JP2021152001A - Bisphenol composition and method for producing the same and method for producing polycarbonate resin - Google Patents

Abstract

To provide a bisphenol composition that is excellent in methanol dissolution color, melting color difference, and polymerization activity and a method for producing the same.SOLUTION: A bisphenol composition has bisphenol and a bisphenol sulfonic acid. The content of the bisphenol is 95 mass% or more relative to the bisphenol composition. In a method for producing the bisphenol composition, a bisphenol sulfonic acid is produced as a by-product in the process of producing the bisphenol.SELECTED DRAWING: None

Description

The present invention relates to a bisphenol composition and a method for producing the same. The present invention also relates to a method for producing a polycarbonate resin.

Bisphenol is useful as a raw material for polymer materials such as polycarbonate resins, epoxy resins, and aromatic polyester resins. As typical bisphenols, for example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and the like are known (Patent Documents 1 and 2). ).

Japanese Unexamined Patent Publication No. 62-138443 Japanese Unexamined Patent Publication No. 2014-40376

Polycarbonate resin, which is a typical use of bisphenol, is required to be colorless and transparent. The color tone of the polycarbonate resin is greatly affected by the color tone of the raw material. Therefore, the color tone of bisphenol, which is a raw material, is also required to be colorless. Here, since it is difficult to directly quantify the color of bisphenol, in the present invention, bisphenol is dissolved in methanol to quantify the color difference, and this color tone is referred to as "methanol-dissolved color".

Further, in the production of the polycarbonate resin, particularly in the melting method, the bisphenol is melted to produce the polycarbonate resin, so that the polycarbonate resin is exposed to a high temperature. Therefore, the thermal color stability of bisphenol is also required. In the present invention, this color tone is referred to as "melt color difference".

Further, when the bisphenol contains a substance that poisons the polymerization catalyst, the polymerization reaction does not proceed, and when the bisphenol contains a substance having a polymerization catalytic action, the polymerization reaction proceeds excessively, and the polycarbonate resin having a desired molecular weight Cannot be obtained. Therefore, in order to obtain a polycarbonate resin having a desired molecular weight, bisphenol having excellent polymerization activity is required.

As for the polycarbonate resin, there is a demand for a polycarbonate resin having a molecular weight as designed and having a good color tone. Therefore, in order to produce such a polycarbonate resin, bisphenol as a raw material is required to have excellent methanol-dissolved color and melt color difference, and also have excellent polymerization activity.

The present invention has been made in view of the above-mentioned conventional circumstances, and an object of the present invention is to provide a bisphenol composition having good methanol-dissolved color, melt-color difference, and polymerization activity, and a method for producing the same. Another object of the present invention is to provide a method for producing a polycarbonate resin having an excellent color tone using this bisphenol composition.

As a result of diligent studies to solve the above problems, the present inventors have found that a bisphenol composition containing a specific compound is excellent in methanol-dissolved color, melt-color difference, and polymerization activity. Further, they have found that a polycarbonate resin having an excellent color tone can be produced by using this bisphenol composition, and have completed the present invention.

一般式（ｉ）及び一般式（ｉｉ）において、Ｘは、水素原子または金属原子を表す。
［４］ 前記ビスフェノールが、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン又は１，１−ビス（４−ヒドロキシ−３−メチルフェニル）シクロヘキサンである前記［１］乃至［３］のいずれかに記載のビスフェノール組成物。
［５］ 前記［１］乃至［４］のいずれかに記載のビスフェノール組成物の製造方法であって、前記ビスフェノールを製造する際に前記ビスフェノールスルホン酸類を副生させるビスフェノール組成物の製造方法。
［６］ 芳香族アルコールと、ケトン又はアルデヒドとを、硫酸を含む酸触媒の存在下で縮合させてビスフェノールを生成させる反応工程（Ｓ１）と、前記反応工程（Ｓ１）で得られた反応液から水相を除去し、ビスフェノールを含有する有機相（Ｏ１）を得る工程（Ｓ２）と、前記有機相（Ｏ１）を、除去する水相のｐＨが８．５以上の塩基性になるように、脱塩水及び／又は塩基性水溶液を用いて洗浄し、有機相（Ｏ２）を得る第１洗浄工程（Ｓ３）と、前記有機相（Ｏ２）を、除去する水相の電気伝導度が１．０μｓ／ｃｍ以上２０μs／ｃｍ以下となるまで、脱塩水を用いて洗浄し、有機相（Ｏ３）を得る第２洗浄工程（Ｓ４）と、前記有機相（Ｏ３）を晶析してビスフェノール組成物を得る晶析工程（Ｓ５）と、を有する前記［５］に記載のビスフェノール組成物の製造方法。
［７］ 前記［１］乃至［４］のいずれかに記載のビスフェノール組成物の製造方法であって、前記ビスフェノールに前記ビスフェノールスルホン酸類を添加するビスフェノール組成物の製造方法。
［８］ 前記［１］乃至［４］のいずれかに記載のビスフェノール組成物を用いたポリカーボネート樹脂の製造方法。
［９］ 粘度平均分子量が１５０００以上、３５０００以下のポリカーボネート樹脂を製造する前記［８］に記載のポリカーボネート樹脂の製造方法。 That is, the gist of the present invention lies in the following [1] to [9].
[1] A bisphenol composition containing bisphenol and bisphenol sulfonic acids, wherein the content of the bisphenol with respect to the bisphenol composition is 95% by mass or more.
[2] The bisphenol composition according to the above [1], wherein the content of the bisphenol sulfonic acids in the bisphenol composition is 2% by mass or more and 600% by mass or less.
[3] The bisphenol composition according to the above [1] or [2], wherein the bisphenol sulfonic acid is a compound represented by the general formula (i) or the general formula (ii).

In the general formula (i) and the general formula (ii), X represents a hydrogen atom or a metal atom.
[4] The above [1] to [3], wherein the bisphenol is 2,2-bis (4-hydroxy-3-methylphenyl) propane or 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane. The bisphenol composition according to any one of.
[5] The method for producing a bisphenol composition according to any one of the above [1] to [4], wherein the bisphenol sulfonic acid is by-produced when the bisphenol is produced.
[6] From the reaction step (S1) in which an aromatic alcohol and a ketone or aldehyde are condensed in the presence of an acid catalyst containing sulfuric acid to produce bisphenol, and the reaction solution obtained in the reaction step (S1). The step (S2) of removing the aqueous phase to obtain the organic phase (O1) containing bisphenol, and the basicity of the aqueous phase from which the organic phase (O1) is removed is 8.5 or more. The electrical conductivity of the first washing step (S3) for washing with desalted water and / or a basic aqueous solution to obtain the organic phase (O2) and the aqueous phase for removing the organic phase (O2) is 1.0 μs. The second washing step (S4) to obtain the organic phase (O3) by washing with desalted water until it becomes / cm or more and 20 μs / cm or less, and the bisphenol composition by crystallizing the organic phase (O3). The method for producing a bisphenol composition according to the above [5], which comprises the obtaining crystallization step (S5).
[7] The method for producing a bisphenol composition according to any one of the above [1] to [4], wherein the bisphenol sulfonic acid is added to the bisphenol.
[8] A method for producing a polycarbonate resin using the bisphenol composition according to any one of the above [1] to [4].
[9] The method for producing a polycarbonate resin according to the above [8], which produces a polycarbonate resin having a viscosity average molecular weight of 15,000 or more and 35,000 or less.

According to the present invention, a bisphenol composition having good methanol-dissolved color, melt color difference, and polymerization activity is provided by containing a specific compound. Further, a polycarbonate resin having an excellent color tone is provided by a method for producing a polycarbonate resin using this bisphenol composition.

It is a flowchart which shows the example of the preferable production method of the bisphenol composition of this invention. It is a chart which shows ^{the 1} H NMR spectrum of the preparative material (holding time 9.5 minutes).

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

[Bisphenol composition]
The bisphenol composition of the present invention is a bisphenol composition containing bisphenol and bisphenol sulfonic acids, and the content of the bisphenol in the bisphenol composition is 95% by mass or more.
By containing 95% by mass or more of bisphenol and containing bisphenol sulfonic acids, a bisphenol composition having excellent methanol-dissolved color, melt color difference, and polymerization activity can be obtained.

<Bisphenol>
The bisphenol contained in the bisphenol composition of the present invention is usually a compound represented by the following general formula (1).

In the general formula (1), ^{examples of R 1 to} R ⁴ include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an aryl group, respectively. The alkyl group, alkoxy group, aryl group and the like may be substituted or unsubstituted. The alkyl group and the alkoxy group have 1 or more carbon atoms, and the upper limit thereof is preferably 12 or less, more preferably 8 or less, and further preferably 6 or less. The aryl group has 6 or more carbon atoms, and the upper limit thereof is preferably 12 or less, more preferably 8 or less.

Examples of R ^{1 to} R ⁴ include hydrogen atom, fluoro group, chloro group, bromo group, iodo group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group. , T-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group , Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentyloxy group, i-pentyloxy group, n-hexyloxy group, n-Heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, Cycloheptyl group, cyclooctyl group, cyclododecyl group, benzyl group, phenyl group, tolyl group, 2,6-dimethylphenyl group and the like can be mentioned.

Of these, R ² and R ³ are preferably hydrogen atoms because if they are sterically bulky, the condensation reaction does not easily proceed when bisphenol is condensed as described later. Further, R ¹ to R ⁴ is more preferably each independently a hydrogen atom or an alkyl group, R ^1, R ⁴ is each independently a hydrogen atom or an alkyl group, R ^2, R ³ is a hydrogen atom Is even more preferable.

In the general formula (1), ^{examples of R 5} and R ⁶ include a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group, respectively. The alkyl group, alkoxy group, aryl group and the like may be substituted or unsubstituted. The alkyl group and the alkoxy group have 1 or more carbon atoms, and the upper limit thereof is preferably 12 or less, more preferably 8 or less, and further preferably 6 or less. The aryl group has 6 or more carbon atoms, and the upper limit thereof is preferably 12 or less, more preferably 8 or less.

For example, hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group. , N-Heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, methoxy group, ethoxy group, n-propoxy group, i -Propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentyloxy group, i-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n -Nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, Examples thereof include a benzyl group, a phenyl group, a tolyl group and a 2,6-dimethylphenyl group.

R ⁵ and R ⁶ may be bonded or crosslinked with each other between the two groups, or R ⁵ and R ⁶ may be bonded together with adjacent carbon atoms to contain a heteroatom. An alkylidene group may be formed. The cycloalkylidene group is a divalent group obtained by removing two hydrogen atoms from one carbon atom of cycloalkane.
For example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene, cycloheptilidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclo Dodecylidene, fluorenilidene, xanthonilidene, thioxanthonilidene and the like can be mentioned.

Specific examples of the bisphenol represented by the general formula (1) include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, and 2, 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene , 3,3-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxy-3-methylphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis ( 4-Hydroxy-3-methylphenyl) pentane, 3,3-bis (4-hydroxyphenyl) heptane, 3,3-bis (4-hydroxy-3-methylphenyl) heptane, 2,2-bis (4-hydroxy) Phenyl) heptane, 2,2-bis (4-hydroxy-3-methylphenyl) heptane, 4,4-bis (4-hydroxyphenyl) heptane, 4,4-bis (4-hydroxy-3-methylphenyl) heptane However, it is not limited to these.

