JP2017200913A - Method for producing bisphenol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method that allows a high-purity bisphenol compound to be obtained in a crystal form with excellent handleability, conveniently and with high yields.SOLUTION: A method for producing a bisphenol compound comprises the step of precipitating a bisphenol compound represented by the formula (1) from a solvent containing at least one aliphatic alcohol solvent. [In formula (1), Ris a C7-C19 alkyl group, Ris a hydrogen atom or a C1-C19 alkyl group, R-Rindependently represent a hydrogen atom or a methyl group].SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a bisphenol compound. In detail, it is related with the manufacturing method of the bisphenol compound excellent in the purification efficiency.

  Bisphenol compounds are useful compounds that are widely used as raw materials for thermoplastic resins such as polycarbonate resins and thermosetting resins such as epoxy resins. In particular, a bisphenol compound having a flexible long-chain alkyl group is expected to be excellent in low melting point and excellent fluidity, and also expected to exhibit elasticity derived from a flexible alkyl group when used as a resin. Since it is expected to give physical properties, it is a particularly important compound. Resins using such bisphenol compounds as raw materials can be applied to various fields including automobiles, electrical and electronic equipment, housing and building materials, and in particular, equipments required in the field of electrical and electronic equipment parts in recent years. In response to the demands for miniaturization and high performance, it is highly expected that a resin excellent in flexibility, heat resistance and water absorption characteristics can be provided.

  By the way, the production of such a bisphenol compound is usually characterized by passing through a crystallization step in which a mixture containing the bisphenol compound is dissolved in a solvent, followed by precipitation of the bisphenol compound and separation of by-products. For example, as a method for producing a bisphenol compound having a long chain alkyl group, Patent Document 1 discloses 1,1-bis (1) 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. 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 59-131623 A Chinese Patent Application No. 1557777

  However, as a result of intensive studies by the present inventors, there is a tendency that by-products remain in the methods of Patent Documents 1 and 2, and the purification effect of the bisphenol compound is not necessarily high, and in order to obtain a high-purity bisphenol compound, a plurality of times are required. A tendency to require purification of was found. Furthermore, it has been clarified that the methods of Patent Documents 1 and 2 have a large loss due to the dissolution of the bisphenol compound in the solvent during the purification process of the bisphenol compound, and the isolation yield tends to decrease. From this, the subject that the bisphenol compound was not able to be refine | purified easily and with a high yield was discovered by the conventional method.

  In view of the above problems, the present invention provides a method for producing a bisphenol compound excellent in purification efficiency, that is, a bisphenol compound capable of easily obtaining a high-purity bisphenol compound in a crystal form excellent in handleability and in a high yield. It aims at providing the manufacturing method of.

As a result of intensive studies, the present inventors have found that a high-purity bisphenol compound can be easily produced through a step of precipitating a specific bisphenol compound from a solvent containing a specific solvent, and complete the present invention. It came to.
That is, the gist of the present invention resides in the following [1] to [6].

[1] A method for producing a bisphenol compound, comprising a step of precipitating a bisphenol compound represented by the following formula (1) from a solution of a solvent containing at least one aliphatic 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 each independently, 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 kind of the aliphatic alcohol solvent is a solvent containing at least one kind of each of the aliphatic alcohol solvent and the hydrocarbon solvent. A method for producing a 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 in the range of diffraction angles 2θ = 4.25 ± 0.15 ° and 2θ = 8.45 ± 0.20 ° in powder X-ray diffraction using CuKα rays. 1,1-bis (4-hydroxyphenyl) dodecane crystal characterized by the following.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the bisphenol compound excellent in the purification efficiency is provided. That is, according to the present invention, a high-purity bisphenol compound can be obtained easily and in a high yield in a crystal form excellent in handleability.

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

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example of the embodiments of the present invention, and the present invention is described below unless the gist of the present invention is exceeded. It is not limited to. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.

[mechanism]
The manufacturing method of the bisphenol compound of this invention includes the process of depositing the specific bisphenol compound demonstrated below from the solution of the solvent containing at least 1 type of aliphatic alcohol solvent.
Thus, 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 aliphatic alcohol solvent is excellent in the purification efficiency of the bisphenol compound is considered as follows. .

  The bisphenol compound represented by the following formula (1) has a polar phenol structure and a nonpolar long-chain alkyl moiety. For this reason, the phenol structure and the aliphatic alcohol solvent are likely to interact with each other, and the interacted part and the nonpolar long-chain alkyl site repel each other and precipitate as a powder, resulting in precipitation with another solvent. It seems that it is easy to make a peculiar crystal body different from the case of making it. Therefore, only the bisphenol compound can be specifically reduced in the aliphatic alcohol solvent with respect to other by-products, so that the purification efficiency is considered to have improved.

[Phenol compound]
<Structure>
A bisphenol compound produced by the method for producing a bisphenol compound of the present invention (hereinafter referred to as a phenol compound of the present invention) is 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 each independently, 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 because the carbon number of R ¹ is equal to or greater than the lower limit, the obtained resin is likely to exhibit excellent characteristics such as flexibility and low water absorption. Preferably, when the phenol compound of the present invention is used as a resin raw material, the obtained resin is preferable because it easily exhibits excellent properties in terms of 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 can easily exhibit low melting point and can be suitably used as a specific developer. become.

Preferred examples of the alkyl group having 7 to 19 carbon atoms of R ¹ include a linear or branched alkyl group, an alkyl group having a partial cyclic structure, and the like. 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 resulting resin is more likely to exhibit excellent properties such as flexibility. It is preferably a group, and more preferably a linear alkyl group.

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

Specific examples of the branched alkyl group for 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. Methylpentadecyl group, methylhexadecyl group, methylheptadecyl group, methyloctadecyl group;
Dimethylpentyl, dimethylhexyl, dimethylheptyl, dimethyloctyl, dimethylnonyl, dimethyldecyl, dimethylundecyl, dimethyldodecyl, dimethyltridecyl, dimethyltetradecyl, dimethylpentadecyl, dimethyl Hexadecyl group, dimethylheptadecyl group;
Trimethylhexyl, trimethylheptyl, trimethyloctyl, trimethylnonyl, trimethyldecyl, trimethylundecyl, trimethyldodecyl, trimethyltridecyl, trimethyltetradecyl, trimethylpentadecyl, trimethylhexadecyl;
Ethylpentyl, ethylhexyl, ethylheptyl, ethyloctyl, ethylnonyl, ethyldecyl, ethylundecyl, ethyldodecyl, ethyltridecyl, ethyltetradecyl, ethylpentadecyl, ethylhexadecyl 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;
Etc.

