from an ether solvent, a ketone solvent, an ester solvent, a chlorine-containing solvent, and an aromatic hydrocarbon solvent in terms of facilitating extraction of the phenol compound of the present invention. It is more preferable to contain at least a solvent selected from any of an ether solvent, a ketone solvent, an ester solvent, a chlorine-containing solvent, and an aromatic hydrocarbon solvent, and particularly preferably to contain at least a solvent selected from the aromatic hydrocarbon solvent. Among them, it is preferable to contain a solvent or xylene, and most preferably to contain a solvent.
These extracts may be used alone or in combination of two or more.

The extraction solvent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more with respect to the reaction mixture. When the amount of the extraction solvent is at least the above lower limit value, the phenol compound of the present invention tends to be efficiently extracted. Further, it is preferably 20 times by mass or less, more preferably 10 times by mass or less, and particularly preferably 5 times by mass or less. When the amount of the extraction solvent is not more than the above upper limit value, the production efficiency of the phenol compound of the present invention tends to be improved.

The amount of water used for washing the extractor layer containing the phenolic compound of the present invention obtained by extraction is usually 0.1% by mass or more, 0.5% by mass or more, based on the total amount of the extraction layer. The above is preferable, and it is particularly preferable that the mass is 1 mass or more. When the amount of water is equal to or higher than the lower limit, the purification efficiency in the crude purification step tends to improve. The amount of water is usually 10 times by mass or less, preferably 5 times by mass or less, and particularly preferably 3 times by mass or less, based on the total amount of the extractor layer. When the amount of water is not more than the above upper limit value, the production efficiency of the phenol compound of the present invention tends to be improved.
The number of times of washing the extractant layer with water is usually about 1 to 20 times, preferably 2 to 10 times, and particularly preferably 3 to 6 times. When the number of washings with water is not less than the lower limit value, the purification efficiency in the crude purification step tends to be improved, and when it is not more than the upper limit value, the production efficiency of the phenol compound of the present invention tends to be improved.

When removing the extraction solvent after the washing with water, it is usually carried out at a temperature of 40 to 200 ° C. under a reduced pressure of 760 to 1 Torr. The above-mentioned temperature represents the temperature of the heat medium used.

The purity of the crude product of the phenolic compound of the present invention obtained through such a crude purification step is usually about 10 to 95% in terms of the absorption area ratio of 254 nm by liquid chromatography (LC) analysis.
The crude purification step may be carried out in combination with the acid catalyst removing step and the concentration step described above.

<Precipitation process>
In the method for producing a bisphenol compound of the present invention, the above-mentioned reaction mixture, preferably a crude product of the phenol compound of the present invention that has undergone the above crude purification step (hereinafter, may be referred to as "a mixture containing the phenol compound of the present invention"). ) Is dissolved in a crystallization solvent containing an aliphatic alcohol solvent to prepare a solution, and then the phenol compound of the present invention is precipitated. Here, the fatty alcohol solvent in the present invention has a melting point of 30 ° C. or lower, preferably 15 ° C. or lower, does not have a carbon-carbon double bond in the molecule, and has at least one hydroxy group being carbon. It represents a compound having a structure bonded to an atom, and also includes a solvent having a hetero atom in addition to a hydroxy group.

Specific examples of the above-mentioned aliphatic alcohol solvent include linear alcohol solvents having 1 to 10 carbon atoms containing one hydroxy group such as methanol, ethanol, n-propanol, n-butanol, and n-octanol; isopropanol and iso. A branched alcohol solvent having 3 to 10 carbon atoms containing one hydroxy group such as butanol, 2-butanol, tert-butanol, 2-pentanol, 3-pentanol, amyl alcohol; hydroxy such as cyclopentanol and cyclohexanol. An alicyclic alcohol solvent having 3 to 10 carbon atoms containing one group; an alcohol solvent having 2 to 10 carbon atoms containing two or more hydroxy groups such as ethylene glycol, propylene glycol, isoprene glycol, and hexylene glycol; 2,2 , 2-Trifluoroethanol, 2-methoxyethanol, acetylmethanol, 2-acetoxyethanol and other alcohol solvents containing heteroatoms and having 2 to 10 carbon atoms. Of these, it is preferable to use an alcohol solvent containing one hydroxy group from the viewpoint of facilitating the production of the phenol compound of the present invention, and it is particularly preferable to use an alcohol solvent containing no hetero atom other than the hydroxy group. It is more preferable to use a branched alcohol solvent having 3 to 10 carbon atoms, and it is particularly preferable to use a branched alcohol solvent having 3 to 5 carbon atoms such as isopropanol, isobutanol, and 2-butanol. These aliphatic alcohol solvents may be used alone or in combination of two or more.