Among these, the bisphenol contained in the bisphenol composition of the present invention includes 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,2-bis (4-hydroxy-3,5-dimethylphenyl). Any one selected from the group consisting of propane and 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane is preferred, 2,2-bis (4-hydroxy-3-methylphenyl) propane or 1,1. -Bis (4-hydroxy-3-methylphenyl) cyclohexane is more preferred, and 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C) is particularly preferred.

The bisphenol composition of the present invention contains 95% by mass or more of bisphenol. The content of bisphenol with respect to the bisphenol composition of the present invention (mass of bisphenol / mass of bisphenol composition × 100 (%)) is preferably 99% by mass or more, more preferably 99.5% by mass or more. If the content of bisphenol is less than the above lower limit, it is not preferable for use as bisphenol. The upper limit of the content of bisphenol in the bisphenol composition of the present invention is to secure the content of bisphenol sulfonic acids, from the viewpoint of production cost, etc. From the viewpoint of mechanical properties of the polycarbonate resin such as brittleness, it is usually about 99.9% by mass.
Detection and quantification of bisphenol can be performed using a standard reverse phase column for high speed analysis. For example, a standard reverse phase column for high-speed analysis includes an ODS column having an inner diameter of 3 to 4.6 mm, a length of 10 to 30 cm, and a particle size of 3 to 5 μm. Specifically, Scherzo SM-C18 manufactured by Imtakat, Cadenza CD-C18, Unison UK-C18 and the like can be used. Details will be described in Examples.

<Bisphenol sulfonic acids>
The bisphenol sulfonic acids contained in the bisphenol composition of the present invention are bisphenol sulfonic acids and / or salts thereof.
The bisphenol sulfonic acid is a compound in which one hydrogen atom of one of the two hydroxyphenyl groups of bisphenol is _{replaced with a sulfonic acid group (SO 2 OH group).} The hydroxyphenyl group of bisphenol sulfonic acid may be one in which a hydrogen atom other than the hydrogen atom substituted with the sulfonic acid group is substituted with a hydroxyl group and a substituent other than the sulfonic acid group.
Examples of the bisphenol sulfonate include sodium salt, potassium salt, lithium salt and the like.

The bisphenol sulfonic acids are 44 bodies (bisphenol sulfonic acids having two hydroxyphenyl groups in which the hydroxyl group is in the 4-position position) and 24 bodies (hydroxyphenyl group in which the hydroxyl group is in the 2-position position and the hydroxyl group is in the 4-position position). (Bisphenol sulfonic acids having a hydroxyphenyl group at the position of), 22 bodies (bisphenol sulfonic acids having two hydroxyphenyl groups at the position of the hydroxyl group), etc., but 44 bodies are preferable, and the following The compound represented by the general formula (I) is more preferable.

^{R 1 to} R ⁴ in the general formula (I) are synonymous with ^{R 1 to} R ⁴ in the general formula (1). Preferable examples and specific examples thereof are as described in the above general formula (1). R ¹ to R ⁴ in R ¹ to R ⁴ and the formula in the formula (I) (1) can be the same, may be different, but are preferably the same.

X in the general formula (I) is a hydrogen atom or a metal atom. Examples of the metal atom include Group 1 elements of the periodic table such as a lithium atom, a sodium atom, a potassium atom, and a cesium atom. Of these, a hydrogen atom or a sodium atom is preferable because it is industrially inexpensive.

Among the compounds represented by the general formula (I), the bisphenol sulfonic acids are preferably bisphenol sulfonic acids represented by the following general formula (i) or general formula (ii).

In the general formula (i) and the general formula (ii), X is synonymous with the general formula (I). Similar to the general formula (I), X is preferably a hydrogen atom or a sodium atom.

The content of bisphenol sulfonic acids with respect to the bisphenol composition of the present invention (mass [μg] of bisphenol sulfonic acids / mass [kg] of bisphenol composition) is preferably 2 mass ppb or more, 3 mass ppb or more or 5 mass. It may be ppb or more. The upper limit thereof is preferably 600 mass ppb or less, more preferably 350 mass ppb or less, and further preferably 100 mass ppb or less.

If the content of bisphenol sulfonic acids with respect to the bisphenol composition is less than the above lower limit, it is difficult to obtain a bisphenol composition having a good methanol-dissolved color and melt color difference. Further, if the content of the bisphenol sulfonic acid in the bisphenol composition exceeds the above upper limit, the polymerization activity deteriorates, and the polymerization reaction may not proceed when the polycarbonate resin is produced.
Detection and quantification of bisphenol sulfonic acids can be performed using a standard reverse phase column for high speed analysis with a particle size of 3 μm. For example, as a standard reverse phase column for high-speed analysis having a particle size of 3 μm, an ODS-based column having an inner diameter of 3 to 4.6 mm, a length of 10 to 30 cm, and a particle size of 3 μm can be mentioned. Specific examples thereof include Scherzo SM-C18 manufactured by Imtakt, Cadenza CD-C18, and Unison UK-C18. Details will be described in Examples.

The content of bisphenol sulfonic acids in the bisphenol composition can be prepared by adding an appropriate amount of bisphenol sulfonic acids to bisphenol containing no or low concentration of purified bisphenol sulfonic acids. Further, as will be described later, a bisphenol product containing bisphenol sulfonic acids can be prepared as the bisphenol composition of the present invention by producing bisphenol sulfonic acids together with bisphenol in the reaction system during the production of bisphenol.

<Methanol-dissolved color of bisphenol composition>
The methanol-dissolved color of the bisphenol composition is a method for evaluating the color tone of the bisphenol composition itself. When the bisphenol composition is the final product, it is important that the methanol-dissolved color of the bisphenol composition is good.

The methanol-dissolved color of the bisphenol composition is used to evaluate the color tone of the bisphenol composition at room temperature. The lower the number of Hazen colors of the methanol-dissolved color of the bisphenol composition, the better the color tone of the bisphenol composition (closer to white). As a cause of deteriorating the methanol-dissolved color of the bisphenol composition, there is an inclusion of an organic coloring component or a metal.
The methanol-dissolved color of the bisphenol composition is measured at room temperature (about 20 ° C.) after the bisphenol composition is dissolved in methanol to prepare a uniform solution. Examples of the measuring method include a method of visually comparing with a standard solution of the number of Hazen colors, and a method of measuring the number of Hazen colors using a color difference meter such as "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd. The solvent used here is methanol. The mass ratio of bisphenol to the solvent is preferably selected as appropriate depending on the type of bisphenol.

The number of Hazen colors of the methanol-dissolved color of the bisphenol composition is preferably 20 or less, more preferably 10 or less, and particularly preferably 5 or less.

<Melted color difference of bisphenol composition>
Since the polycarbonate resin inherits the color tone of the raw material, it is important to use a bisphenol composition having a good color tone as the raw material for the polycarbonate resin that is required to be colorless and transparent.
Further, in the melt polymerization method, which is one of the methods for producing a polycarbonate resin, the color tone of the bisphenol composition at the time of melting (melt color difference of the bisphenol composition) is important because the polymerization reaction is carried out at a high temperature.

The melt color difference of the bisphenol composition is used to evaluate the color tone of the bisphenol composition at a temperature close to the polymerization temperature of polycarbonate. The measurement temperature of the melt color difference is the melting point of bisphenol + 50 ° C. The melt color difference of the bisphenol composition indicates that the lower the number of Hazen colors, the better the color tone of the bisphenol composition (closer to white). As a cause of exacerbating the melt color difference of the bisphenol composition, there are components that are colored by heating in addition to organic coloring components and metal contamination.
The melt color difference of the bisphenol composition is measured in advance by melting the bisphenol composition at a temperature close to the polymerization temperature and measuring the time at which the temperature is stable. Examples of the measuring method include a method of visually comparing with a standard solution of the number of Hazen colors, and a method of measuring the number of Hazen colors using a color difference meter such as "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd.

The number of Hazen colors in the melt color difference of the bisphenol composition is preferably 40 or less, more preferably 30 or less, and particularly preferably 20 or less.

<Polymerization activity of bisphenol composition>
In the melt polymerization method, which is one of the methods for producing a polycarbonate resin, a very small amount of polymerization catalyst is used for the bisphenol composition. Therefore, in the melt polymerization method, when the bisphenol composition contains a polymerization catalyst toxic substance such as an acid catalyst (hydrogen chloride, sulfuric acid, sulfonic acid) used when synthesizing the bisphenol composition, the polymerization catalyst It is deactivated and the polymerization reaction does not proceed. Further, when the bisphenol composition contains a polymerization promoting substance such as sodium hydroxide or sodium carbonate, the polymerization activity becomes excessive, and it becomes difficult to obtain a polycarbonate resin having a predetermined molecular weight. Therefore, the polymerization activity of the bisphenol composition is important.
The polymerization activity of the bisphenol composition is, for example, preferably 240 minutes or less, more preferably 220 minutes or less, and further preferably 200 minutes or less in the subsequent polymerization time under the conditions for producing the polycarbonate resin described later in the examples. Further, under the same conditions, 120 minutes or more is preferable, 130 minutes or more is more preferable, and 140 minutes or more is further preferable.

In particular, in order to produce a polycarbonate resin having a predetermined molecular weight and having a good color tone, the methanol-dissolved color of the bisphenol composition, the melt color difference of the bisphenol composition, and the polymerization activity of the bisphenol composition are important.

[Manufacturing method of bisphenol composition]
The method for producing the bisphenol composition of the present invention containing 95% by mass or more of bisphenol and containing bisphenol sulfonic acids in a predetermined ratio is not particularly limited, and examples thereof include the following methods.
-Method (1) Method of adding bisphenol sulfonic acids to bisphenol-Method (2) Method of obtaining bisphenol products containing bisphenol sulfonic acids by by-producing bisphenol sulfonic acids when producing bisphenol

The method of adding bisphenol sulfonic acids to bisphenol of the method (1) may be a method of adding bisphenol sulfonic acids to solid bisphenol or a method of adding bisphenol sulfonic acids to molten bisphenol. In the method of adding bisphenol sulfonic acids to the bisphenol of the method (1), since it is necessary to separately prepare the bisphenol sulfonic acids, the bisphenol sulfonic acids are by-produced in the reaction system for producing the bisphenol of the method (2). A method in which the bisphenol product contains bisphenol sulfonic acids in a predetermined ratio is preferable.

<Manufacturing method of method (2)>
A suitable method as the method (2) is a reaction step (S1) in which an aromatic alcohol and a ketone or an aldehyde are condensed in the presence of an acid catalyst containing sulfuric acid to produce bisphenol, and a reaction step (S1). The step (S2) of removing the aqueous phase from the obtained reaction solution to obtain the organic phase (O1) containing bisphenol, and the pH of the aqueous phase from which the obtained organic phase (O1) is removed are 8.5 or more. The first washing step (S3) to obtain the organic phase (O2) and the obtained organic phase (O2) are removed by washing with desalted water and / or a basic aqueous solution so as to be basic. The second washing step (S4) of washing with desalted water until the electrical conductivity of the aqueous phase becomes 1.0 μs / cm or more and 20 μs / cm or less to obtain the organic phase (O3), and the obtained organic phase ( This is a method having a crystallization step (S5) of crystallizing O3) to obtain a bisphenol composition (hereinafter, referred to as “method (2-1)”).