  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 preferred, and ethylpentyl group and ethylhexyl group are preferred. More preferred is an ethylpentyl group.

  In the example of the branched alkyl group, the position of branching is arbitrary.

Specific examples of the alkyl group having a partial 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;
Cyclohexylethyl group, cycloheptylethyl group, cyclooctylethyl group, cyclononylethyl group, cyclodecylethyl group, cycloundecylethyl group, cyclododecylethyl group;
A cyclohexylpropyl group, a cycloheptylpropyl group, a cyclooctylpropyl group, a cyclononylpropyl group, a cyclodecylpropyl group, a cycloundecylpropyl group, a 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;
An ethylcyclohexyl group, an ethylcycloheptyl group, an ethylcyclooctyl group, an ethylcyclononyl group, an ethylcyclodecyl group, an ethylcycloundecyl group, an 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;
A methylcyclohexylmethyl group, a methylcycloheptylmethyl group, a methylcyclooctylmethyl group, a methylcyclononylmethyl group, a methylcyclodecylmethyl group, a methylcycloundecylmethyl group, a 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;
Etc.

  Among these, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclohexylethyl group, cycloheptylethyl group, cyclooctylethyl group An alkyl group having a partial cyclic structure having 7 to 10 carbon atoms such as a cyclohexylmethyl group, a cycloheptylmethyl group, and a cyclooctylmethyl group is preferable, and a cycloheptyl group and a cyclooctyl group are more preferable.

  In the alkyl group having a partial 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 less than or equal to the above upper limit, 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 in that the characteristics are easily developed. Furthermore, when the number of carbon atoms is less than or equal to the above upper limit value, low melting point properties are easily developed, and it can be suitably used as a specific developer. R ² is a raw material that is easily available and the phenolic compound of the present invention is easily available, and when the phenolic compound of the present invention is used as a resin raw material, the obtained resin is excellent in terms of mechanical strength, heat resistance, and the like. In view of easily exhibiting the characteristics, a hydrogen atom or an alkyl group having 12 or less carbon atoms is preferable, a hydrogen atom or an alkyl group having 6 or less carbon atoms is particularly preferable, and a hydrogen atom or a methyl group is preferable. Is more preferable, and a hydrogen atom is more preferable.

Preferred examples of the alkyl group having 1 to 19 carbon atoms of R ² include a linear or branched alkyl group, an alkyl group having a partial cyclic structure, and the like. 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 resulting resin is more likely to exhibit excellent properties such as flexibility. Is preferably a straight-chain alkyl group.

Specific examples of the linear alkyl group represented by R ² include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and 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, linear alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, butyl group and undecyl group are preferable, and methyl group is particularly preferable.

Specific examples of the branched alkyl group represented by R ² include isopropyl group, methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group. Methyldodecyl group, methyltridecyl group, methyltetradecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl group, methyloctadecyl group;
t-butyl, dimethylethyl, methylpropyl, dimethylbutyl, dimethylpentyl, dimethylhexyl, dimethylheptyl, dimethyloctyl, dimethylnonyl, dimethyldecyl, dimethylundecyl, dimethyldodecyl Dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethylhexadecyl group, dimethylheptadecyl group;
Trimethylpropyl, trimethylbutyl, trimethylpentyl, trimethylhexyl, trimethylheptyl, trimethyloctyl, trimethylnonyl, trimethyldecyl, trimethylundecyl, trimethyldodecyl, trimethyltridecyl, trimethyltetradecyl Group, trimethylpentadecyl group, trimethylhexadecyl group;
Ethylpropyl, ethylbutyl, ethylpentyl, ethylhexyl, ethylheptyl, ethyloctyl, ethylnonyl, ethyldecyl, ethylundecyl, ethyldodecyl, ethyltridecyl, ethyltetradecyl, ethylpenta Decyl group, ethylhexadecyl group, ethylheptadecyl group;
Propylbutyl, propylpentyl, propylhexyl, propylheptyl, propyloctyl, propylnonyl, propyldecyl, propylundecyl, propyldodecyl, propyltridecyl, propyltetradecyl, propylpenta Decyl group, propylhexadecyl group;
Butylpentyl, butylhexyl, butylheptyl, butyloctyl, butylnonyl, butyldecyl, butylundecyl, butyldodecyl, butyltridecyl, butyltetradecyl, butylpentadecyl;
Etc.

  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 preferred, and ethylpentyl group and ethylhexyl group are preferred. More preferred is an ethylpentyl group. In the example of the branched alkyl group, the position of branching is arbitrary.

Specific examples of the alkyl group having a partial cyclic structure of R ² include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclo 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, propylcyclobutyl, propylcyclopentyl, propylcyclopropyl, propylcyclobutyl, propylcyclopentyl, propylcyclohexyl, propylcycloheptyl, propylcyclooctyl, propylcyclononyl, propylcyclodecyl Group, propylcycloundecyl group, propylcyclododecyl group;
Hexylcyclohexyl group, hexylcycloheptyl group, hexylcyclooctyl group, hexylcyclononyl group, hexylcyclodecyl group, hexylcycloundecyl group, hexylcyclododecyl group;
A methylcyclohexylmethyl group, a methylcycloheptylmethyl group, a methylcyclooctylmethyl group, a methylcyclononylmethyl group, a methylcyclodecylmethyl group, a methylcycloundecylmethyl group, a 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;
Etc.

  Among these, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclohexylethyl group, cycloheptylethyl group, cyclohexane An alkyl group having a partial 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 alkyl group having a partial cyclic structure, the substitution position of the substituent is arbitrary.

In said formula, R < ³ > -R < ⁶ > represents a hydrogen atom or a methyl group each independently. R ^{3 to} R ⁶ are these substituents, and therefore, when the phenol compound of the present invention is used as a resin raw material, the obtained resin is preferable in that it easily expresses excellent properties such as mechanical strength and heat resistance. . Among 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. At this time, it is preferable in that the purification efficiency can be further increased, R ⁴ and R ⁶ are more preferably hydrogen atoms, and R ^{3 to} R ⁶ are particularly preferably all hydrogen atoms.

<Melting point>
The phenolic compound of the present invention usually becomes a 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 not less than the lower limit, 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 above upper limit value, when the phenolic 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 a temperature at which the melting start of the phenol compound of the present invention is observed in the measurement in which the temperature is raised at a rate of 2 ° C./min using a melting point measuring device.