The above-mentioned crystallization solvent may contain a solvent other than the aliphatic alcohol solvent as the second solvent. Specific examples of the second 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 5 to 18 carbon atoms such as isooctane. Branched chain hydrocarbon solvent; cyclic hydrocarbon solvent having 5 to 18 carbon atoms such as cyclohexane, cyclooctane, and methylcyclohexane; water; nitrile solvent such as acetonitrile; ether solvent such as dibutyl ether; methylethylketone, methylisobutylketone, etc. Ketone solvent; ester solvent such as ethyl acetate and butyl acetate; nitrogen-containing solvent such as dimethylformamide and dimethylacetamide; sulfur-containing solvent such as dimethylsulfoxide and sulfolane; chlorine-containing solvent such as methylene chloride, chloroform and dichloroethane; Examples include aromatic hydrocarbon solvents such as xylene. These solvents may be used alone or in combination of two or more. Of these, it is preferable to use water or a hydrocarbon solvent as the second solvent because the purification efficiency of the phenol compound of the present invention is improved and the production is facilitated, and the hydrocarbon solvent is used as the second solvent. It is particularly preferable to use a saturated chain hydrocarbon solvent such as the above-mentioned linear hydrocarbon solvent having 5 to 18 carbon atoms and a branched chain hydrocarbon solvent having 5 to 18 carbon atoms. These second solvents may be used alone or in combination of two or more.

The mixing ratio of the second solvent and the aliphatic alcohol solvent is not particularly specified and may be appropriately set and used. However, the composition ratio of the aliphatic alcohol solvent in the total crystallization solvent is usually 2 to 98% by mass. It is preferably 2.5 to 90% by mass, and particularly preferably 3 to 30% by mass. When the composition ratio of the aliphatic alcohol solvent in the total crystallization solvent is at least the above lower limit value, the phenol compound of the present invention can be easily obtained with high purity, and when it is at least the above upper limit value, the phenol compound of the present invention can be obtained. It is preferable because it tends to prevent it from being removed in the solvent, that is, it tends to improve the yield.

The melting point of the crystallization solvent is usually 30 ° C. or lower, but it is preferably 15 ° C. or lower, more preferably 5 ° C. or lower, and −10 ° C. or lower in terms of facilitating the production of the phenol compound of the present invention. Is particularly preferable. The lower limit of the melting point is not particularly specified as long as the boiling point of the solvent is within the range described later. Here, the melting point of the crystallization solvent represents the melting point of the mixed solvent when two or more kinds of solvents are mixed and used.

The boiling point of the crystallization solvent is usually 40 ° C. or higher, preferably 50 ° C. or higher, and more preferably 60 ° C. or higher. On the other hand, it is usually 150 ° C. or lower, preferably 135 ° C. or lower, and more preferably 120 ° C. or lower. When the boiling point is at least the above lower limit value, the phenol compound of the present invention tends to be preferentially precipitated, and when it is at least the above upper limit value, the solvent is efficiently removed from the phenol compound of the present invention. It is preferable because the phenol compound of the present invention tends to be easily produced. Here, the boiling point of the crystallization solvent represents the boiling point of the mixed solvent when two or more kinds of solvents are mixed and used.

The precipitation step is usually carried out by mixing a mixture containing the phenol compound of the present invention with the above-mentioned crystallization solvent to prepare a solution, and then precipitating the phenol compound of the present invention from this solution.
The mixing ratio of the mixture containing the phenol compound of the present invention and the above-mentioned crystallization solvent is not particularly specified as long as the phenol compound of the present invention can be efficiently precipitated, but it is usually compared with the mixture containing the phenol compound of the present invention. The mass ratio of the whole crystallization solvent is preferably 0.2 times or more, more preferably 0.5 times or more, and particularly preferably 1 time or more. On the other hand, it is preferably 100 times or less, more preferably 50 times or less, and particularly preferably 10 times or less. When the mass ratio of the total crystallization solvent is at least the above lower limit value, the phenol compound of the present invention tends to be preferentially precipitated, while when it is at least the above upper limit value, the phenol compound of the present invention is produced. It tends to improve efficiency, which is preferable.