By the method (2-1), an appropriate amount of bisphenol sulfonic acids produced as a by-product during the bisphenol production reaction can be contained in the bisphenol composition.
Further, by cleaning the first cleaning step so that the pH of the aqueous phase becomes equal to or higher than the above lower limit and the electrical conductivity of the aqueous phase in the second cleaning step falls within the above range, bisphenol sulfonic acids are appropriately retained. , By-products, residual catalyst, residual thiol and other impurities in the produced bisphenol can be highly removed. As a result, it is possible to obtain a bisphenol composition having a good hue, high polymerization reaction efficiency when used as a raw material bisphenol for a polycarbonate resin, and capable of producing a polycarbonate resin having an excellent hue. In particular, in the condensation reaction using thiol as a co-catalyst, acidic thionium is produced from the thiol, which is contained in the bisphenol composition and inhibits the polymerization reaction during the production of the polycarbonate resin. By performing a cleaning step in which the electrical conductivity of the aqueous phase is controlled, thionium can be efficiently removed and polymerization inhibition by thionium can be prevented.

FIG. 1 shows a flowchart of the method (2-1). Hereinafter, each step of the method (2-1) will be described.

<Reaction step (S1)>
In the reaction step (S1), bisphenol is produced by condensing an aromatic alcohol with a ketone or an aldehyde in the presence of an acid catalyst containing sulfuric acid.
The reaction for producing bisphenol is carried out according to the reaction formula (2) shown below. Further, in this bisphenol production reaction, bisphenol sulfonic acids are by-produced as one of the by-products.

^{R 1 to} R ⁶ in the reaction formula (2) are synonymous with those in the general formula (1).

(Aromatic alcohol)
The aromatic alcohol used for producing bisphenol is usually a compound represented by the following general formula (3).

^{R 1 to} R ⁴ in the general formula (3) ^{have the same meaning as R 1 to} R ⁴ in the general formula (1), and suitable examples and specific examples thereof are described in the general formula (1). It's a street.

Specific examples of the compound represented by the general formula (3) include phenol, methylphenol (cresol), dimethylphenol (xylenol), ethylphenol, propylphenol, butylphenol, methoxyphenol, ethoxyphenol, propoxyphenol, and butoxy. Phenol, benzylphenol, phenylphenol and the like can be mentioned.

Among them, any one selected from the group consisting of phenol, methylphenol and dimethylphenol is preferable, methylphenol or dimethylphenol is more preferable, and methylphenol is further preferable.

(Ketone or aldehyde)
The ketone or aldehyde used in the production of bisphenol is usually a compound represented by the following general formula (4).

Specific examples of the compound represented by the general formula (4) include formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde, and undecylaldehyde. Ketones such as dodecylaldehyde, acetone, butanone, pentanone, hexanone, heptanone, octanon, nonanone, decanone, undecanone, dodecanone and other ketones, benzaldehyde, phenylmethylketone, phenylethylketone, phenylpropylketone, cresylmethylketone, Arylalkyl ketones such as cresyl ethyl ketone, cresyl propyl ketone, xylyl methyl ketone, xylyl ethyl ketone, xsilyl propyl ketone, cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, Cyclic alcan ketones such as cyclononanone, cyclodecanone, cycloundecanone, and cyclododecanone; heterocyclic ketones such as fluorenone, xanthone, and thioxanthone can be mentioned.
Of these, acetone or cyclohexanone is preferable.

In the reaction of condensing aromatic alcohol with ketone or aldehyde, the molar ratio of aromatic alcohol to ketone or aldehyde ((number of moles of aromatic alcohol / number of moles of ketone) or (number of moles of aromatic alcohol / number of moles of aldehyde) )), If the amount is small, the amount of ketone or aldehyde increases, but if the amount is large, the aromatic alcohol is lost unreacted. From these facts, the molar ratio of the aromatic alcohol to the ketone or aldehyde is preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more. Further, it is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

(Acid catalyst)
The acid catalyst used in the production of bisphenol contains sulfuric acid.
Sulfuric acid is an acidic liquid represented by the chemical formula H ₂ SO _4. Generally, sulfuric acid is used as an aqueous solution of sulfuric acid diluted with water, and is called concentrated sulfuric acid or dilute sulfuric acid depending on its concentration. For example, dilute sulfuric acid is an aqueous sulfuric acid solution having a mass concentration of less than 90% by mass.
Production when the concentration of sulfuric acid (concentration of aqueous sulfuric acid solution _{(H 2 SO 4 + H 2} O) in H ₂ SO ₄₎ is low, the amount of water increases, it produces a reaction of bisphenol hardly proceeds, the bisphenol used The reaction time is long, and it may be difficult to efficiently produce bisphenol. Therefore, the concentration of sulfuric acid used is preferably 70% by mass or more, more preferably 75% by mass or more, and further preferably 80% by mass or more. The upper limit of the concentration of sulfuric acid used is usually 99.5% by mass or less or 99% by mass or less.

Moreover, the acid catalyst may contain other acids other than sulfuric acid. Examples of other acids include aromatic sulfonic acids such as hydrochloric acid, hydrogen chloride gas, phosphoric acid and p-toluene sulfonic acid, and aliphatic sulfonic acids such as methane sulfonic acid.

If the molar ratio of the acid catalyst to the ketone or aldehyde used for condensation ((number of moles of acid catalyst / number of moles of ketone) or (number of moles of acid catalyst / number of moles of aldehyde)) is small, as the condensation reaction progresses. The acid catalyst is diluted by the by-produced water and the reaction takes time. In addition, when the amount is large, the amount of ketones or aldehydes may increase. From these facts, the molar ratio of the acid catalyst to the ketone or aldehyde used for condensation is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more. The upper limit is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.

(Thiol)
In the production of bisphenol, thiol can be used as a co-catalyst in the reaction of condensing a ketone or aldehyde with an aromatic alcohol.
By using thiol as a co-catalyst, for example, in the production of 2,2-bis (4-hydroxy-3-methylphenyl) propane, 24 bodies (2- (2-hydroxy-3-methylphenyl) -2- (4) -Hydroxy-3-methylphenyl) Propane) is suppressed, and the selectivity of 44 bodies (2,2-bis (4-hydroxy-3-methylphenyl) propane) is increased, as well as the polymerization activity during the production of polycarbonate resin. The effect of improving the color tone of the obtained polycarbonate resin can be obtained. Although the details of the reason why the effect of improving the polymerization activity during the production of the polycarbonate resin and the effect of improving the color tone of the obtained polycarbonate resin are exhibited are not clear, the use of thiol is an inhibitor of the polymerization reaction for producing the polycarbonate resin. It is presumed that this is due to the fact that it is possible to suppress the production and the production of color-deteriorating substances.

Examples of the thiol used as a co-catalyst include mercaptocarboxylic acids such as mercaptoacetic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid and 4-mercaptobutyric acid, methyl mercaptan, ethyl mercaptan, propyl mercaptan and butyl. Mercaptan, Pentyl mercaptan, Hexyl mercaptan, Heptyl mercaptan, Octyl mercaptan, Nonyl mercaptan, Decyl mercaptan (decane thiol), Undecyl mercaptan (undecanthiolu), Dodecyl mercaptan (dodecane thiol), Tridecyl mercaptan, Tetradecyl mercaptan Examples thereof include alkyl thiols such as decyl mercaptan and aryl thiols such as mercaptophenol.

If the molar ratio of thiol to ketone or aldehyde used for condensation ((number of moles of thiol / number of moles of ketone) or (number of moles of thiol / number of moles of aldehyde)) is small, the reaction selectivity of bisphenol by using thiol is small. The effect of improvement cannot be obtained, and if it is too much, it may be mixed with bisphenol and the quality may deteriorate. From these facts, the lower limit of the molar ratio of thiol to ketone and aldehyde is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more. The upper limit thereof is preferably 1 or less, more preferably 0.5 or less, and further preferably 0.1 or less.

(Organic solvent)
In the production of bisphenol, an organic solvent is usually used to dissolve or disperse the produced bisphenol.
The organic solvent is not particularly limited as long as it does not inhibit the reaction for producing bisphenol, and examples thereof include aromatic hydrocarbons, aliphatic alcohols, and aliphatic hydrocarbons. Here, the substrate aromatic alcohol, ketone or aldehyde, co-catalyst thiol, and product bisphenol are removed from the organic solvent. These organic solvents may be used alone or in combination of two or more.

Examples of the aromatic hydrocarbon include benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, mesitylene and the like, and these organic solvents may be used alone or in combination of two or more. .. After using the aromatic hydrocarbon for the production of bisphenol, it can be recovered and purified by distillation or the like and reused. When reusing aromatic hydrocarbons, those having a low boiling point are preferable. One of the preferred aromatic hydrocarbons is toluene.

The aliphatic alcohol is an alkyl alcohol in which an alkyl group and a hydroxyl group are bonded. The fatty alcohol may be a monohydric aliphatic alcohol in which an alkyl group and one hydroxyl group are bonded, or may be a polyhydric aliphatic alcohol in which an alkyl group and two or more hydroxyl groups are bonded. Further, the alkyl group may be linear or branched, may be unsubstituted, or a part of the carbon atom of the alkyl group may be substituted with an oxygen atom.

The lipophilicity of the aliphatic alcohol increases as the number of carbon atoms increases, and it becomes difficult to mix with sulfuric acid and it becomes difficult to generate monoalkyl sulfate, which will be described later. Therefore, the aliphatic alcohol preferably has 12 or less carbon atoms, and preferably 8 or less carbon atoms. More preferred.

Further, the aliphatic alcohol is preferably an alcohol in which an alkyl group and one hydroxyl group are bonded, and more preferably an alcohol in which an alkyl group having 1 to 8 carbon atoms and one hydroxyl group are bonded. More preferably, it is an alcohol in which an alkyl group having 1 to 5 carbon atoms and one hydroxyl group are bonded.

Specific aliphatic alcohols include, for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol, i-pentanol, n-hexanol, n. -Heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, ethylene glycol, diethylene glycol, triethylene glycol and the like can be mentioned. One of the preferred aliphatic alcohols is methanol.

Examples of aliphatic hydrocarbons include linear hydrocarbons having 5 to 18 carbon atoms such as n-pentane, n-hexane, n-heptane, and n-octane, and branched chain hydrocarbons having 5 to 18 carbon atoms such as isooctane. , Cyclohexane, cyclooctane, methylcyclohexane and other cyclic hydrocarbons having 5 to 18 carbon atoms.

If the mass ratio of the organic solvent to the ketone or aldehyde used for condensation ((mass of organic solvent / mass of ketone) or (mass of organic solvent / mass of aldehyde)) is too large, the ketone or aldehyde and the aromatic alcohol Is difficult to react and it takes a long time to react. If it is too small, the amount of ketones or aldehydes will be increased, and the bisphenol produced may solidify. From these facts, the mass ratio of the organic solvent to the ketone or aldehyde at the time of preparation is preferably 0.5 or more, and more preferably 1 or more. The upper limit thereof is preferably 100 or less, more preferably 50 or less.
As will be described later, the organic solvent may be supplied in divided portions, and when the organic solvent is supplied in divided portions, the total amount of the organic solvent used for preparing the reaction solution with respect to the ketone or aldehyde is within the above range. Is preferable.

It is more difficult for bisphenol to decompose when the generated bisphenol is dispersed without being completely dissolved in an organic solvent. Further, it is preferable to use a solvent having a low solubility of bisphenol at room temperature because it is possible to reduce the loss when recovering bisphenol from the reaction solution after the reaction is completed (for example, the loss to the filtrate during crystallization). Examples of the organic solvent having low solubility of bisphenol at room temperature include aromatic hydrocarbons. Therefore, the organic solvent preferably contains aromatic hydrocarbons as a main component, preferably contains 55% by mass or more of aromatic hydrocarbons, more preferably 70% by mass or more, and 80% by mass. It is more preferable to contain% or more.