<Moisture content>
The phenol 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. It is preferable that the water content is equal to or more than the lower limit value, because 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 tends to be handled safely in terms of handling such as suppressing generation of static electricity. On the other hand, when the phenol content of the present invention is used as a resin raw material such as a polycarbonate resin or an epoxy resin, the foaming or bumping of the resin raw material derived from the generation of water vapor is suppressed because the water content is not more than the above upper limit value. It tends to be safe to handle and is preferable.

<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, still more preferably 10% by mass or less, and further preferably 5% by mass or less. It is particularly preferable that it is particularly preferably 1% by mass or less. When the phenolic compound of the present invention is used as a resin raw material such as a polycarbonate resin or an epoxy resin, the solvent content is not more than the above upper limit value, which is safe in terms of handling such as suppressing poisoning and ignition risk due to volatilization of organic solvents. This is preferable. The lower limit of the solvent content is not particularly defined, but is preferably 0.0001% by mass or more and more preferably 0.0005% by mass or more in terms of easy availability of the phenolic compound of the present invention. preferable.

<Example>
Hereinafter, the structure of bisphenol compounds represented by formula (1), illustrated by showing the combination of the substituents R ¹ to R ⁶ in the formula (1). The phenol compound of the present invention is not limited to the following examples.

Among these, as the phenolic compound of the present invention,
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 preferred,
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 preferred,
1,1-bis (4-hydroxyphenyl) dodecane 1,1-bis (4-hydroxyphenyl) undecane 1,1-bis (4-hydroxyphenyl) decane 1,1-bis (4-hydroxyphenyl) nonane is particularly preferred preferable. Such a bisphenol compound can be particularly suitably used as a resin raw material or a developer raw material.

[Production 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 do. As an example, for example, there is 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).

[In formula (2), ^{R 1} and ^{R 2} have the same meanings as ^{R 1} and ^{R 2} in the formula (1). ]

[In formula (3), ^{R 3} and ^{R 4} are the same as ^{R 3} and ^{R 4} in Formula (1). ]

<Aldehydes or ketones>
The aldehydes and ketones used in the production of the phenolic 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, etc. However, it is preferably an aldehyde compound or a ketone compound from the viewpoint that the production amount of by-products is small, and that the main by-product is water, thereby simplifying the purification process and reducing waste. In the case where a phenol compound is used as a resin raw material, an aldehyde compound is particularly preferable from the viewpoint of easily exhibiting characteristics such as mechanical strength of the obtained resin.

The aldehyde compound refers to a compound in which R ² is a hydrogen atom in the formula (2). Specific examples thereof include linear alkyl aldehydes, branched alkyl aldehydes, and alkyl aldehydes having a partial cyclic structure. Of these, when the phenolic compound of the present invention is used as a resin raw material, it is preferably a linear alkyl aldehyde or a branched alkyl aldehyde in terms of easily expressing properties such as mechanical strength of the obtained resin, A linear alkyl aldehyde is particularly preferred.

  Specific examples of the linear alkyl aldehyde include n-octanal, n-nonanal, n-decanal, n-undecanal, n-dodecanal, n-tridecanal, n-tetradecanal, n-pentadecanal, n -Hexadecanal, n-heptadecanal, n-octadecanal, n-nonadecanal, n-nonadecylaldehyde, n-icosylaldehyde, etc. are mentioned, n-octanal, n-nonanal, n-decanal, Linear alkyl aldehydes having 8 to 19 carbon atoms such as n-undecanal, n-dodecanal, n-tridecanal, n-heptadecanal, n-octadecanal and n-nonadecanal are preferred, and n-nonal, n -Decanal, n-undecanal, n-dodecanal are more preferred, n-do Canard is particularly preferred.

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, methyl tetradecyl aldehyde, Methyl pentadecyl aldehyde, methyl hexadecyl aldehyde, methyl heptadecyl aldehyde, methyl octadecyl aldehyde, methyl nonadecyl aldehyde;
Dimethylpentylaldehyde, dimethylhexylaldehyde, dimethylheptylaldehyde, dimethyloctylaldehyde, dimethylnonylaldehyde, dimethyldecylaldehyde, dimethylundecylaldehyde, dimethyldodecylaldehyde, dimethyltridecylaldehyde, dimethyltetradecylaldehyde, dimethylpentadecylaldehyde, dimethyl Hexadecylaldehyde, dimethylheptadecylaldehyde, dimethyloctadecylaldehyde;
Trimethylhexylaldehyde, trimethylheptylaldehyde, trimethyloctylaldehyde, trimethylnonylaldehyde, trimethyldecylaldehyde, trimethylundecylaldehyde, trimethyldodecylaldehyde, trimethyltridecylaldehyde, trimethyltetradecylaldehyde, trimethylpentadecylaldehyde, trimethylhexadecylaldehyde, Trimethylheptadecyl aldehyde;
Ethyl pentyl aldehyde, ethyl hexyl aldehyde, ethyl heptyl aldehyde, ethyl octyl aldehyde, ethyl nonyl aldehyde, ethyl decyl aldehyde, ethyl undecyl aldehyde, ethyl dodecyl aldehyde, ethyl tridecyl aldehyde, ethyl tetradecyl aldehyde, ethyl pentadecyl aldehyde, ethyl hexa Decyl aldehyde, ethyl heptadecyl aldehyde, ethyl octadecyl aldehyde;
Propylhexylaldehyde, propylheptylaldehyde, propyloctylaldehyde, propylnonylaldehyde, propyldecylaldehyde, propylundecylaldehyde, propyldodecylaldehyde, propyltridecylaldehyde, propyltetradecylaldehyde, propylpentadecylaldehyde, propylhexadecylaldehyde, 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;
Etc.

  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, ethyl pentadecyl aldehyde, etc. are preferred, ethyl pentyl aldehyde, ethyl hexyl aldehyde are more preferred, Ethylhexyl aldehyde is particularly preferred.

  In addition, in the example of the branched alkyl aldehyde, the position of branching is arbitrary.

Specific examples of the alkyl aldehyde having a partial 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;
Formyldiethylcyclohexane, formyldiethylcycloheptane, formyldiethylcyclooctane, formyldiethylcyclononane, formyldiethylcyclodecane, formyldiethylcycloundecane, formyldiethylcyclododecane;
Formylpropylcyclohexane, formylpropylcycloheptane, formylpropylcyclooctane, formylpropylcyclononane, formylpropylcyclodecane, formylpropylcycloundecane, formylpropylcyclododecane, formylcyclohexylcyclohexane;
Etc.