When the mixture containing the phenol compound of the present invention and the crystallization solvent are mixed, when the above-mentioned second solvent is used in combination as the crystallization solvent, the aliphatic alcohol solvent and the second solvent may be added separately in advance. It may be mixed with a mixture containing the phenol compound of the present invention in a mixed state. From the viewpoint of improving the production efficiency of the phenol compound of the present invention, it is preferable that the aliphatic alcohol solvent and the second solvent are mixed in advance. Here, the temperature at which the mixture containing the phenol compound of the present invention and the crystallization solvent are mixed is usually 0 ° C. or higher, preferably 20 ° C. or higher, particularly preferably 40 ° C. or higher, and usually below the boiling point of the crystallization solvent. It is preferably (boiling point of the crystallization solvent −5) ° C. or lower, more preferably (boiling point of the crystallization solvent −10) ° C. or lower, and particularly preferably (boiling point of the crystallization solvent −20) ° C. or lower. When the temperature at the time of mixing is equal to or higher than the above lower limit, the solvent solubility of the phenol compound of the present invention can be improved and the phenol compound can be efficiently dissolved, which is preferable. On the other hand, when the temperature at the time of mixing is not more than the above upper limit value, boiling and volatilization of the solvent can be suppressed and the phenol compound of the present invention can be efficiently dissolved, which is preferable. Here, when two or more of the above-mentioned solvents are mixed and used as the crystallization solvent, the boiling point of the above-mentioned solvent represents the boiling point of the mixed solvent.

In the step of precipitating the phenol compound of the present invention from a solution in which the mixture containing the phenol compound of the present invention is dissolved in a crystallization solvent, precipitation is performed by cooling, a poor solvent for the phenol compound of the present invention is added, the solvent is evaporated, and the like. Various methods commonly used for crystallization from solution can be applied. Of these, it is preferable to include a step of precipitating by cooling because the phenol compound of the present invention can be easily produced. The temperature at which the phenolic compound of the present invention is precipitated is not particularly limited as long as the characteristics of the phenolic compound of the present invention are not impaired, and can be appropriately set, but is usually −20 ° C. or higher, preferably −10 ° C. Above, more preferably 0 ° C. or higher. On the other hand, it is usually lower than the above mixing temperature, preferably 70 ° C. or lower, preferably 65 ° C. or lower, more preferably 60 ° C. or lower, particularly preferably 55 ° C. or lower, still more preferably 50 ° C. or lower. is there. When the temperature at the time of precipitation is within the above range, the production efficiency of the phenol compound of the present invention tends to be improved, which is preferable.

In the step of precipitating the phenol compound of the present invention from a solution in which the mixture containing the phenol compound of the present invention is dissolved in a crystallization solvent, seed crystals of the phenol compound of the present invention may be added in order to improve the precipitation efficiency. .. The amount of seed crystals is usually 0.0001 to 10% by mass ratio to 0.0005 to 5% with respect to the mixture containing the phenol compound of the present invention from the viewpoint of improving the production efficiency of the phenol compound of the present invention. Is preferable, and 0.001 to 1% is particularly preferable.

After the phenol compound of the present invention is precipitated in the above-mentioned precipitation step, the powder of the phenol compound of the present invention is recovered from the crystallization solvent used by solid-liquid separation by filtration, centrifugation, decantation or the like.

The number of precipitation steps is variously selected according to the degree of purification of the phenol compound of the present invention, but is usually preferably 3 times or less, and more preferably 2 times or less, from the viewpoint of simplifying the purification process. It is preferable, and it is particularly preferable that it is once.

<Washing process>
The powder of the phenol compound of the present invention obtained in the above precipitation step may be further washed with a solvent for the purpose of surface cleaning. Specific examples of the solvent used in this washing step include the above-mentioned aliphatic alcohol solvent and the solvent exemplified as the second solvent. The temperature of this cleaning treatment is usually −20 ° C. or higher, preferably −10 ° C. or higher, particularly preferably 0 ° C. or higher, and usually 70 ° C. or lower, preferably 60 ° C. or lower, particularly preferably 50 ° C. or lower. When the washing temperature is within the above range, it tends to be possible to suppress excessive dissolution of the phenol compound of the present invention in the cleaning solvent, which is preferable.