Further, since the acid catalyst contains sulfuric acid, when the organic solvent contains an aliphatic alcohol, the sulfuric acid reacts with the aliphatic alcohol to generate monoalkyl sulfate, and the catalytic action can also be obtained by this monoalkyl sulfate. The effect is obtained. Therefore, the organic solvent is preferably an organic solvent containing an aliphatic alcohol. Further, the aliphatic alcohol is preferably an alkyl alcohol having 8 or less carbon atoms because the lipophilicity increases as the number of carbon atoms increases, it becomes difficult to mix with sulfuric acid, and it becomes difficult to generate monoalkyl sulfate.
By reacting sulfuric acid with an aliphatic alcohol in this way to generate monoalkyl sulfate, the acid strength of the acid catalyst can be controlled, and condensation (mass increase) and coloring of the raw material ketone or aldehyde can be suppressed. .. Therefore, it is possible to easily and efficiently produce bisphenol in which excessive production of bisphenol sulfonic acids and production of other by-products are suppressed and coloration is reduced.

When sulfuric acid is reacted with an aliphatic alcohol to generate monoalkyl sulfate and its catalytic action is also used, if the molar ratio of the aliphatic alcohol to sulfuric acid (the number of moles of the aliphatic alcohol / the number of moles of the sulfuric acid) is small, the raw material Condensation (enhancement) and coloring of the ketone or aldehyde of the above becomes remarkable. On the other hand, if the amount is too large, the sulfuric acid concentration decreases and the reaction becomes slow. From these facts, the lower limit of the molar ratio of the aliphatic alcohol to sulfuric acid is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.1 or more. The upper limit is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.

From the above, the organic solvent can contain, for example, aromatic hydrocarbons and aliphatic alcohols, and the organic solvent contains 1 to 99.9% by mass of aromatic hydrocarbons and 0.1 by mass of the aliphatic alcohol. It can contain from 10% by mass.

As described above, the organic solvent preferably contains an aromatic hydrocarbon as a main component, and 90 to 99.9% by mass: 0.1 to 10% by mass of the aromatic hydrocarbon: aliphatic alcohol in the organic solvent. Is more preferable, and 90 to 99% by mass: 1 to 10% by mass is further preferable.

(Preparation of reaction solution)
The method for preparing the reaction solution is not particularly limited, and a method of supplying an acid catalyst to a mixed solution of an aromatic alcohol and a ketone or an aldehyde, or a method of supplying an acid catalyst to a mixed solution of an acid catalyst and an aromatic alcohol can be used as a ketone. Or a method of supplying an aldehyde, a method of supplying an acid catalyst to a mixed solution of a mixture of aromatic alcohol, an organic solvent, a ketone or an aldehyde, a method of supplying an acid catalyst, a method of supplying a mixed solution of an acid catalyst, an aromatic alcohol and an organic solvent, and a ketone. Alternatively, a method of supplying aldehyde and the like can be mentioned.

In order to suppress an increase in the amount of ketone or aldehyde due to self-condensation, it is preferable to mix a solution containing an aromatic alcohol and an acid catalyst with a solution containing a ketone or an aldehyde, and the aromatic alcohol and the acid catalyst are contained. A method of supplying a solution containing a ketone or an aldehyde to the solution is more preferable. As a method for supplying ketones and aldehydes, a method of supplying them all at once and a method of supplying them in divided amounts can be used. The method of supplying the mixture is preferable.

The solution containing the ketone or aldehyde may contain the ketone or aldehyde alone, or may contain a thiol or an organic solvent. The thiol is preferably mixed with a ketone or aldehyde in advance and then subjected to the reaction, and the solution containing the ketone or aldehyde preferably contains a thiol.
As a method for mixing a thiol with a ketone or an aldehyde, a ketone or an aldehyde may be mixed with the thiol, or a thiol may be mixed with the ketone or the aldehyde.
Further, as described above, in the method of mixing the mixed solution of thiol and ketone or aldehyde and the acid catalyst, the acid catalyst may be supplied to the mixed solution of thiol and ketone or aldehyde, and the thiol and ketone may be supplied to the acid catalyst. Alternatively, a mixed solution with an aldehyde may be supplied, but it is preferable to supply a mixed solution of a thiol and a ketone or an aldehyde to the acid catalyst.

When an organic solvent is used, a solution containing an aromatic alcohol and an acid catalyst and a solution containing a ketone or an aldehyde may be separately mixed.

(Reaction condition)
The reaction temperature of the bisphenol production reaction is appropriately adjusted according to the type of bisphenol to be produced, the production scale, and the like, but is preferably −30 ° C. to 50 ° C. The reaction for producing bisphenol is a condensation reaction, but if the reaction temperature of the production reaction is too high, oxidative decomposition of thiol proceeds, so it is more preferable in the order of 45 ° C. or lower and 40 ° C. or lower. Further, if the reaction temperature is too low, the time required for the reaction becomes long, so it is more preferable in the order of −20 ° C. or higher, −15 ° C. or higher, −5 ° C. or higher, and 0 ° C. or higher.

The reaction time of the production reaction is appropriately adjusted according to the type of bisphenol to be produced, the reaction temperature, the production scale, and the like, but is usually 0.5 hours to 500 hours. The reaction time of the production reaction may be 400 hours or less or 350 hours or less, but if it is too long, the produced bisphenol is decomposed, so that it is preferably within 30 hours, more preferably within 25 hours, and further preferably within 20 hours. Is. The lower limit of the reaction time is preferably 1 hour or more, more preferably 1.5 hours or more.

Since the condensation reaction occurs when the aromatic alcohol and the ketone or aldehyde come into contact with each other under the acid catalyst, the contact between the aromatic alcohol and the ketone or the aldehyde starts at the start point of the reaction time. (At the start of the condensation reaction). For example, when a mixed solution of an aromatic alcohol and an acid catalyst is supplied with a ketone or aldehyde over 1 hour and then reacted for 1 hour, the reaction time is 2 hours.

<Step of obtaining organic phase (O1) (S2)>
In the step (S2) of obtaining the organic phase (O1), the aqueous phase is removed from the reaction solution obtained in the reaction step (S1) to obtain an organic phase (O1) containing bisphenol.
By allowing the reaction solution after the reaction step (S1) to stand, it is separated into an organic phase (O1) containing bisphenol and an aqueous phase containing water produced by condensation with an acid catalyst. By removing the aqueous phase, an organic phase (O1) containing bisphenol can be obtained.
To reduce the sulfuric acid concentration by adding water equal to or more than the sulfuric acid used or a basic aqueous solution such as a sodium hydroxide aqueous solution so that the sulfuric acid concentration is 45% by mass or less after the reaction step (S1). Therefore, it is also possible to deactivate the acid catalyst to stop the reaction. Therefore, a mixed solution obtained by adding water or a basic aqueous solution to the reaction solution after the reaction step (S1) is allowed to stand, and water containing an organic phase (O1) containing bisphenol and water generated by condensation with an acid catalyst. After separating into phases, the aqueous phase can be removed to obtain an organic phase (O1).
Further, an extraction solvent or the like may be added and allowed to stand so that the reaction solution after the reaction step (S1) can be easily separated into the aqueous phase and the organic phase (O1).

When bisphenol is precipitated in the reaction solution, it is preferable to dissolve the bisphenol by heating to obtain an organic phase (O1) in which the bisphenol is dissolved. For example, it is heated to 50 ° C. to 100 ° C. (preferably 55 ° C. to 85 ° C.) to dissolve bisphenol. In order to obtain the organic phase (O1) in which bisphenol is dissolved, the reaction solution before removing the aqueous phase may be heated to dissolve the bisphenol, or the organic phase (O1) after removing the aqueous phase may be heated to obtain bisphenol. May be dissolved. Dissolving bisphenol enhances the cleaning effect and makes it easier to remove impurities.

<First cleaning step (S3)>
In the first washing step (S3), the organic phase (O1) obtained in the step (S2) for obtaining the organic phase (O1) is removed so that the pH of the aqueous phase is 8.5 or more basic. Wash with desalted water and / or basic aqueous solution to obtain an organic phase (O2).
Specifically, after mixing the organic phase (O1) containing bisphenol with desalted water or a basic aqueous solution, the organic phase and the aqueous phase are separated into phases, and the aqueous phase is removed to obtain an organic phase. The organic phase (O1) is repeatedly washed with desalinated water and / or a basic aqueous solution until the pH of the removed aqueous phase becomes 8.5 or higher.

Here, the demineralized water is water that has undergone ion exchange treatment, pure water, or the like and has an electrical conductivity of 1.5 μS / cm or less. The desalinated water to be used is selected according to the set value of the electrical conductivity of the aqueous phase to be removed in the second cleaning step. For example, in the second cleaning step, when cleaning is performed until the electrical conductivity of the aqueous phase to be removed reaches 1.0 μS / cm, a demineralized water to be used having an electrical conductivity lower than 1.0 μS / cm is selected. do.
The pH of the aqueous phase is preferably measured at room temperature (20 to 30 ° C.), preferably 25 ° C., for example.
Examples of the basic aqueous solution include an aqueous solution in which a basic substance such as sodium hydroxide or sodium hydrogen carbonate is dissolved. When washing is performed a plurality of times, the same basic aqueous solution may be used, or different basic aqueous solutions may be used.

In the cleaning of the organic phase (O1) using desalted water or a basic aqueous solution, when the pH of the removed aqueous phase is lower than 7, it is preferable to perform the cleaning using a basic aqueous solution.

Here, since the basicity of the aqueous phase is weak (low pH) and the cleaning effect on the organic phase (O1) is low, the first cleaning step may be performed until the pH of the aqueous phase becomes pH 9 or higher. preferable. On the other hand, if the aqueous phase is strongly basic (high pH), the bisphenol in the organic phase becomes a bisphenol salt, and the loss of bisphenol in the organic phase increases by moving to the aqueous phase. The upper limit of the pH of is usually 14 or less, preferably 13 or less, and more preferably 12 or less.

The temperature in the first washing step (S3) is preferably 90 ° C. or lower so that bisphenol can be efficiently precipitated by cooling in the crystallization step (S5) described later without evaporating the organic solvent. More preferably, it is 85 ° C. or lower. Further, 50 ° C. or higher is preferable, and 55 ° C. or higher is more preferable. The cleaning time (time for adding a basic aqueous solution or desalinated water to the organic phase and mixing them) is usually about 1 to 120 minutes.

<Second cleaning step (S4)>
In the second cleaning step (S4), the organic phase (O2) obtained in the first cleaning step (S3) is removed until the electrical conductivity of the aqueous phase is 1.0 μS / cm or more and 20 μS / cm or less. Wash with desalinated water to obtain the organic phase (O3).
Specifically, after mixing the organic phase (O2) obtained in the first washing step (S3) with desalinated water, the organic phase and the aqueous phase are separated from each other, the aqueous phase is removed, and the organic phase is prepared. obtain. The organic phase (O2) is repeatedly washed with desalinated water until the electrical conductivity of the removed aqueous phase is 1.0 μS / cm or more and 20 μS / cm or less.

In the second cleaning step (S4), the measurement temperature of the electrical conductivity of the aqueous phase is preferably room temperature (20 to 30 ° C.), for example 25 ° C.
In the second cleaning step (S4), cleaning is performed until the electrical conductivity of the aqueous phase to be removed becomes 20 μS / cm or less, but it is preferable to perform cleaning until the electrical conductivity of the removed aqueous phase becomes 10 μS / cm or less, and 5 μS / cm or less. It is more preferable to wash until it becomes.
Further, in order to contain an appropriate amount of bisphenol sulfonic acids, in the second cleaning step (S4), cleaning is performed so that the electrical conductivity of the aqueous phase to be removed is 1.0 μS / cm or more, but 1.2 μS /. It may be managed with cm or more or 1.5 μS / cm or more as the lower limit.