  Of these, formylcycloheptane, formylcyclooctane, formylcyclononane, formylcyclodecane, formylmethylcyclohexane, formylmethylcycloheptane, formylmethylcyclooctane, formyldimethylcyclohexane, formyldimethylcycloheptane, formylethylcyclohexane, formylethylcyclohexane Alkyl aldehydes having a partial cyclic structure having 8 to 11 carbon atoms such as heptane are preferred, and formylcycloheptane and formylcyclooctane are more preferred.

  In the example of an alkyl aldehyde having a partial cyclic structure, the substitution position of the formyl group is arbitrary.

The said ketone compound points out the compound whose R < ² > is a C1-C19 alkyl group in the said 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-heneicosanone, 12-tricosanone, 14-heptacosanone, 16-hentriacontanone, 18-pentacanone Triacontanon etc. are mentioned. Among these, R ² such as 2-nonanone, 2-decanone, 2-undecanone, 2-dodecanone, 2-tridecanone, 2-tetradecanone, 2-pentadecanone, or the like, or 9-heptadecanone, 11- Preferred are those in which R ¹ and R ² are the same, such as heneicosanone, 10-nonadecanone, 12-tricosanone, 16-hentriacontanone, 18-pentatriacontanone, 2-nonanone, 2-decanone, 2-undecanone, 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 addition, in the manufacturing process of the phenol compound of this invention, it is preferable to use these aldehydes or ketones independently from a viewpoint of improving the purification efficiency of the phenol compound of this invention.

<Monophenols>
Specific examples of 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. Among these, when the phenol compound of the present invention is used as a resin raw material, it is preferable to use phenol or o-cresol, and phenol is used in that excellent properties such as mechanical strength of the obtained resin are easily exhibited. It is particularly preferred. These monophenols may be used alone or in combination of two or more. In addition, in the manufacturing process of the phenol compound of this invention, it is preferable to use these phenols independently from a viewpoint of improving the purification efficiency of the phenol compound of this invention.

<Ratio of monophenols / aldehydes or ketones>
The ratio of aldehydes or ketones to monophenols in the production of the phenolic compound of the present invention is not particularly limited as long as the phenolic compound of the present invention is generated. Is usually 1 mol times or more, preferably 2 mol times or more, and more preferably 3 mol times or more. It exists in the tendency which can manufacture the phenolic compound of this invention efficiently because the quantity of monophenol is more than the said lower limit, and 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, particularly preferably 10 mol times or less. It is preferable that the amount of monophenols is not more than the above upper limit value because the load of the step of separating unreacted monophenols tends to be reduced during the production of the phenol compound of the present invention.

<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 acids, heterogeneous acid catalysts such as cation exchange resins, and the like. The types and amounts 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 during production, and cost. In addition, these acid catalysts may be used independently and may be used in mixture of 2 or more types.

<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. Specific examples of the third component include quaternary ammonium salts such as tetraethylammonium bromide, tetrabutylammonium hydrosulfate, and tetrabutylammonium chloride; methanethiol, ethanethiol, butanethiol, octanethiol, dodecanethiol, mercaptoacetic acid , 3-mercaptopropionic acid, 2-mercaptoethanol, 2-aminoethanethiol, ethyl thiolactate, thiobutyric acid, pentaerythritol tetrakis (mercaptoacetic acid), 1,4-butanediol bis (thioglycolic acid), 2-ethylhexyl ( And sulfur-containing compounds such as thioglycolic acid. Among these, it is preferable to use a sulfur-containing compound as the third component because the production of the phenol compound of the present invention is easy. On the other hand, it is preferable not to include these third components in that the separation of the phenol compound of the present invention from the third component becomes unnecessary and the purification process of the phenol compound of the present invention can be simplified. 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 phenolic compound of the present invention is not particularly defined as long as the phenolic compound of the present invention can be produced efficiently, but the amount of the third component relative to the aldehydes or ketones subjected to the reaction is not limited. Usually, it is 0.001 mol times or more, preferably 0.005 mol times or more, particularly preferably 0.01 mol times or more. It exists in the tendency which can manufacture the phenolic compound of this invention efficiently because the quantity of a 3rd component is more than the said lower limit, and is preferable. Further, 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, particularly preferably 0.2 mol times or less. . It is preferable that the amount of the third component is not more than the above upper limit value because the load of the step of separating the third component after the reaction tends to be reduced during the production of the phenol compound of the present invention. In addition, these 3rd components may be used independently and may be used in mixture of 2 or more types.

<Solvent>
When producing the phenol 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; branching 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 A branched alcohol solvent such as acetonitrile; a nitrile solvent such as acetonitrile; an ether solvent such as dibutyl ether; a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone; an ester solvent such as ethyl acetate and butyl acetate; and a nitrogen-containing solvent such as dimethylformamide and dimethylacetamide. Dimethylsulfoxy , Sulfur-containing solvents such as sulfolane; methylene chloride, chloroform, chlorine-containing solvents such as dichloroethane; benzene, toluene, and aromatic hydrocarbon solvents such as xylene. In addition, it is preferable to use these solvents from the viewpoint that the operability of the reaction can be improved, for example, by suppressing the solidification of the raw material during the reaction or by preventing an unexpected side reaction due to internal heat generation. It is preferable to use a solvent containing at least one of water and a hydrocarbon solvent from the viewpoint of preventing side reactions and facilitating removal of by-products during production of the phenol compound of the present invention. On the other hand, it is preferable not to use these solvents in that the separation of the phenol compound of the present invention and the solvent becomes unnecessary and the purification process of the phenol compound of the present invention can be simplified.

  The amount of the solvent used for producing the phenolic compound of the present invention is not particularly defined as long as the phenolic compound of the present invention can be produced efficiently, but the amount of the solvent with respect to aldehydes or ketones is usually 0.1 mass times. It is above, Preferably it is 0.2 mass times or more, Most preferably, it is 0.5 mass times or more. It is preferable that the amount of the solvent is equal to or more than the lower limit value because the effect of the solvent can be more efficiently exhibited during the production of the phenol compound of the present invention. The amount of the solvent with respect to aldehydes or ketones is usually 20 times by mass or less, preferably 10 times by mass or less, and particularly preferably 5 times by mass or less. It exists in the tendency which can manufacture the phenolic compound of this invention efficiently because the quantity of a solvent is below the said upper limit, and is preferable.

<Reaction temperature>
The reaction temperature for 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, the reaction mixture tends to be prevented from solidifying, which is preferable. On the other hand, the reaction temperature is usually 150 ° C. or lower, preferably 120 ° C. or lower, particularly preferably 90 ° C. or lower. It exists in the tendency which can manufacture the phenol compound of this invention efficiently because reaction temperature is below the said upper limit, and is preferable.