<Drying process>
The phenol compound of the present invention obtained through the above-mentioned precipitation step or the precipitation step and the washing step is further subjected to solvent removal treatment by heating, reduced pressure, air drying, etc. to obtain a phenol compound of the present invention which is substantially free of solvent. Is also good. The temperature during the desolvation treatment in this drying step is usually 20 ° C. or higher, preferably 40 ° C. or higher in order to allow the desolvation treatment to proceed smoothly. The upper limit of the temperature is usually lower than the melting point of the phenol compound of the present invention, preferably 100 ° C. or lower, further preferably 75 ° C. or lower, and particularly preferably 72 ° C. or lower.

[Crystal form]
According to the method for producing a bisphenol compound of the present invention, the phenol compound of the present invention obtained through the above-mentioned precipitation step can take a plurality of (for example, 2 to 3) crystalline forms (crystal polyform). Among the phenol compounds of the present invention obtained by the method for producing a bisphenol compound of the present invention, 1,1-bis (4-hydroxyphenyl) dodecane has a diffraction angle of 2θ = 4.25 ° in the powder X-ray diffraction method using CuKα rays. It is preferable that the crystal has at least one peak in the range of ± 0.15 ° and 2θ = 8.45 ° ± 0.20 °. That is, such a crystal is preferable because it is a crystal obtained as a result of the interaction between the phenol compound of the present invention and the aliphatic alcohol solvent of the present invention. Here, "± 0.15 °" and "± 0.20 °" are values in consideration of the difference due to the solvent for producing the crystal, that is, the crystallization solvent, and the measurement error. Specifically, when isopropanol was used as a component of the crystallization solvent to prepare the crystal, 2θ = 4.30 ° ± 0.05 ° and 2θ = 8.58 ° ± 0.05 °, 2- When butanol is used as a component of the crystallization solvent, 2θ = 4.22 ° ± 0.05 ° and 2θ = 8.45 ° ± 0.05 °, and when isobutanol is used as a component of the solvent. Preferably has at least one X-ray crystal diffraction peak at 2θ = 4.15 ° ± 0.05 ° and 2θ = 8.30 ° ± 0.05 °, respectively.

The crystal body in the present invention may consist of only one crystal form or may be a mixture of a plurality of crystal forms. A crystal exhibiting the above-mentioned X-ray diffraction peak behavior can sufficiently exert the effect of the present invention of being excellent in purification efficiency when producing the phenol compound of the present invention.

[Use]
The phenol compound of the present invention includes polyether resins, polyester resins, polycarbonate resins, polyurethane resins, acrylic resins and the like used for various purposes such as optical materials, recording materials, insulating materials, transparent materials, electronic materials, adhesive materials and heat resistant materials. It can be used for various thermoplastic resins, components such as various thermosetting resins such as epoxy resin, unsaturated polyester resin, phenol resin, polybenzoxazine resin, and cyanate resin, additives, or precursors thereof. .. The phenolic compound of the present invention can also be used as a pH adjuster, a surfactant, a color developer and the like.

Examples of the present invention are shown below, but the present invention is not limited thereto. The various analysis methods in the examples are as follows. The symbols of the respective compounds are according to Table 1 of the above-mentioned example of the bisphenol compound represented by the formula (1).

[Liquid Chromatography (LC) Analysis]
50 mg of the sample was dissolved in 10 ml of acetonitrile. The obtained solution was analyzed by an HPLC analyzer (LC-2010 manufactured by Shimadzu Corporation). The conditions were as follows.
(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 velocity 1.0 ml / min Injection volume: 5 μl
Elution conditions: 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
The LC purity was determined from the area% at 254 nm. The reaction selectivity and yield were determined by preparing a calibration curve of the target compound in advance and using the absolute calibration curve method.