The temperature and cleaning time in the second cleaning step (S4) are the same as those in the first cleaning step (S3).

<Crystalization step (S5)>
In the crystallization step (S5), the organic phase obtained in the second washing step (S4) is crystallized to obtain a bisphenol composition. By cooling from the temperature of the second washing step (S4) to the cooling temperature, the bisphenol composition is precipitated.

The cooling temperature is preferably 10 to 120 ° C. lower than the temperature of the second cleaning step (S4). Specifically, the cooling temperature is preferably 40 ° C. or lower, more preferably 30 ° C. or lower. Further, −20 ° C. or higher is preferable, and −10 ° C. or higher is more preferable. By cooling to such a temperature, the bisphenol composition can be efficiently precipitated.

The bisphenol composition precipitated in the crystallization step (S5) can be recovered by solid-liquid separation by filtration, centrifugation, decantation or the like.

Crystallization may be performed multiple times. On the other hand, if the number of crystallizations is large, it is difficult to contain an appropriate amount of bisphenol sulfonic acids, so the number of crystallizations is preferably once.

The bisphenol composition may be subjected to suspension washing or drying using an aromatic hydrocarbon or the like as a washing solvent. The drying method may be vacuum drying or normal pressure drying. The drying temperature can be appropriately determined, and for example, it can be dried at 50 to 120 ° C. for 2 to 15 hours.

The method (2) for obtaining the bisphenol composition of the present invention by by-producing bisphenol sulfonic acids when producing bisphenol is preferably method (2-1), but is not limited to this method.

When too much bisphenol sulfonic acid is produced as a by-product in the bisphenol reaction system, the bisphenol composition of the present invention can be obtained by removing a part of the bisphenol sulfonic acid contained in the bisphenol product. At this time, if the purification conditions can be adjusted so that the bisphenol sulfonic acids are within the specified range of the present invention, crystallization, suspension washing, sprinkling washing, etc. may be appropriately combined in addition to the purification method of method (2-1). Purification may be performed. It may be purified by a method such as column chromatography.

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

[Manufacturing method of polycarbonate resin]
The polycarbonate resin of the present invention is a polycarbonate resin having at least a repeating structural unit represented by the following general formula (A).

(In the general formula (A), R ^{1 to} R ⁶ are synonymous with those in the general formula (1).)

As a method for producing the polycarbonate resin of the present invention using the bisphenol composition of the present invention, the bisphenol composition of the present invention and diphenyl carbonate or the like are used in the presence of an alkali metal compound and / or an alkaline earth metal compound. Examples thereof include a method of transesterifying.
The bisphenol composition of the present invention may contain only one type of bisphenol, or may contain two or more types. A copolymerized polycarbonate resin can be produced by using two or more kinds of bisphenols. Further, a dihydroxy compound other than the bisphenol composition of the present invention can be used in combination for reaction.
The transesterification reaction can be carried out by appropriately selecting a known method, and an example of a method for producing a polycarbonate resin using the bisphenol composition of the present invention and diphenyl carbonate as raw materials will be described below.

In the above method for producing a polycarbonate resin, it is preferable to use diphenyl carbonate in an excess amount with respect to the bisphenol in the bisphenol composition of the present invention. The amount of diphenyl carbonate used for bisphenol is preferably large in that the produced polycarbonate resin has few terminal hydroxyl groups and is excellent in thermal stability of the polymer, and the transesterification reaction rate is high, and the polycarbonate having a desired molecular weight. It is preferable that the amount is small in that the resin can be easily produced. From these facts, the amount of diphenyl carbonate used per 1 mol of bisphenol is usually 1.001 mol or more, preferably 1.002 mol or more. In addition, it is usually 1.3 mol or less, preferably 1.2 mol or less.

As a method for supplying the raw materials, the bisphenol composition and diphenyl carbonate of the present invention can be supplied as a solid, but it is preferable that one or both of them are melted and supplied in a liquid state.

When a polycarbonate resin is produced by a transesterification reaction between diphenyl carbonate and bisphenol, a transesterification catalyst is usually used. In the above method for producing a polycarbonate resin, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound as the transesterification catalyst. These may be used alone or in any combination and ratio of two or more. Practically, it is desirable to use an alkali metal compound.

The amount of the catalyst used is usually 0.05 μmol or more, preferably 0.08 μmol or more, and more preferably 0.10 μmol or more with respect to 1 mol of bisphenol or diphenyl carbonate. The upper limit thereof is usually 100 μmol or less, preferably 50 μmol or less, and more preferably 20 μmol or less.
When the amount of the catalyst used is within the above range, it is easy to obtain the polymerization activity required for producing a polycarbonate resin having a desired molecular weight, the polymer hue is excellent, and excessive polymer branching does not proceed. It is easy to obtain a polycarbonate resin with excellent fluidity during molding.

In order to produce the polycarbonate resin by the above method, it is preferable that both of the above raw materials are continuously supplied to the raw material mixing tank, and the obtained mixture and the transesterification catalyst are continuously supplied to the polymerization tank.
In the production of the polycarbonate resin by the transesterification method, usually, both raw materials supplied to the raw material mixing tank are uniformly stirred and then supplied to the polymerization tank to which the transesterification catalyst is added to produce a polymer.

In the production of the polycarbonate resin using the bisphenol composition of the present invention, the polymerization reaction temperature is preferably 80 to 400 ° C, particularly 150 to 350 ° C. The post-stage polymerization time is appropriately adjusted depending on the ratio of the raw materials, the desired molecular weight of the polycarbonate resin, etc., but if the post-stage polymerization time is long, quality deterioration such as color tone deterioration becomes apparent, so it is 10 hours or less. It is preferably 8 hours or less, and more preferably 8 hours or less. The lower limit of the post-stage polymerization time is usually 0.1 hours or more, or 0.3 hours or more.

According to the bisphenol composition of the present invention, a polycarbonate resin having a good hue and excellent transparency can be produced. For example, a polycarbonate resin having a viscosity average molecular weight (Mv) of 1000 to 100,000, preferably 1500 to 35,000, and having a pellet YI of 10 or less, having a good hue and excellent transparency can be produced in a short time.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.

[Raw materials and reagents]
In the following examples and comparative examples, orthocresol, toluene, sodium hydroxide, sulfuric acid, dodecanethiol, acetone, sodium hydrogen carbonate, cesium carbonate, acetonitrile, acetic acid, ammonium acetate, and bisphenol C are used by Fuji Film Wako Pure Chemical Industries, Ltd. A reagent made from the above was used.
As diphenyl carbonate, a product manufactured by Mitsubishi Chemical Corporation was used.
As the desalinated water, one having an electric conductivity of about 0.85 to 1.0 μs / cm was selected and used according to the electric conductivity of the aqueous phase in the step (S4).

[analysis]
<Analysis of bisphenol C in bisphenol C composition>
The composition analysis of the bisphenol C composition was performed by high performance liquid chromatography under the following procedure and conditions. Since the purity of bisphenol C in the bisphenol C composition produced below is usually 99% by mass or more and the amount of bisphenol other than bisphenol C produced is very small, the purity of bisphenol C is determined in the bisphenol C composition. It can be regarded as the bisphenol C content (BPC content).
・ Equipment: "LC-2010A" manufactured by Shimadzu Corporation
Imtaket ScherzoSM-C18 3μm 250mm x 3.0mm ID
・ Low pressure gradient method ・ Analysis temperature: 40 ℃
-Eluent composition:
Solution Ammonium acetate: Acetic acid: Demineralized water = 3.000 g: 1 mL: 1 L solution Solution B Ammonium acetate: Acetic acid: Acetonitrile: Demineralized water = 1.500 g: 1 mL: 900 mL: 150 mL solution The liquid composition is liquid A: liquid B = 60:40 (volume ratio, the same applies hereinafter).
The analysis time of 0 to 41.67 minutes was gradually changed to liquid A: liquid B = 10:90.
Analysis time 41.67 to 50 minutes is maintained at liquid A: liquid B = 10:90,
The analysis was performed at a flow rate of 0.34 mL / min.

<Analysis of bisphenol C sulfonic acid in bisphenol C composition, measurement of molecular weight>
The bisphenol C sulfonic acid analysis and the molecular weight measurement in the bisphenol C composition were carried out by high performance liquid chromatography mass spectrometry (LCMS) under the following procedure and conditions.
・ Equipment: "LC-2010A" manufactured by Shimadzu Corporation
Unison UK C18 3 μm 250 × 4.6 mm I. D
・ Low pressure gradient method ・ Analysis temperature: 40 ℃
-Eluent composition:
Liquid A Ammonium acetate 3.0 g + acetic acid 1 mL / pure water 1 L
Solution B (0.225 g of ammonium acetate + 0.15 mL of acetic acid / 150 mL of pure water) + 900 mL of acetonitrile ・ When the analysis time is 0 minutes, the eluent composition is solution A: solution B = 60:40 (volume ratio, the same applies hereinafter).
The analysis time is gradually changed from solution A: solution B = 10:90 for 0 to 15 minutes.
The analysis time is maintained at 10:90 for solution A: solution B for 15 to 30 minutes.
The analysis was performed at a flow rate of 1.0 mL / min.
-Mass spectrometer: "Agilent LC / MS 6130" manufactured by Agilent Technologies, Inc.
-Ion source: ESI (Postive / Negative) AJS probe used

<Distribution of bisphenol C sulfonic acid>
The bisphenol C sulfonic acid in the bisphenol C composition was separated by the following procedure by high performance liquid chromatography for separation.
・ Equipment: "LC10A" manufactured by Shimadzu Corporation
Unison UK C18 3 μm 250 × 4.6 mm I. D
・ Analysis temperature: 40 ° C
-Eluent composition:
Liquid A Water Liquid B Acetonitrile ・ When the analysis time is 0 to 5 minutes, the eluent composition is Liquid A: Liquid B = 90:10 (volume ratio, the same applies hereinafter).
The analysis time was gradually changed to solution A: solution B = 60:40 for 5 to 15 minutes.
The analysis time was gradually changed to solution A: solution B = 10:90 for 15 to 20 minutes.
The analysis time of 20 to 25 minutes was maintained at liquid A: liquid B = 10:90.
The analysis was performed at a flow rate of 10.0 mL / min.
・ Performed 30 times with an injection volume of 400 μL / time.

<NMR>
For nuclear magnetic resonance (NMR) measurement, the solution obtained by preparative bisphenol C sulfonic acid is dried by an evaporator, and as a deuterated chloroform solution, "JNM-ECS400 type" manufactured by JEOL Ltd. is used for ¹ H. NMR was performed.
Equipment: JEOL ECS400
Probe: H5XAT / FG2 (inverse)
Measurement conditions: single_pulse. ex2
Number of measurements: 128 Measurement temperature: Room temperature

<Measurement of pH>
The pH was measured using a pH meter "pH METER ES-73" manufactured by HORIBA, Ltd. for an aqueous phase at 25 ° C. taken out from the flask.

<Electrical conductivity>
The measurement of the electric conductivity was carried out using an electric conductivity meter "COND METER D-71" manufactured by HORIBA, Ltd. for an aqueous phase at 25 ° C. taken out from the flask.