<Acid catalyst removal step>
The step of producing the phenol compound of the present invention preferably includes a step of removing the used acid catalyst after the reaction. Specific examples of the acid catalyst removal step include a neutralization step with a base, 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 efficiently included. The catalyst tends to be removed, which is preferable. These acid catalyst removal steps may be used alone or in combination of two or more.

  Moreover, when implementing these removal processes, it is preferable to implement in the state which melt | dissolved or suspended the mixture containing the phenolic compound of this invention in a solvent. Specific examples thereof include a solvent that can be used in producing the phenol compound of the present invention. Of these solvents, it is preferable to use a solvent selected from at least one of hydrocarbon solvents in terms of facilitating the purification treatment of the phenol compound of the present invention and reducing the production cost. It is particularly preferable to use a solvent containing a hydrocarbon solvent. In addition, these solvents may be used independently and may be used in mixture of 2 or more types. Moreover, when using a solvent for the reaction process of the phenolic compound of this invention, you may use the solvent as it is as a solvent of the said removal process.

  Specific examples of the base used in the neutralization step with a base include sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium hydroxide, potassium hydroxide, phosphorus An inorganic base having an alkali metal atom or an alkaline earth metal atom, such as sodium monohydrogen phosphate, potassium monohydrogen phosphate, sodium phosphate, potassium phosphate, magnesium hydroxide, calcium hydroxide, sodium hydride, sodium amide; An organic base having an alkali metal atom or an alkaline earth metal atom such as sodium citrate, potassium citrate, sodium succinate, potassium succinate, calcium succinate, sodium methoxide, potassium methoxide, potassium tert-butoxide; Jin, aniline, triethylamine, N, N-dimethylaniline, morpholine, 1,4-diazabicyclo [2,2,2] octane, a nitrogen-containing compounds such as diazabicycloundecene and the like. Of these, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium hydroxide, potassium hydroxide, sodium monohydrogen phosphate, potassium monohydrogen phosphate, A base having an alkali metal atom or an alkaline earth metal atom 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 the neutralized salt can be easily removed. 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. And acids containing. The type and amount of the second component are variously selected depending on the acid catalyst used in the reaction step and the type and amount of the base used in the neutralization step, and the target value of the acidity of the reaction mixture after neutralization.

  The reaction mixture after the neutralization step is preferably weakly acidic or weakly basic because the stability of the phenol compound of the present invention tends to be improved. Note that the reaction mixture is weakly acidic or weakly basic means that when water is added to the mixture and the weight ratio of water to other components is adjusted to 1: 3, the pH of the aqueous layer is usually 2 or more. , Preferably 3 or more, particularly preferably 4 or more, usually 11 or less, preferably 10 or less, 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. Among these, it is preferable to use water in that the purification process can be simplified.
In the above step, a second component may be added to increase the removal efficiency. Specific examples thereof include organic salts such as sodium methanesulfonate; inorganic salts such as sodium chloride and sodium sulfate. The kind and amount of the second component are variously selected depending on the removal efficiency of the acid catalyst.

Filtering agents used in the acid catalyst removal step by filtration include activated carbon, silica gel, activated clay, diatomaceous earth and other powdered, crushed or spherical filter agents; filter paper, filter cloth, thread wound filter and other fibrous or cloth-like forms And the like, and the like. These filtering agents are variously selected based on the properties of the acid catalyst used, the possibility of reuse of the acid catalyst, and the like.
In addition, these removal processes include unreacted raw materials, by-products, a part of components other than the phenolic compound of the present invention such as the second and third components used in the reaction or the removal process of the acid catalyst and the acid catalyst, or You may serve as the process of removing all.

<Concentration process>
The method for producing a phenol compound of the present invention comprises a step of removing low boiling components such as a solvent and unreacted raw material from the mixture containing the phenol compound of the present invention by concentration (hereinafter sometimes referred to as a concentration step). It is preferable to include. By carrying out this step, the extraction efficiency of 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 reduced pressure conditions. The heating temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and particularly preferably 80 ° C. or higher. Moreover, it is 200 degrees C or less normally, it is preferable that it is 180 degrees C or less, and it is especially preferable that it is 160 degrees C or less. It exists in the tendency which can implement a concentration process efficiently and can suppress decomposition | disassembly of the phenolic compound of this invention because heating temperature is in the said temperature range. In addition, the heating temperature in this concentration process refers to the temperature of the heat medium used for heating. The degree of vacuum is usually less than 760 Torr, preferably 200 Torr or less, more preferably 100 Torr or less, and particularly preferably 50 Torr or less. It exists in the tendency which can implement a concentration process efficiently because a pressure reduction degree is below the said upper limit. On the other hand, the lower limit value of the degree of decompression is not particularly defined, but is usually 0.1 Torr or more, preferably 1 Torr or more, more preferably 10 Torr or more, from the viewpoint that a widely used decompression device can be used. Particularly preferably, it is 20 Torr or more.

<Rough purification process>
When producing the phenol compound of the present invention, a reaction mixture usually obtained through the reaction of the above-mentioned aldehydes or ketones with monophenols, the subsequent step of removing the acid catalyst, or the step of removing and concentrating the acid catalyst. Becomes a mixture mainly composed of the phenol compound of the present invention. 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 sometimes referred to as “crystallization solvent”). After that, the step of precipitating the phenol compound of the present invention (hereinafter sometimes referred to as “deposition step”) is included. It is preferable to include a rough purification step of roughly removing the components.
In this rough purification step, preferably, after extracting the phenol compound of the present invention from the reaction mixture with an extraction solvent, the extract layer containing the phenol compound of the present invention is washed with water, and then the extract layer is subjected to reduced pressure. By removing the extraction solvent.

The extraction solvent used for this extraction is not particularly limited as long as it is a good solvent for the phenolic compound of the present invention. Specific examples thereof include solvents that can be used for producing the phenolic compound of the present invention. Among these, those excluding water are listed. Among these, it is preferable that 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 is included from the viewpoint of easy extraction of the phenol compound of the present invention, It is more preferable to include at least a solvent selected from any of ether solvents, ketone solvents, ester solvents, chlorine-containing solvents, and aromatic hydrocarbon solvents, and particularly preferable to include at least a solvent selected from aromatic hydrocarbon solvents, Among these, it is preferable that toluene or xylene is included, and it is most preferable that toluene is included.
These extractions may be used alone or in combination of two or more.