[Powder X-ray diffraction (XRD) measurement]
Using an XRD diffractometer (X'pert Pro MPD manufactured by PANalytical), measurements were made under the following conditions, and diffraction peaks in the range of 2θ = 3.00 to 10.00 ° were compared.
X-ray output (CuKα): 40kV, 30mA
Scanning range (2θ): 3.00 to 70.00 °
Measurement mode: Continuus

[Example 1]
<Production of compound (P-1)>
Phenol (220 g, 2.3 mol) was heated to 40 ° C. to melt it, and then 35% concentrated hydrochloric acid (2.9 g, 0.028 mol) was added. A mixed solution of n-dodecanal (86 g, 0.47 mol) and toluene (51 g) was added dropwise thereto at an internal temperature of 45 ° C. or lower over 4 hours. After the dropping, the mixture was aged at 40 ° C. for 1 hour, and then the reaction was stopped with an aqueous sodium hydrogen carbonate solution. The selectivity of compound (P-1) in the reaction mixture was 50.2%. Phenol was distilled off from the reaction mixture at 160 ° C. and 20 Torr under reduced pressure, and then the residue (181 g) was extracted with toluene (340 g) and washed 3 times with water (215 g). The solvent was distilled off at 90 ° C. under reduced pressure (20 Torr) to obtain a crude product (170 g).

<Purification of compound (P-1)>
Isopropanol (77 g) and heptane (430 g) were added to the obtained crude product, and the mixture was heated to 60 ° C. to dissolve it. The temperature was lowered to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained slurry was filtered and washed with a mixed solution of isopropanol (15 g) and heptane (86 g) at 15 ° C. The obtained solid was dried under reduced pressure at 40 ° C. to obtain a white solid of compound (P-1). The purity of the compound (P-1) obtained by LC analysis was 99.6%, and the yield was 43.2%. The X-ray crystal diffraction peaks (2θ) of the obtained solid were 4.02 °, 4.30 ° and 8.61 °.

[Example 2]
After obtaining a crude product of compound (P-1) in the same manner as in Example 1, isopropanol (30 g) and heptane (430 g) were added, and the mixture was heated to 60 ° C. and dissolved. The temperature was lowered to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained slurry was filtered and washed at 15 ° C. with a mixed solution of isopropanol (6.0 g) and heptane (86 g). The obtained solid was dried under reduced pressure at 40 ° C. to obtain a white solid of compound (P-1). The purity of the compound (P-1) obtained by LC analysis was 99.0%, and the yield was 43.4%. The X-ray crystal diffraction peaks (2θ) of the obtained solid were 4.30 °, 4.87 °, and 8.60 °.

[Example 3]
After obtaining a crude product of compound (P-1) in the same manner as in Example 1, 2-butanol (77 g) and heptane (430 g) were added, and the mixture was heated to 60 ° C. and dissolved. The temperature was lowered to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The resulting slurry was filtered and washed at 15 ° C. with a mixture of 2-butanol (15 g) and heptane (86 g). The obtained solid was dried under reduced pressure at 40 ° C. to obtain a white solid of compound (P-1). The purity of the compound (P-1) obtained by LC analysis was 99.3%, and the yield was 42.1%. The X-ray crystal diffraction peaks (2θ) of the obtained solid were 4.22 °, 4.86 °, and 8.45 °.

[Example 4]
After obtaining a crude product of compound (P-1) in the same manner as in Example 1, isobutanol (77 g) and heptane (430 g) were added, and the mixture was heated to 60 ° C. and dissolved. The temperature was lowered to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The resulting slurry was filtered and washed at 15 ° C. with a mixture of 2-butanol (15 g) and heptane (86 g). The obtained solid was dried under reduced pressure at 40 ° C. to obtain a white solid of compound (P-1). The purity of the compound (P-1) obtained by LC analysis was 99.2%, and the yield was 40.3%. The X-ray crystal diffraction peaks (2θ) of the obtained solid were 4.15 °, 4.86 °, and 8.32 °.

[Example 5]
<Production of compound (P-1)>
Phenol (220 g, 2.3 mol) was heated to 40 ° C. to melt it, and then 35% concentrated hydrochloric acid (2.9 g, 0.028 mol) was added. N-dodecanal (86 g, 0.47 mol) was added dropwise thereto at an internal temperature of 45 ° C. or lower over 4 hours. After the dropping, the mixture was aged at 40 ° C. for 1 hour, and then the reaction was stopped with an aqueous sodium hydrogen carbonate solution. The selectivity of compound (P-1) in the reaction mixture was 49.8%. After distilling off phenol from the reaction mixture at 160 ° C. and 20 Torr under reduced pressure, the residue (180 g) was extracted with toluene (340 g) and washed 3 times with water (215 g). The solvent was distilled off at 90 ° C. under reduced pressure (20 Torr) to obtain a crude product (169 g).