<Methanol-dissolved color of bisphenol C composition>
The color of the bisphenol C composition dissolved in methanol is determined by adding 10 g of the bisphenol C composition and 10 g of methanol to a test tube "P-24" (24 mmφ x 200 mm) manufactured by Nichiden Rika Glass Co., Ltd. to make a uniform solution, and then at room temperature (about 20). The number of Hazen colors was measured using "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd. at (° C.).

<Melted color difference of bisphenol C composition>
The melt color difference of the bisphenol C composition is as follows: 20 g of the bisphenol C composition is placed in a test tube "P-24" (24 mmφ x 200 mm) manufactured by Nichiden Rika Glass Co., Ltd., melted at 190 ° C. for 30 minutes, and manufactured by Nippon Denshoku Kogyo Co., Ltd. The number of Hazen colors was measured using "SE6000".

<Evaluation of polymerization activity of bisphenol>
A polycarbonate resin (PC) was produced using the bisphenol composition, and the time from the temperature rise to 280 ° C. to the end of polymerization (post-stage polymerization time) was evaluated as the polymerization activity of bisphenol. The polymerization activity of bisphenol was evaluated based on the following criteria.
◯: 140 minutes or more and 200 minutes or less Δ: Less than 140 minutes or more than 200 minutes ×: Polymerization reaction does not proceed

<Viscosity average molecular weight>
The viscosity average molecular weight (Mv) of the polycarbonate resin is determined by dissolving the polycarbonate resin in methylene chloride (concentration 6.0 g / L), measuring the specific viscosity (ηsp) at 20 ° C. using an Ubbelohde viscous tube, and using the following formula. The viscosity average molecular weight (Mv) was calculated.
ηsp / C = [η] (1 + 0.28ηsp)
[η] = 1.23 × 10 ^-4 Mv ^0.83

<Pellet YI>
The pellet YI (transparency of the polycarbonate resin (PC)) was evaluated by measuring the YI value (yellowness index value) in the reflected light of the polycarbonate resin pellet in accordance with ASTM D1925. A spectrocolorimeter "CM-5" manufactured by Konica Minolta Co., Ltd. was used as an apparatus, and a measurement diameter of 30 mm and SCE were selected as measurement conditions.
The calibration glass "CM-A212" for petri dish measurement was fitted into the measuring section, and the zero calibration box "CM-A124" was placed over it to perform zero calibration, and then white calibration was performed using the built-in white calibration plate. .. Next, measurement was performed using the white calibration plate "CM-A210", where L * was 99.40 ± 0.05, a * was 0.03 ± 0.01, and b * was -0.43 ± 0.01. , YI was confirmed to be −0.58 ± 0.01.
YI was measured by packing pellets to a depth of about 40 mm in a cylindrical glass container having an inner diameter of 30 mm and a height of 50 mm. The operation of taking out the pellets from the glass container and then performing the measurement again was repeated twice, and the average value of the measured values of a total of three times was used.

<Example 1>
(1-1) Production of Bisphenol C Composition [Step (S1)]
In a separable flask equipped with a thermometer, a dropping funnel, a jacket and an anchor-type stirring blade, 280.0 g of toluene, 12.0 g of methanol and 230.4 g of orthocresol were placed in a nitrogen atmosphere, and the internal temperature was maintained at 10 ° C. or lower. While stirring, 76.0 g of 98 mass% sulfuric acid was added to prepare a mixed solution A1.
Next, 65.0 g of acetone (1.12 mol of substance), 5.4 g of dodecanethiol, and 50.0 g of toluene were added to the dropping funnel to prepare a mixed solution B1.
While the mixed solution A1 was maintained at 10 ° C. or lower, the mixed solution B1 in the dropping funnel was added dropwise to the mixed solution A1 over 45 minutes while stirring, and the mixture was further stirred for 1 hour while being maintained at 10 ° C., and bisphenol. The reaction solution C1 of C was obtained.

[Step (S2)]
120 g of a 25% sodium hydroxide solution was added to the reaction solution C1 of bisphenol C, the mixture was stirred, the temperature was raised to 75 ° C., and the mixture was allowed to stand for oil-water separation. After the oil-water separation, the aqueous phase was removed from the bottom of the separable flask to obtain an organic phase D1 (corresponding to the organic phase (O1)).

[Step (S3)]
At 75 ° C., a 3 wt% sodium hydrogen carbonate solution was added to the obtained organic phase D1 and stirred to neutralize, and oil-water separation was performed. After the oil-water separation, the aqueous phase was removed from the bottom of the separable flask to obtain the organic phase E1 (corresponding to the organic phase (O2)). At this time, the pH of the removed aqueous phase was 9.2.

[Step (S4)]
100 g of demineralized water was added to the organic phase E1, the mixture was stirred, the temperature was raised to 83 ° C., and the mixture was allowed to stand to separate oil and water. After oil-water separation, the aqueous phase was removed from the bottom of the separable flask. This operation was repeated to wash the organic phase E1 until the electrical conductivity of the removed aqueous phase reached 1.9 μS / cm. The obtained organic phase was designated as the organic phase F1 (corresponding to the organic phase (O3)).

[Step (S5)]
The organic phase F1 was gradually cooled from 83 ° C. to 5 ° C. to precipitate bisphenol C-containing crystals. The obtained liquid containing bisphenol C-containing crystals was subjected to solid-liquid separation using a centrifuge to obtain a bisphenol C-containing cake.

To this bisphenol C-containing cake, 175 g of toluene was supplied, suspension washing was carried out while loosening the cake, and solid-liquid separation was carried out using a centrifuge. This operation was repeated twice more to obtain a fine cake.
A white bisphenol C composition was obtained by distilling off a light boiling point at an oil bath temperature of 100 ° C. under reduced pressure using an evaporator equipped with an oil bath.

(1-2) Composition Analysis of Bisphenol C Composition When the quality of the bisphenol C composition obtained in (1-1) was confirmed, the holding time was 22.5 minutes on high performance liquid chromatograph mass spectrometry (LCMS). In addition to the peak derived from bisphenol C, a characteristic peak was detected with a retention time of 9.5 minutes. In order to identify the component of the peak having a retention time of 9.5 minutes, it was measured by high performance liquid chromatography equipped with a mass meter, and it was found that the molecular weight was 336 g / mol.

1.6 g of the bisphenol C composition obtained in (1-1) was dissolved in an acetonitrile solution, and the above-mentioned characteristic peak was fractionated using liquid chromatography for preparative use. The solution obtained by preparative separation was dried to dryness, the obtained dry matter was dissolved in heavy methanol, and 1H-NMR (Fig. 2) was measured. As a result, 2- (4-hydroxy-3-methylphenyl)- It was confirmed that it was 2- (4-hydroxy-3-methyl-5-sulfonylphenyl) propane (bisphenol C sulfonic acid, a compound in which X is a hydrogen atom in the general formula (i)).
Bisphenol C Sulfonic Acid; ¹ NMR (400MHz, CDCl ₃ ) 1.48 (Me, s, 6H), 2.01 (Me, s, 3H), 2.03 (Me, s, 3H), 6.52 ( Since CH, d, 1H), 6.74 (CH, dd, 1H), 6.75 to 6.85 (CH, m, 3H) and deuterated methanol were used, no peak corresponding to OH was detected.

The obtained bisphenol C composition contained 4% by mass ppb of bisphenol C sulfonic acid (BPC-SA).
The bisphenol C content in the obtained bisphenol C composition was 99.8% by mass.

(1-3) Color tone of bisphenol C composition When the methanol-dissolved color of the bisphenol C composition obtained in (1-1) was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C composition was measured, the number of Hazen colors was 10.

(1-4) Polymerization activity of bisphenol C composition and color tone of polycarbonate resin The bisphenol C composition obtained in (1-1) was placed in a glass reaction vessel having an internal volume of 150 mL and equipped with a stirrer and a distillate. 100.00 g (0.39 mol), 86.49 g (0.4 mol) of diphenyl carbonate, and 480 μL of a 400 mass ppm cesium carbonate aqueous solution were added. The operation of reducing the pressure of the glass reaction vessel to about 100 Pa and then restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reaction vessel with nitrogen. Then, the reaction vessel was immersed in an oil bath at 200 ° C. to melt the contents.

The rotation speed of the stirrer was set to 100 times per minute, and the pressure in the reaction vessel was increased over 40 minutes while distilling off the phenol produced by the oligomerization reaction of purified bisphenol C and diphenyl carbonate in the reaction vessel. The pressure was reduced from 101.3 kPa to 13.3 kPa. Subsequently, the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the reaction vessel at 13.3 kPa and further distilling off phenol. Then, the temperature outside the reaction vessel was raised to 250 ° C., and the pressure inside the reaction vessel was reduced from 13.3 kPa to 399 Pa in absolute pressure over 40 minutes to remove the distilled phenol from the system.

Then, the outside temperature of the reaction vessel was raised to 280 ° C., the absolute pressure of the reaction vessel was reduced to 30 Pa, and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the stirrer in the reaction tank became a predetermined stirring power.

The time from the temperature rise to 280 ° C. to the end of the polymerization (post-stage polymerization time) was 170 minutes.

Next, the reaction vessel was repressurized to 101.3 kPa with nitrogen at an absolute pressure, and then the pressure was increased to 0.2 MPa with a gauge pressure, and the polycarbonate resin was extracted from the bottom of the reaction vessel in a strand shape to obtain a strand-shaped polycarbonate resin. .. Then, the strands were pelletized using a rotary cutter to obtain a pellet-shaped polycarbonate resin.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 6.9.

<Example 2>
(2-1) Production of Bisphenol C Composition [Step (S1)]
In a separable flask equipped with a thermometer, a dropping funnel, a jacket and an anchor-type stirring blade, 280.0 g of toluene, 15.0 g of methanol and 230.4 g of orthocresol were placed in a nitrogen atmosphere, and the internal temperature was maintained at 10 ° C. or lower. While stirring, 95.0 g of 98 mass% sulfuric acid was added to prepare a mixed solution A2.
Next, 65.0 g of acetone (1.12 mol of substance), 5.4 g of dodecanethiol, and 50.0 g of toluene were added to the dropping funnel to prepare a mixed solution B2.
While the mixed solution A2 was maintained at 10 ° C. or lower, the mixed solution B2 in the dropping funnel was added dropwise to the mixed solution A2 over 45 minutes while stirring, and the mixture was further stirred for 1 hour while being maintained at 10 ° C., and bisphenol. The reaction solution C2 of C was obtained.

[Step (S2)]
120 g of a 25% sodium hydroxide solution was added to the reaction solution C2 of bisphenol C, the mixture was stirred, the temperature was raised to 75 ° C., and the mixture was allowed to stand for oil-water separation. After the oil-water separation, the aqueous phase was removed from the bottom of the separable flask to obtain the organic phase D2.

[Step (S3)]
At 75 ° C., a 3 wt% sodium hydrogen carbonate solution was added to the obtained organic phase D2, stirred and neutralized, and oil-water separation was performed. After the oil-water separation, the aqueous phase was removed from the bottom of the separable flask to obtain the organic phase E2. At this time, the pH of the removed aqueous phase was 9.1.

[Step (S4)]
100 g of desalinated water was added to the organic phase E2, the mixture was stirred, the temperature was raised to 83 ° C., and the mixture was allowed to stand to separate oil and water. After oil-water separation, the aqueous phase was removed from the bottom of the separable flask. This operation was repeated, and the organic phase E2 was washed until the electrical conductivity of the removed aqueous phase reached 2.1 μS / cm. The obtained organic phase was designated as the organic phase F2.