  The extraction solvent is preferably used in an amount of 0.1 mass times or more, more preferably 0.5 mass times or more, and particularly preferably 1 mass times or more based on the reaction mixture. It exists in the tendency which can extract the phenolic compound of this invention efficiently because the quantity of an extraction solvent is more than the said lower limit. Moreover, it is preferable that it is 20 mass times or less, It is more preferable that it is 10 mass times or less, It is especially preferable that it is 5 mass times or less. It exists in the tendency for the manufacturing efficiency of the phenolic compound of this invention to improve because the quantity of an extraction solvent is below the said upper limit.

In addition, the amount of water used for washing the extractant layer containing the phenolic compound of the present invention obtained by extraction is usually 0.1 mass times or more, and 0.5 mass times the total amount of the extractant layer. It is preferable that it is above, and it is particularly preferable that it is 1 mass or more. It exists in the tendency for the purification efficiency in a rough refinement | purification process to improve because the amount of water is more than the said lower limit. 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 extractant layer. It exists in the tendency which the manufacturing efficiency of the phenolic compound of this invention improves because the amount of water is below the said upper limit.
The number of washings of the extractant layer is usually about 1 to 20 times, preferably 2 to 10 times, and particularly preferably 3 to 6 times. When the number of water washings is equal to or higher than the lower limit, the purification efficiency in the rough purification step tends to be improved, and when the number is less than the upper limit, the production efficiency of the phenol compound of the present invention tends to be improved.

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

The purity of the crude product of the phenol 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 at 254 nm by liquid chromatography (LC) analysis.
In addition, you may implement this rough refinement | purification process combining the above-mentioned acid catalyst removal process and concentration process.

<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-described rough purification step (hereinafter sometimes referred to as “mixture containing the phenol compound of the present invention”). Is dissolved in a crystallization solvent containing an aliphatic alcohol solvent to form a solution, and then the phenol compound of the present invention is precipitated. Here, the aliphatic alcohol solvent in the present invention has a melting point of 30 ° C. or less, preferably 15 ° C. or less, has no carbon-carbon double bond in the molecule, and at least one hydroxy group is carbon. It represents a compound having a structure bonded to an atom, and includes a solvent having a hetero atom in addition to a hydroxy group.

  Specific examples of the aliphatic alcohol solvent described above include C1-C10 linear alcohol solvents containing one hydroxy group such as methanol, ethanol, n-propanol, n-butanol, and n-octanol; isopropanol, isopropanol C3-C10 branched alcohol solvent containing one hydroxy group such as butanol, 2-butanol, tert-butanol, 2-pentanol, 3-pentanol and 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-trifluoroethanol, 2- Butoxy ethanol, acetyl methanol, an alcohol solvent having 2 to 10 carbon atoms which contains a hetero atom, such as 2-acetoxyethyl ethanol. Among these, it is preferable to use an alcohol solvent containing one hydroxy group from the viewpoint of easy production of the phenol compound of the present invention, and an alcohol solvent containing no hetero atom other than the hydroxy group is particularly preferable. 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 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; C 5-18 such as isooctane. A branched hydrocarbon solvent such as cyclohexane, cyclooctane, methylcyclohexane, etc., a cyclic hydrocarbon solvent having 5 to 18 carbon atoms; water; a nitrile solvent such as acetonitrile; an ether solvent such as dibutyl ether; a methyl ethyl ketone, a methyl isobutyl ketone, etc. Ketone solvents; ester solvents such as ethyl acetate and butyl acetate; nitrogen-containing solvents such as dimethylformamide and dimethylacetamide; sulfur-containing solvents such as dimethylsulfoxide and sulfolane; chlorine-containing solvents such as methylene chloride, chloroform and dichloroethane; benzene, toluene, Xylene and other good Such as family hydrocarbon solvents. 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 in terms of improving the purification efficiency of the phenol compound of the present invention and facilitating production, and using the hydrocarbon solvent as the second solvent. It is particularly preferable to use a saturated chain hydrocarbon solvent such as the above-mentioned straight chain hydrocarbon solvent having 5 to 18 carbon atoms or a branched chain hydrocarbon solvent having 5 to 18 carbon atoms. In addition, these 2nd solvents may be used individually or in mixture of 2 or more types.

  The mixing ratio of the second solvent and the aliphatic alcohol solvent is not particularly specified, and may be appropriately set and used. Usually, the constituent ratio of the aliphatic alcohol solvent in the total crystallization solvent is 2 to 98% by weight, It is preferable that it is 2.5-90 mass%, and it is especially preferable that it is 3-30 mass%. When the constituent ratio of the aliphatic alcohol solvent in the total crystallization solvent is not less than the above lower limit value, the phenol compound of the present invention is easily obtained with high purity, and the phenol compound of the present invention is not more than the above upper limit value. This is preferable because it tends to be suppressed from being removed in the solvent, that is, the yield can be improved.

  The melting point of the crystallization solvent is usually 30 ° C. or lower, but is preferably 15 ° C. or lower, more preferably 5 ° C. or lower, and −10 ° C. or lower in terms of easy production of the phenol compound of the present invention. It is particularly preferred that The lower limit of the melting point is not particularly defined as long as the boiling point of the solvent is within the range described below. Here, the melting point of the crystallization solvent represents the melting point of the solvent after mixing when two or more solvents are mixed.

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

The precipitation step is usually carried out by mixing the mixture containing the phenolic compound of the present invention and the crystallization solvent described above into a solution, and then precipitating the phenolic compound of the present invention from this solution.
The mixing ratio of the mixture containing the phenolic compound of the present invention and the above-mentioned crystallization solvent is not particularly defined as long as the phenolic compound of the present invention can be efficiently precipitated. The mass ratio of the total 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 not less than the above lower limit value, the phenol compound of the present invention tends to be preferentially precipitated, whereas the phenol compound of the present invention is not more than the above upper limit value. It tends to improve efficiency, which is preferable.