<Purification of compound (P-1)>
Isopropanol (57 g) and heptane (260 g) were added to the obtained crude product, and the mixture was heated to 60 ° C. to dissolve it. After lowering the temperature to 55 ° C. and holding, a seed crystal (compound (P-1), 52 mg) was added and held for 1 hour. Then, the temperature was lowered to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained slurry was filtered and washed at 15 ° C. with a mixed solution of isopropanol (4 g) and heptane (96 g). The obtained solid was dried under reduced pressure at 40 ° C. to obtain a white solid of compound (P-1). The purity of the compound (P-1) obtained by LC analysis was 99.5%, and the yield was 43.8%. The X-ray crystal diffraction peaks (2θ) of the obtained solid were 4.27 ° and 8.51 °.

[Example 6]
<Manufacturing of compound (P-6)>
Phenol (220 g, 2.3 mol) was heated to 40 ° C. to melt it, and then 35% concentrated hydrochloric acid (2.9 g, 0.028 mol) was added. To this, n-octadecanal (125 g, 0.47 mol) was added in portions over 4 hours at an internal temperature of 45 ° C. or lower. After the dropping, the mixture was aged at 40 ° C. for 1 hour, and then the reaction was stopped with an aqueous sodium hydrogen carbonate solution. The selectivity of compound (P-6) in the reaction mixture was 47.6%. Phenol was distilled off from the reaction mixture at 160 ° C. and 20 Torr under reduced pressure, and then the residue (220 g) was extracted with toluene (340 g) and washed 3 times with water (215 g). The solvent was distilled off at 90 ° C. under reduced pressure (20 Torr) to obtain a crude product (209 g).

<Purification of compound (P-6)>
Isopropanol (72 g) and heptane (590 g) were added to the obtained crude product, and the mixture was heated to 60 ° C. to dissolve it. The temperature was lowered to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained slurry was filtered and washed at 15 ° C. with a mixed solution of isopropanol (4 g) and heptane (96 g). The obtained solid was dried under reduced pressure at 40 ° C. to obtain a white solid of compound (P-6). The purity of the compound (P-6) obtained by LC analysis was 96.7%, and the yield was 40.6%.

[Example 7]
<Manufacturing of compound (P-19)>
Phenol (18.8 g, 0.200 mol) was heated to 40 ° C. to melt it, and then p-toluenesulfonic acid monohydrate (0.76 g, 4.0 mmol) was added. 2-Tridecanone (4.00 g, 20.2 mmol) and 3-mercaptopropionic acid (0.053 g, 0.50 mmol) were added thereto, and the mixture was heated and stirred at 60 ° C. for 24 hours. An aqueous sodium hydrogen carbonate solution was added to the obtained reaction solution to stop the reaction. The selectivity of compound (P-19) in the reaction mixture was 62.6%. Phenol was distilled off from the reaction mixture at 160 ° C. and 20 Torr under reduced pressure, and then the residue (8.8 g) was extracted with toluene (15 g) and washed 3 times with water (10 g). The solvent was distilled off at 90 ° C. under reduced pressure (20 Torr) to obtain a crude product (7.4 g).

<Purification of compound (P-19)>
Isopropanol (1.6 g) and heptane (16 g) were added to the obtained crude product, and the mixture was heated to 70 ° C. to dissolve it. After lowering the temperature to 42 ° C. and holding, a seed crystal (compound (P-19), 2.4 mgg) was added and held for 1 hour. Then, the temperature was lowered to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained slurry was filtered and washed by sprinkling with a mixed solution of isopropanol (0.080 g) and heptane (7.9 g) at 15 ° C. The obtained solid was dried under reduced pressure at 30 ° C. to obtain a white solid of compound (P-19). The purity of the compound (P-19) obtained by LC analysis was 90.1%, and the yield was 54.5%.

[Comparative Example 1]
After obtaining a crude product of compound (P-1) in the same manner as in Example 1, methylene chloride (310 g) was added and heated to 40 ° C. to dissolve it. The temperature was lowered to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained slurry was filtered and washed by sprinkling with methylene chloride (62 g) at 15 ° C. The obtained solid was dried under reduced pressure at 40 ° C. to obtain a white solid of compound (P-1). The purity of the compound (P-1) obtained by LC analysis was 82.9%, and it was found that the purity was insufficient. The yield of the compound (P-1) obtained by LC yield analysis was 27.2%. Further, the same method was repeated to obtain a solid having a purity of 99.5%. The X-ray crystal diffraction peaks (2θ) of the obtained solid were 4.43 °, 4.71 °, 4.93 °, 8.30 °, 8.78 ° and 9.39 °.