[Step (S5)]
The organic phase F2 was gradually cooled from 83 ° C. to 5 ° C. to precipitate bisphenol C-containing crystals. The obtained liquid containing bisphenol C-containing crystals was subjected to solid-liquid separation using a centrifuge to obtain a bisphenol C-containing cake.

To this bisphenol C-containing cake, 175 g of toluene was supplied, suspension washing was carried out while loosening the cake, and solid-liquid separation was carried out using a centrifuge. This operation was repeated twice more to obtain a fine cake.
A white bisphenol C composition was obtained by distilling off a light boiling point at an oil bath temperature of 100 ° C. under reduced pressure using an evaporator equipped with an oil bath.

(2-2) Composition Analysis of Bisphenol C Composition It was analyzed in the same manner as in Example 1, and it was confirmed that the obtained bisphenol C composition contained 40 mass ppb of bisphenol C sulfonic acid.
The bisphenol C content in the obtained bisphenol C composition was 99.8% by mass.

(2-3) Color tone of bisphenol C composition When the methanol-dissolved color of the bisphenol C composition obtained in (2-1) was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C composition was measured, the number of Hazen colors was 10.

(2-4) Polymerization activity of bisphenol C composition and color tone of polycarbonate resin The bisphenol C composition obtained in (2-1) was placed in a glass reaction vessel having an internal volume of 150 mL equipped with a stirrer and a distillate. 100.00 g (0.39 mol), 86.49 g (0.4 mol) of diphenyl carbonate, and 480 μL of a 400 mass ppm cesium carbonate aqueous solution were added. The operation of reducing the pressure of the glass reaction vessel to about 100 Pa and then restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reaction vessel with nitrogen. Then, the reaction vessel was immersed in an oil bath at 200 ° C. to melt the contents.
After that, the same procedure as in Example 1 was carried out, and the time from the temperature rise to 280 ° C. to the completion of the polymerization (post-stage polymerization time) was 165 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 6.7.

<Example 3>
(3-1) Production of Bisphenol C Composition [Step (S1)]
In a separable flask equipped with a thermometer, a dropping funnel, a jacket and an anchor-type stirring blade, 280.0 g of toluene, 6.0 g of methanol and 230.4 g of orthocresol were placed in a nitrogen atmosphere, and the internal temperature was maintained at 10 ° C. or lower. While stirring, 80.0 g of 98% by mass of sulfuric acid was added to prepare a mixed solution A3.
Next, 65.0 g of acetone (1.12 mol of substance), 5.4 g of dodecanethiol, and 50.0 g of toluene were added to the dropping funnel to prepare a mixed solution B3.
While the mixed solution A3 was maintained at 10 ° C. or lower, the mixed solution B3 in the dropping funnel was added dropwise to the mixed solution A3 over 45 minutes while stirring, the temperature was raised to 30 ° C., and the mixture was further stirred for 1 hour to obtain bisphenol C. Reaction solution C3 was obtained.

[Step (S2)]
90 g of a 25% sodium hydroxide solution was added to the reaction solution C3 of bisphenol C, the mixture was stirred, the temperature was raised to 75 ° C., and the mixture was allowed to stand for oil-water separation. After the oil-water separation, the aqueous phase was removed from the bottom of the separable flask to obtain the organic phase D3. A part of the removed aqueous phase was set aside and used as the aqueous phase d3.

[Step (S3)]
At 75 ° C., a 3 wt% sodium hydrogen carbonate solution was added to the obtained organic phase D3, stirred and neutralized, and oil-water separation was performed. After the oil-water separation, the aqueous phase was removed from the bottom of the separable flask to obtain the organic phase E3. At this time, the pH of the removed aqueous phase was 9.2.

[Step (S4)]
To this organic phase E3, 100 g of desalinated water was added, stirred, the temperature was raised to 83 ° C., and the mixture was allowed to stand to separate oil and water. After oil-water separation, the aqueous phase was removed from the bottom of the separable flask. This operation was repeated, and the organic phase E3 was washed until the electrical conductivity of the removed aqueous phase reached 2.4 μS / cm. The obtained organic phase was designated as F3.

[Step (S5)]
The organic phase F3 was gradually cooled from 83 ° C. to 5 ° C. to precipitate bisphenol C-containing crystals. The obtained liquid containing bisphenol C-containing crystals was subjected to solid-liquid separation using a centrifuge to obtain a bisphenol C-containing cake.

To this bisphenol C-containing cake, 175 g of toluene was supplied, suspension washing was carried out while loosening the cake, and solid-liquid separation was carried out using a centrifuge. This operation was repeated twice more to obtain a fine cake.
A white bisphenol C composition was obtained by distilling off a light boiling point at an oil bath temperature of 100 ° C. under reduced pressure using an evaporator equipped with an oil bath.

(3-2) Composition Analysis of Bisphenol C Composition It was analyzed in the same manner as in Example 1, and it was confirmed that the obtained bisphenol C composition contained 340 mass ppb of bisphenol C sulfonic acid.
The bisphenol C content in the obtained bisphenol C composition was 99.8% by mass.

(3-3) Color tone of bisphenol C composition When the methanol-dissolved color of the bisphenol C composition obtained in (3-1) was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C composition was measured, the number of Hazen colors was 15.

(3-4) Polymerization activity of bisphenol C composition and color tone of polycarbonate resin The bisphenol C composition obtained in (3-1) was placed in a glass reaction vessel having an internal volume of 150 mL equipped with a stirrer and a distillate. 100.00 g (0.39 mol), 86.49 g (0.4 mol) of diphenyl carbonate, and 570 μL of a 1000 mass ppm cesium carbonate aqueous solution were added. The operation of reducing the pressure of the glass reaction vessel to about 100 Pa and then restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reaction vessel with nitrogen. Then, the reaction vessel was immersed in an oil bath at 200 ° C. to melt the contents.
After that, the same procedure as in Example 1 was carried out, and the time from the temperature rise to 280 ° C. to the completion of the polymerization (post-stage polymerization time) was 171 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 7.2.

<Example 4>
(4-1) Production of Bisphenol C Composition [Step (S1)] [Step (S2)]
The same procedure as in Example 3 was carried out to obtain an organic phase D3 and an aqueous phase d3.

[Step (S3)]
At 75 ° C., 20 g of the separated aqueous phase d3 was added to the obtained organic phase D3, a 3 wt% sodium hydrogen carbonate solution was added, the mixture was stirred and neutralized, and oil-water separation was performed. After oil-water separation, the aqueous phase was removed from the bottom of the separable flask to obtain the organic phase E4. At this time, the pH of the removed aqueous phase was 9.3.

[Step (S4)]
To this organic phase E4, 100 g of desalinated water was added, stirred, the temperature was raised to 83 ° C., and the mixture was allowed to stand to separate oil and water. After oil-water separation, the aqueous phase was removed from the bottom of the separable flask. This operation was repeated, and the organic phase E4 was washed until the electrical conductivity of the removed aqueous phase reached 15.0 μS / cm. The obtained organic phase was designated as the organic phase F4.

[Step (S5)]
The organic phase F4 was gradually cooled from 83 ° C. to 5 ° C. to precipitate bisphenol C-containing crystals. The obtained liquid containing bisphenol C-containing crystals was subjected to solid-liquid separation using a centrifuge to obtain a bisphenol C-containing cake.

To this bisphenol C-containing cake, 175 g of toluene was supplied, suspension washing was carried out while loosening the cake, and solid-liquid separation was carried out using a centrifuge. This operation was repeated twice more to obtain a fine cake.
A white bisphenol C composition was obtained by distilling off a light boiling point at an oil bath temperature of 100 ° C. under reduced pressure using an evaporator equipped with an oil bath.

(4-2) Composition Analysis of Bisphenol C Composition It was analyzed in the same manner as in Example 1, and it was confirmed that the obtained bisphenol C composition contained 632 mass ppb of bisphenol C sulfonic acid.
The bisphenol C content in the obtained bisphenol C composition was 99.8% by mass.

(4-3) Color tone of bisphenol C composition When the methanol-dissolved color of the bisphenol C composition obtained in (4-1) was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C composition was measured, the number of Hazen colors was 20.

(4-4) Polymerization activity of bisphenol C composition and color tone of polycarbonate resin The bisphenol C composition obtained in (4-1) was placed in a glass reaction vessel having an internal volume of 150 mL equipped with a stirrer and a distillate. 100.00 g (0.39 mol), 86.49 g (0.4 mol) of diphenyl carbonate, and 570 μL of a 1000 mass ppm cesium carbonate aqueous solution were added. The operation of reducing the pressure of the glass reaction vessel to about 100 Pa and then restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reaction vessel with nitrogen. Then, the reaction vessel was immersed in an oil bath at 200 ° C. to melt the contents.
After that, the same procedure as in Example 1 was carried out, and the time from the temperature rise to 280 ° C. to the completion of the polymerization (post-stage polymerization time) was 165 minutes.
The obtained polycarbonate resin had a viscosity average molecular weight (Mv) of 24800 and a pellet YI of 11.1.

<Comparative example 1>
The composition, methanol-dissolved color, and melt-color difference of the reagent bisphenol C (reagent bisphenol C) manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. were determined. In addition, a polycarbonate resin was produced using the reagent bisphenol C, and the polymerization activity and the color tone of the polycarbonate resin were evaluated.

(Ratio 1-1) Composition analysis of reagent bisphenol C Analysis was carried out in the same manner as in Example 1, and it was confirmed that reagent bisphenol C did not contain bisphenol C sulfonic acid.
The content of bisphenol C in the reagent bisphenol C was 99.8% by mass.

(Ratio 1-2) Color tone of reagent bisphenol C When the methanol-dissolved color of reagent bisphenol C was measured, the number of Hazen colors was 16. When the melt color difference of the reagent bisphenol C was measured, the number of Hazen colors was 46.

(Ratio 1-3) Polymerization activity of bisphenol C composition and color tone of polycarbonate resin In a glass reaction tank with an internal volume of 150 mL equipped with a stirrer and a distilling tube, 100.00 g (0.39 mol) of reagent bisphenol C was added. ), 86.49 g (0.4 mol) of diphenyl carbonate and 480 μL of a 400 mass ppm cesium carbonate aqueous solution were added. The operation of reducing the pressure of the glass reaction vessel to about 100 Pa and then restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reaction vessel with nitrogen. Then, the reaction vessel was immersed in an oil bath at 200 ° C. to melt the contents.
After that, the same procedure as in Example 1 was carried out, and the time from the temperature rise to 280 ° C. to the end of the polymerization (post-stage polymerization time) was 210 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 10.7.

<Comparative example 2>
(Ratio 2-1) Production of bisphenol C composition [Step (S1)]
In a separable flask equipped with a thermometer, a dropping funnel, a jacket and an anchor-type stirring blade, 280.0 g of toluene, 15.0 g of methanol and 230.4 g of orthocresol were placed in a nitrogen atmosphere, and the internal temperature was maintained at 10 ° C. or lower. While stirring, 75.0 g of 98 mass% sulfuric acid was added to prepare a mixed solution A5.
Next, 65.0 g of acetone (1.12 mol of substance), 5.4 g of dodecanethiol, and 50.0 g of toluene were added to the dropping funnel to prepare a mixed solution B5.
While the mixed solution A5 was maintained at 10 ° C. or lower, the mixed solution B5 in the dropping funnel was added dropwise to the mixed solution A5 over 45 minutes while stirring, and the mixture was further stirred for 1 hour while being maintained at 10 ° C., and bisphenol. A reaction solution C5 of C was obtained.