  When mixing the mixture containing the phenolic compound of the present invention and the crystallization solvent, when the aforementioned second solvent is used in combination as the crystallization solvent, the aliphatic alcohol solvent and the second solvent may be added separately, You may mix with the mixture containing the phenolic compound of this invention in the mixed state. In addition, it is preferable to mix an aliphatic alcohol solvent and a 2nd solvent previously from a viewpoint of improving the manufacturing efficiency of the phenolic compound of this invention. Here, the temperature at the time of mixing the mixture containing the phenolic compound of the present invention and the crystallization solvent is usually 0 ° C. or higher, preferably 20 ° C. or higher, particularly preferably 40 ° C. or higher, and usually the boiling point of the crystallization solvent or lower. It is preferably (boiling point of crystallization solvent−5) ° C. or less, more preferably (boiling point of crystallization solvent−10) ° C. or less, particularly preferably (boiling point of crystallization solvent−20) ° C. or less. It is preferable that the temperature at the time of mixing is equal to or higher than the above lower limit value, whereby the solvent solubility of the phenol compound of the present invention can be improved and dissolved efficiently. On the other hand, when the temperature at the time of mixing is less than or equal to the above upper limit value, it is preferable because the boiling and volatilization of the solvent can be suppressed and the phenol compound of the present invention can be efficiently dissolved. Here, when two or more of the above-mentioned solvents are used as a crystallization solvent, the boiling point of the solvent represents the boiling point of the solvent after mixing.

  In the step of precipitating the phenol compound of the present invention from a solution obtained by dissolving the mixture containing the phenol compound of the present invention in a crystallization solvent, the solution is precipitated by cooling, the poor solvent of the phenol compound of the present invention is added, the solvent is evaporated, etc. Various methods generally used for crystallization from a solution can be applied. Among these, it is preferable to include a step of precipitation by cooling because the production of the phenol compound of the present invention becomes easy. The temperature at which the phenolic compound of the present invention is precipitated is not particularly limited as long as it does not impair the properties of the phenolic compound of the present invention, and can be appropriately set, but is usually −20 ° C. or higher, preferably −10 ° C. As described above, more preferably 0 ° C or higher. On the other hand, it is usually lower than the above mixing temperature, 70 ° C. or lower, preferably 65 ° C. or lower, more preferably 60 ° C. or lower, particularly preferably 55 ° C. or lower, 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 obtained by dissolving the mixture containing the phenol compound of the present invention in a crystallization solvent, a seed crystal of the phenol compound of the present invention may be added to improve the precipitation efficiency. . The amount of the seed crystal is usually 0.0001 to 10% by mass ratio with respect to the mixture containing the phenol compound of the present invention in terms of improving the production efficiency of the phenol compound of the present invention, and 0.0005 to 5%. It is preferable that it is 0.001-1%.

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

  The number of the precipitation steps is variously selected depending on the degree of purification of the phenolic compound of the present invention. However, from the viewpoint that the purification treatment can be simplified, it is usually preferably 3 times or less and more preferably 2 times or less. Preferably, it is particularly preferably once.

<Washing process>
You may wash | clean the powder of the phenolic compound of this invention obtained at the said precipitation process using the solvent for the purpose of surface washing | cleaning further. Specific examples of the solvent used in the washing step include the aliphatic alcohol solvent and the solvent exemplified as the second solvent. The temperature of the main 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. It exists in the tendency which can suppress dissolving the phenol compound of this invention excessively in the solvent for washing | cleaning because washing | cleaning temperature is in the said range, and it is preferable.

<Drying process>
The phenol compound of the present invention obtained through the 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 substantially free of a solvent. Also good. The temperature at the time of the solvent removal treatment in this drying step is usually 20 ° C. or higher, and preferably 40 ° C. or higher in order to allow the solvent removal treatment to proceed smoothly. The upper limit of the temperature is usually not higher than the melting point of the phenol compound of the present invention, preferably 100 ° C. or lower, more preferably 75 ° C. or lower, and particularly preferably 72 ° C. or lower.

[Crystal form]
By the method for producing a bisphenol compound of the present invention, the phenol compound of the present invention obtained through the above-described precipitation step can take a plurality of (for example, 2 to 3) crystal forms (crystal polymorph). 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 2θ = 4.25 ° in a powder X-ray diffraction method using CuKα rays. Crystals having at least one peak each in the range of ± 0.15 ° and 2θ = 8.45 ° ± 0.20 ° are preferred. 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 a difference in a solvent used when forming a crystal, that is, a crystallization solvent, and a measurement error. Specifically, when isopropanol is used as one component of the crystallization solvent for the preparation of the crystal, 2θ = 4.30 ° ± 0.05 ° and 2θ = 8.58 ° ± 0.05 °, When butanol is used as one component of the crystallization solvent, 2θ = 4.22 ° ± 0.05 ° and 2θ = 8.45 ° ± 0.05 °, and when isobutanol is used as one 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 °.

  The crystal body in the present invention may be composed of only one crystal form or a mixture of a plurality of crystal forms. If it is a crystal | crystallization which shows the said X-ray-diffraction peak behavior, when manufacturing the phenolic compound of this invention, the effect of this invention of being excellent in refinement | purification efficiency can fully be exhibited.

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

  Examples of the present invention are shown below, but the present invention is not limited thereto. In addition, the various analysis methods in an Example are as follows. Moreover, the symbol of each compound is based on Table 1 of the illustration mentioned above of the bisphenol compound represented by Formula (1).

[Liquid chromatography (LC) analysis]
A 50 mg sample was dissolved in 10 ml acetonitrile. The obtained solution was analyzed with an HPLC analyzer (LC-2010 manufactured by Shimadzu Corporation). The conditions were as follows.
(Measurement condition)
Controller: SCL-10AVP manufactured by Shimadzu Corporation
Column: Inertsil ODS3V (4.6 × 150 mm, 5 μm) manufactured by GL Sciences Inc.
Column oven: Shimadzu CTO-10AVP, 40 ° C
Pump: Shimadzu LC-10ADVP, flow rate 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 (concentration change linearly, 5-30 minutes)
K1 / K2 = 95/5 (30-80 minutes)
(Ratio is volume ratio)
Detector: Shimadzu Corporation SPD-10AVP UV254nm
(Analysis conditions)
Software: LC-solution ver. 1.22SP1
Setting: Width = 5, Slope = 200, Drift = 0, T.P. DBL = 1000, Min. Area = 500
LC purity was determined from area% at 254 nm. The reaction selectivity and yield were determined by an absolute calibration curve method by preparing a calibration curve for the target compound in advance.