[Comparative Example 2]
After obtaining a crude product of compound (P-1) in the same manner as in Example 1, toluene (258 g) and heptane (258 g) were added, and the mixture was heated to 60 ° C. and dissolved. The temperature was lowered to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained slurry was filtered, and a mixed solution of toluene (52 g) and heptane (52 g) was added at 15 ° C. and sprinkled and washed. The obtained solid was dried under reduced pressure at 40 ° C. to obtain a white solid of compound (P-1). The purity of the compound (P-1) obtained by LC analysis was 86.7%, and it was found that the purity was insufficient. The yield of the compound (P-1) obtained by LC yield analysis was 35.1%. Further, the same method was repeated to obtain a solid having a purity of 99.2%. The X-ray crystal diffraction peaks (2θ) of the obtained solid were 4.94 °, 8.26 °, and 8.71 °.

[Comparative Example 3]
A crude product of compound (P-19) was obtained in the same manner as in Example 7. The obtained crude product was subjected to a precipitation step with various concentrations of toluene / heptane, ethyl acetate / heptane, and methylene chloride / heptane, and the compound (P-19) could be obtained as a solid. could not.

[Comparative Example 4]
A crude product of compound (P-19) was obtained in the same manner as in Example 7. The obtained crude product was purified by silica gel column chromatography (ethyl acetate / heptane eluent) to obtain an ethyl acetate / heptane solution of the compound (P-19) having an LC purity of 93.3%. Was concentrated to dryness under reduced pressure conditions to remove the solvent, and the obtained compound (P-19) was oily.

The results of Examples 1 to 7 and Comparative Examples 1 to 4 are summarized in Table 2 below.
The XRD crystal diffraction patterns of the compounds (P-1) obtained in Examples 1 to 4 and Comparative Examples 1 and 2 are shown in FIGS. 1 to 6, respectively.

When crystallized with a solvent containing an aliphatic alcohol solvent as in Examples 1 to 7, it is clear that a bisphenol compound having sufficient purity can be obtained in one precipitation step and the yield is high. When another solvent was used as the crystallization solvent as in Comparative Examples 1 and 2, the isolation yield was low and the purity was insufficient, and further purification was required to obtain a high-purity product. Further, comparing Example 7 with Comparative Examples 3 and 4, when other solvents are used or when the obtained bisphenol compound becomes oily even if a bisphenol compound having sufficient purity is obtained by silica gel column chromatography. Also, it can be seen that it can be obtained as a powder by undergoing the precipitation step by the method of the present invention.
By the method of the present invention, such efficient purification can be performed because the aliphatic alcohol solvent easily interacts with only the phenol compound of the present invention to form a specific crystal, and the effect of removing by-products is high. It is probable that it was relaxed and the crystallinity was improved. The fact that the crystal of the bisphenol compound obtained through the precipitation step by the method of the present invention has a unique crystal structure is that the results of the X-ray crystal diffraction peaks are compared with Examples 1 to 4 and Comparative Examples 1 and 1. This is supported by the fact that the two are significantly different from each other.

Claims (4)

A method for producing a bisphenol compound, which comprises a step of precipitating a bisphenol compound represented by the following formula (1) from a solution of a solvent containing at least one fatty alcohol solvent.
A method for producing a bisphenol compound, wherein the aliphatic alcohol solvent is a branched alcohol solvent having 3 to 5 carbon atoms.

[In formula (1), R ¹ represents an alkyl group having 7 to 19 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 19 carbon atoms, and R ^{3 to} R ⁶ are independent of each other. Represents a hydrogen atom or a methyl group. ] The method for producing a bisphenol compound according to claim 1, wherein the solvent containing at least one of the fatty alcohol solvents is a solvent containing at least one of each of the fatty alcohol solvent and the hydrocarbon solvent. The method for producing a bisphenol compound according to claim 1 or 2 ^{, wherein R 2} in the formula (1) is a hydrogen atom. The method for producing a bisphenol compound according to claim 3 ^{, wherein R 3 to} R ⁶ in the formula (1) are hydrogen atoms.

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