[Step (S2)]
120 g of a 25% sodium hydroxide solution was added to the reaction solution C5 of bisphenol C, the mixture was stirred, the temperature was raised to 75 ° C., and the mixture was allowed to stand for oil-water separation. After the oil-water separation, the aqueous phase was removed from the bottom of the separable flask to obtain the organic phase D5.

[Step (S3)]
At 75 ° C., a 3 wt% sodium hydrogen carbonate solution was added to the obtained organic phase D5, stirred and neutralized, and oil-water separation was performed. After the oil-water separation, the aqueous phase was removed from the bottom of the separable flask to obtain the organic phase E5. At this time, the pH of the removed aqueous phase was 9.2.

[Washing (comparison of process (S4))]
To this organic phase E5, 100 g of desalinated water was added, stirred, the temperature was raised to 83 ° C., and the mixture was allowed to stand to separate oil and water. After oil-water separation, the aqueous phase was removed from the bottom of the separable flask. This operation was repeated, and the organic phase E5 was washed until the electrical conductivity of the removed aqueous phase reached 0.9 μS / cm. The obtained organic phase was designated as F5.

[Crystalization (compared to step (S5))]
The organic phase F5 was gradually cooled from 83 ° C. to 5 ° C. to precipitate bisphenol C-containing crystals. The obtained liquid containing bisphenol C-containing crystals was subjected to solid-liquid separation using a centrifuge to obtain a bisphenol C-containing cake.

To this bisphenol C-containing cake, 175 g of toluene was supplied, suspension washing was carried out while loosening the cake, and solid-liquid separation was carried out using a centrifuge. This operation was repeated twice more to obtain a fine cake.
A white bisphenol C composition was obtained by distilling off a light boiling point at an oil bath temperature of 100 ° C. under reduced pressure using an evaporator equipped with an oil bath.

(Ratio 2-2) Composition analysis of bisphenol C composition Analysis was performed in the same manner as in Example 1, and it was confirmed that the bisphenol C composition obtained in (Ratio 2-1) did not contain bisphenol C sulfonic acid. bottom.
The bisphenol C content in the bisphenol C composition obtained in (Ratio 2-1) was 99.8% by mass.

(Ratio 2-3) Color tone of bisphenol C composition When the methanol-dissolved color of the bisphenol C composition obtained in (Ratio 2-1) was measured, the number of Hazen colors was 5. When the melt color difference of the bisphenol C composition obtained in (Ratio 2-1) was measured, the number of Hazen colors was 32.

(Ratio 2-4) Polymerization activity of bisphenol C composition and color tone of polycarbonate resin The bisphenol C composition obtained in (Ratio 2-1) was placed in a glass reaction vessel having an internal volume of 150 mL equipped with a stirrer and a distillate. 100.00 g (0.39 mol) of the product, 86.49 g (0.4 mol) of diphenyl carbonate, and 480 μL of a 400 mass ppm cesium carbonate aqueous solution were added. The operation of reducing the pressure of the glass reaction vessel to about 100 Pa and then restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reaction vessel with nitrogen. Then, the reaction vessel was immersed in an oil bath at 200 ° C. to melt the contents.
After that, the same procedure as in Example 1 was carried out, and the time from the temperature rise to 280 ° C. to the completion of the polymerization (post-stage polymerization time) was 170 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 12.2.

Table 1 shows the content of bisphenol C (BPC content), the content of bisphenol sulfonic acid (content of BPC-SA), and the dissolved color of methanol (MeOH dissolved color) in Examples 1 to 4 and Comparative Examples 1 and 2. ), Molten color difference, polymerization activity, and evaluation results of pellet YI of polycarbonate resin (PC) are shown.

<Example 5>
(5-1) Production of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (BPOCZ) composition [Step (S1)]
A full-jacket type 1 L separable flask equipped with a thermometer, a stirrer and a dropping funnel was charged with 100 g of toluene, 115 g (1.06 mol) of orthocresol and 6 g of methanol under a nitrogen atmosphere to obtain a mixed solution. After cooling the temperature of the obtained mixed solution to 5 ° C., 48 g of 98 mass% sulfuric acid was slowly added to prepare an orthocresol mixed solution, which was set to 10 ° C. or lower. A cyclohexanone mixture of 25 g of toluene, 48 g (0.49 mol) of cyclohexanone and 3 g of dodecanethiol was prepared and placed in the dropping funnel. The cyclohexanone mixture was slowly added dropwise to the orthocresol mixture over 1 hour to obtain a reaction solution. Then, the obtained reaction solution was heated to 50 ° C. and mixed for 1 hour to obtain a 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane reaction solution.

[Step (S2)]
After adding 140 g of a 25 mass% sodium hydroxide aqueous solution to the obtained 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane reaction solution, the temperature was raised to 80 ° C. After reaching 80 ° C., toluene was added to dissolve the precipitated 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane. Then, it was allowed to stand and separated into oil and water. The aqueous phase of the lower phase was discarded to obtain organic phase 1 (corresponding to organic phase (O1)).

[Step (S3)]
100 g of desalinated water was added to the obtained organic phase 1, mixed until the temperature reached 80 ° C. or higher, and the mixture was allowed to stand to separate oil and water. The aqueous phase of the lower phase was discarded to obtain the organic phase 2. 100 g of 5% by mass aqueous sodium hydrogen carbonate was added to the obtained organic phase 2, mixed until the temperature reached 80 ° C. or higher, and the mixture was allowed to stand to separate oil and water. The aqueous phase of the lower phase was discarded to obtain organic phase 3 (corresponding to organic phase (O2)). At this time, the pH of the aqueous phase of the lower phase was 8.9.

[Step (S4)]
100 g of desalinated water was added to the obtained organic phase 3, mixed at 80 ° C. or higher, and allowed to stand to separate oil and water. The aqueous phase of the lower phase was discarded to obtain organic phase 4 (corresponding to organic phase (O3)). At this time, the electrical conductivity of the aqueous phase of the lower phase was 3.2 μS / cm.

[Step (S5)]
The temperature of the obtained organic phase 4 was lowered to 20 ° C. to obtain a slurry liquid. The obtained slurry liquid was used as a solid-liquid separator to obtain a cake.

The obtained cake was distilled off with a light boiling point at an oil bath temperature of 100 ° C. under reduced pressure using an evaporator equipped with an oil bath to obtain white 1,1-bis (4-hydroxy-3-methylphenyl). ) Cyclohexane (BPOCZ) composition 63 g was obtained.

(5-2) Composition analysis of BPOCZ composition BPOCZ composition obtained by using high-speed liquid chromatograph mass spectrometry (LMCS) in the same manner as <Analysis of bisphenol C sulfonic acid in bisphenol C composition, measurement of molecular weight>. When the composition of the substance was analyzed, a characteristic peak was detected at a retention time of 9.6 minutes. In order to identify the component of the peak having a retention time of 9.6 minutes, it was measured by high performance liquid chromatography equipped with a mass meter, and it was found that the molecular weight was 376 g / mol. Similar to bisphenol C, it is easily inferred that it is a compound in which a sulfone group is added to BPOCZ (hereinafter, referred to as "BPOCZ sulfonic acid" or "BPOCZ-SA").

When this BPOCZ sulfonic acid was converted to bisphenol C sulfonic acid and the content of BPOCZ sulfonic acid in the BPOCZ composition was calculated, it was 500 mass ppb, and the BPOCZ purity of the BPOCZ composition was 99.8 mass%. there were.

(5-3) Color tone of BPOCZ composition The methanol-dissolved color of the BPOCZ composition obtained in (5-1) was measured by the same method as <Metall-dissolved color of bisphenol C composition>. The number was 5. Since BPOCZ has a high melting point, 10 g of the BPOCZ composition obtained in (5-1) and 10 g of diphenyl carbonate are placed in a Nichiden Rika Glass test tube "P-24" (24 mmφ x 200 mm) and melted at 190 ° C. for 30 minutes. The value obtained by doubling the number of Hazen colors measured by "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd. at that time was defined as the melt color difference of the BPOCZ composition. When the melt color difference was measured by this method, the number of Hazen colors was 45.

<Comparative example 3>
The composition analysis of the reagent BPOCZ (reagent BPOCZ) manufactured by Tokyo Chemical Industry Co., Ltd., the methanol dissolution color, and the melt color difference were evaluated by the same method as in Example 5.

(Ratio 3-1) Composition Analysis of BPOCZ Composition Analysis was carried out in the same manner as in Example 5, and it was confirmed that BPOCZ sulfonic acid was not contained. The BPOCZ purity of the reagent BPOCZ was 99.8% by mass.

(Ratio 3-2) Color tone of BPOCZ composition When the methanol-dissolved color of the reagent BPOCZ was measured, the number of Hazen colors was 12. When the melt color difference of the reagent BPOCZ was measured by the same method as in Example 5, the number of Hazen colors was 82.

Table 2 shows the evaluation results of Example 5 and Comparative Example 3.

The bisphenol composition of the present invention is useful as a resin raw material such as a polycarbonate resin, an epoxy resin, and an aromatic polyester resin, and as an additive such as a curing agent, a color developer, a fading inhibitor, and other bactericidal agents and antibacterial and antifungal agents. Is.

Claims (9)

A bisphenol composition containing bisphenol and bisphenol sulfonic acids.
A bisphenol composition in which the content of the bisphenol with respect to the bisphenol composition is 95% by mass or more. The bisphenol composition according to claim 1, wherein the content of the bisphenol sulfonic acids with respect to the bisphenol composition is 2% by mass or more and 600% by mass or less. The bisphenol composition according to claim 1 or 2, wherein the bisphenol sulfonic acids are compounds represented by the general formula (i) or the general formula (ii).

In the general formula (i) and the general formula (ii), X represents a hydrogen atom or a metal atom. According to any one of claims 1 to 3, the bisphenol is 2,2-bis (4-hydroxy-3-methylphenyl) propane or 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane. The described bisphenol composition. The method for producing a bisphenol composition according to any one of claims 1 to 4.
A method for producing a bisphenol composition in which the bisphenol sulfonic acids are by-produced when the bisphenol is produced. A reaction step (S1) of condensing an aromatic alcohol with a ketone or aldehyde in the presence of an acid catalyst containing sulfuric acid to produce bisphenol.
A step (S2) of removing the aqueous phase from the reaction solution obtained in the reaction step (S1) to obtain an organic phase (O1) containing bisphenol.
The first organic phase (O2) is obtained by washing the organic phase (O1) with desalinated water and / or a basic aqueous solution so that the pH of the aqueous phase to be removed becomes 8.5 or more basic. Cleaning step (S3) and
The second washing step of washing the organic phase (O2) with desalted water until the electrical conductivity of the aqueous phase to be removed becomes 1.0 μs / cm or more and 20 μs / cm or less to obtain the organic phase (O3). (S4) and
The method for producing a bisphenol composition according to claim 5, further comprising a crystallization step (S5) for crystallizing the organic phase (O3) to obtain a bisphenol composition. The method for producing a bisphenol composition according to any one of claims 1 to 4.
A method for producing a bisphenol composition, in which the bisphenol sulfonic acids are added to the bisphenol. A method for producing a polycarbonate resin using the bisphenol composition according to any one of claims 1 to 4. The method for producing a polycarbonate resin according to claim 8, wherein the polycarbonate resin having a viscosity average molecular weight of 15,000 or more and 35,000 or less is produced.

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