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

[Example 1]
<Production of Compound (P-1)>
Phenol (220 g, 2.3 mol) was heated to 40 ° C. for melting, and 35% concentrated hydrochloric acid (2.9 g, 0.028 mol) was added. There, the liquid mixture of n-dodecanal (86g, 0.47mol) and toluene (51g) was dripped over 4 hours at 45 degrees C or less of internal temperature. After dripping, after aging at 40 ° C. for 1 hour, the reaction was stopped with an aqueous sodium hydrogen carbonate solution. The selectivity of compound (P-1) in the reaction mixture was 50.2%. After phenol was distilled off from the reaction mixture under reduced pressure at 160 ° C. and 20 Torr, the residue (181 g) was extracted with toluene (340 g) and washed with water (215 g) three times. 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 resulting crude product and heated to 60 ° C. to dissolve. 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 with a mixture 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%. 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 resulting slurry was filtered and washed with a mixture of isopropanol (6.0 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 99.0%, and the yield was 43.4%. The obtained solid had X-ray crystal diffraction peaks (2θ) of 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 heated to 60 ° C. to dissolve. 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 with a mixture of 2-butanol (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 99.3%, and the yield was 42.1%. The obtained solid had X-ray crystal diffraction peaks (2θ) of 4.22 °, 4.86 ° and 8.45 °.

[Example 4]
After obtaining a crude product of compound (P-1) as in Example 1, isobutanol (77 g) and heptane (430 g) were added, and the mixture was heated to 60 ° C. to dissolve. 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 with a mixture of 2-butanol (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 99.2%, and the yield was 40.3%. The obtained solid had X-ray crystal diffraction peaks (2θ) of 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. for melting, and 35% concentrated hydrochloric acid (2.9 g, 0.028 mol) was added. Thereto, n-dodecanal (86 g, 0.47 mol) was added dropwise at an internal temperature of 45 ° C. or less over 4 hours. After dripping, after aging at 40 ° C. for 1 hour, 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 the phenol was distilled off from the reaction mixture under reduced pressure at 160 ° C. and 20 Torr, the residue (180 g) was extracted with toluene (340 g) and washed with water (215 g) three times. 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)>
To the obtained crude product, isopropanol (57 g) and heptane (260 g) were added and heated to 60 ° C. to dissolve. After cooling to 55 ° C. and holding, seed crystals (compound (P-1), 52 mg) were added and held for 1 hour. Thereafter, 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 with a mixture of isopropanol (4 g) and heptane (96 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 99.5%, and the yield was 43.8%. The obtained solid had X-ray crystal diffraction peaks (2θ) of 4.27 ° and 8.51 °.

[Example 6]
<Production of Compound (P-6)>
Phenol (220 g, 2.3 mol) was heated to 40 ° C. for melting, and 35% concentrated hydrochloric acid (2.9 g, 0.028 mol) was added. Thereto, n-octadecanal (125 g, 0.47 mol) was added in portions at an internal temperature of 45 ° C. or less over 4 hours. After dripping, after aging at 40 ° C. for 1 hour, the reaction was stopped with an aqueous sodium hydrogen carbonate solution. The selectivity of compound (P-6) in the reaction mixture was 47.6%. After the phenol was distilled off from the reaction mixture under reduced pressure at 160 ° C. and 20 Torr, the residue (220 g) was extracted with toluene (340 g) and washed three 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 resulting crude product and heated to 60 ° C. to dissolve. 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 with a mixture of isopropanol (4 g) and heptane (96 g) at 15 ° C. 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]
<Production of Compound (P-19)>
Phenol (18.8 g, 0.200 mol) was heated to 40 ° C. and melted, 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. A sodium hydrogen carbonate aqueous 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%. After the phenol was distilled off from the reaction mixture under reduced pressure at 160 ° C. and 20 Torr, the residue (8.8 g) was extracted with toluene (15 g) and washed three 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 heated to 70 ° C. to dissolve. After the temperature was lowered to 42 ° C. and held, seed crystals (compound (P-19), 2.4 mgg) were added and held for 1 hour. Thereafter, 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 with a mixture 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 the mixture was heated to 40 ° 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 by spraying 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 obtained solid had X-ray crystal diffraction peaks (2θ) of 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 heated to 60 ° C. to dissolve. 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 mixture of toluene (52 g) and heptane (52 g) was added and washed at 15 ° C. by sprinkling. 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 obtained solid had X-ray crystal diffraction peaks (2θ) of 4.94 °, 8.26 ° and 8.71 °.

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

[Comparative Example 4]
In the same manner as in Example 7, a crude product of compound (P-19) was obtained. 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%, and the solution Was concentrated to dryness under reduced pressure to remove the solvent, but 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.
Moreover, the XRD crystal diffraction patterns of the compound (P-1) obtained in Examples 1 to 4 and Comparative Examples 1 and 2 are shown in FIGS.

When crystallizing with a solvent containing an aliphatic alcohol solvent as in Examples 1 to 7, it is clear that a bisphenol compound with sufficient purity can be obtained in one precipitation step and the yield is high. When other solvents were used as crystallization solvents 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. In addition, when Example 7 and Comparative Examples 3 and 4 are compared, the bisphenol compound obtained is oily even when other solvents are used or even when a bisphenol compound of sufficient purity is obtained by silica gel column chromatography. However, it can be seen that it can be obtained as a powder through the precipitation step according to the method of the present invention.
Such an efficient purification can be achieved by the method of the present invention because the aliphatic alcohol solvent easily interacts with only the phenolic compound of the present invention to form a specific crystal and has a high byproduct removal effect. This is probably because the crystallinity is improved. The fact that the crystal of the bisphenol compound obtained through the precipitation step according to the method of the present invention has a unique crystal structure indicates that the results of X-ray crystal diffraction peaks are those of Examples 1 to 4, Comparative Example 1 and This is supported by the fact that the two differ greatly.

Claims (6)

The manufacturing method of the bisphenol compound characterized by including the process of depositing the bisphenol compound represented by following formula (1) from the solution of the solvent containing at least 1 type of aliphatic 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 each independently, Represents a hydrogen atom or a methyl group. ]   The method for producing a bisphenol compound according to claim 1, wherein the aliphatic alcohol solvent is a branched alcohol solvent having 3 to 10 carbon atoms.   The method for producing a bisphenol compound according to claim 1 or 2, wherein the solvent containing at least one kind of the aliphatic alcohol solvent is a solvent containing at least one kind of each of the aliphatic alcohol solvent and the hydrocarbon solvent. . The method for producing a bisphenol compound according to any one of claims 1 to 3, wherein R ² in the formula (1) is a hydrogen atom. The method for producing a bisphenol compound according to claim 4, wherein R ^{3 to} R ⁶ in the formula (1) are hydrogen atoms.   It has at least one X-ray diffraction peak in the range of diffraction angles 2θ = 4.25 ± 0.15 ° and 2θ = 8.45 ± 0.20 ° in powder X-ray diffractometry using CuKα rays. A crystal of 1,1-bis (4-hydroxyphenyl) dodecane.

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