WO2020189201A1

WO2020189201A1 - Method for producing bisphenol and method for producing polycarbonate resin

Info

Publication number: WO2020189201A1
Application number: PCT/JP2020/007747
Authority: WO
Inventors: 馨内山; 幸恵中嶋; 岸田　真; 芳恵 ▲高▼見
Original assignee: 三菱ケミカル株式会社
Priority date: 2019-03-18
Filing date: 2020-02-26
Publication date: 2020-09-24
Also published as: CN113574041A; TWI818160B; TW202039410A; JPWO2020189201A1; CN113574041B; JP7371682B2

Abstract

This method for producing bisphenol includes: a step for mixing an organic phase 1 that contains bisphenol, the organic phase 1 being in a mixed solution 1 of an aqueous phase 1 and the organic phase 1, with a chelating agent to obtain a mixed solution 2 of an aqueous phase having a pH of 6 or less and an organic phase; a step for mixing the resultant mixed solution 2 and a base to obtain a mixed solution 3 of an aqueous phase having a pH of 8 or higher and an organic phase; and a step for removing the aqueous phase having a pH of 8 or higher from the resultant mixed solution 3 to obtain an organic phase 3A, the method being such that the solubility of the chelating agent in the aqueous phase of the mixed solution 3 is higher than the solubility in the organic phase of the mixed solution 3.

Description

Method for producing bisphenol and method for producing polycarbonate resin

The present invention relates to a method for producing bisphenol and a method for producing a polycarbonate resin using the obtained bisphenol.
The bisphenol produced by the method of the present invention contains resin raw materials such as polycarbonate resin, epoxy resin and aromatic polyester resin, and addition of a curing agent, a color developer, a fading inhibitor, and other bactericidal agents and antibacterial and antifungal agents. It is useful as an agent.

Bisphenol is useful as a raw material for polymer materials such as polycarbonate resin, epoxy resin, and aromatic polyester resin. 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 Document 1). A method for producing bisphenol containing a fluorene skeleton is also known (Patent Document 2).

Japanese Unexamined Patent Publication No. 2014-40376 Japanese Unexamined Patent Publication No. 2000-26349

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.
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".

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".

In the production of the polycarbonate resin, since the polymerization reaction is carried out after the bisphenol is melted, thermal color stability before the start of the polymerization is also required.
In the present invention, this color tone is referred to as "thermal color tone stability".

In the production of polycarbonate resin, if bisphenol is thermally decomposed before the start of polymerization, the amount of substance of bisphenol decreases, and the amount of substance ratio with diphenyl carbonate, which is a raw material, deviates from the predetermined amount of substance ratio. Since it becomes impossible to obtain a polycarbonate resin having a desired molecular weight, thermal stability of bisphenol is also required.
In the present invention, this stability is referred to as "pyrolysis stability".

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

When hydrogen chloride gas or hydrochloric acid is used as a catalyst for the bisphenol production reaction, hydrogen chloride volatilizes, corrodes the equipment, and the corroded components are mixed with bisphenol, which tends to deteriorate the quality of bisphenol. Is not easy.
Therefore, in order to obtain high quality bisphenol, it is important to efficiently wash and efficiently recover bisphenol.

As a method for recovering bisphenol, for example, as in the method described in Patent Document 1, water is supplied to the reaction solution to reduce the concentration of the acid catalyst to terminate (stop) the reaction, and then recover the bisphenol. The method is known. However, if heating or the like is performed at the time of recovery of bisphenol in a state where the aqueous phase is highly acidic after the bisphenol formation reaction, bisphenol is easily decomposed and another problem such as an increase in by-products occurs.
In order to suppress the decomposition of bisphenol, a method is known in which the acidity of the reaction solution is lowered by neutralizing the acid catalyst with a basic aqueous solution to terminate the reaction (for example, Patent Document 2). However, with this method, the concentration of the aqueous phase after the bisphenol formation reaction becomes pH 4 to 6, and it is difficult to improve the quality of bisphenol deteriorated by equipment corrosion.

Under such circumstances, in the production of bisphenol using hydrogen chloride gas or hydrochloric acid as a catalyst, a method for improving the quality of bisphenol deteriorated due to equipment corrosion was required.

The present invention provides a method for producing high-quality bisphenol and a method for producing a polycarbonate resin using the bisphenol by devising a recovery process for bisphenol produced using hydrogen chloride gas or hydrochloric acid as an acid catalyst. The purpose is to provide.

The present inventor can produce high-quality bisphenol by adding and mixing a chelating agent to an organic phase containing bisphenol under specific conditions after the reaction for producing bisphenol, and then adding and mixing a basic aqueous solution. I found. The present inventor has also found that the produced bisphenol can be used to produce a polycarbonate resin having a good color tone.
The gist of the present invention lies in the following [1] to [9].

[1] A step of mixing the organic phase 1 of the mixed solution 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol with a chelating agent to obtain a mixed solution 2 of the aqueous phase and the organic phase having a pH of 6 or less. A step of mixing the obtained mixed solution 2 with a base to obtain a mixed solution 3 of an aqueous phase having a pH of 8 or higher and an organic phase, and removing the aqueous phase having a pH of 8 or higher from the obtained mixed solution 3 to obtain an organic phase. A method for producing bisphenol, which comprises a step of obtaining 3A, wherein the solubility of the chelating agent in the aqueous phase of the mixed solution 3 is higher than the solubility of the mixed solution 3 in the organic phase.

[2] The method for producing bisphenol according to [1], wherein the organic phase 1 is the organic phase 1A obtained by removing the aqueous phase from the mixed solution 1.

[3] The bisphenol according to [2], wherein the aqueous phase is removed from the mixed solution 1 so that the mixing ratio of the aqueous phase and the organic phase 1A after removing the aqueous phase is 1: 700 or less by weight. Manufacturing method.

[4] Production of the bisphenol according to any one of [1] to [3], wherein the mixing ratio of the aqueous phase and the organic phase in the mixed solution 2 is 0.001: 100 to 1000: 700 by weight. Method.

[5] The description according to any one of [1] to [4], which comprises a step of removing the aqueous phase from the mixed solution 4 obtained by mixing the organic phase 3A and desalted water to obtain the organic phase 4. Method for producing bisphenol.

[6] The method for producing bisphenol according to any one of [1] to [5], wherein the bisphenol is a bisphenol obtained by condensing a ketone or aldehyde and an aromatic alcohol in the presence of hydrogen chloride. ..

[7] The bisphenols are 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) dodecane, and 2,2-bis (4-hydroxy-3, The method for producing bisphenol according to any one of [1] to [6], which is one of the group consisting of 5-dimethylphenyl) methane.

[8] A method for producing a polycarbonate resin using bisphenol produced by the method for producing bisphenol according to any one of [1] to [7].

[9] A method for producing a metal-coordinating organic compound containing a partial structure represented by the following formula (I) in the molecule, wherein the aqueous phase 1'and the organic phase 1'containing the organic compound are produced. The step of mixing the organic phase 1'of the mixed solution 1'with and the chelating agent to obtain a mixed solution 2'of an aqueous phase and an organic phase having a pH of 6 or less, and the obtained mixed solution 2'and a base. A step of mixing to obtain a mixed solution 3'of an aqueous phase having a pH of 8 or more and an organic phase, and a step of removing the aqueous phase having a pH of 8 or more from the obtained mixed solution 3'to obtain an organic phase 3A'. The solubility of the organic compound in the organic phase of the mixed solution 3'is higher than the solubility of the mixed solution 3'in the aqueous phase, and the solubility of the chelating agent in the aqueous phase of the mixed solution 3'is the mixing. A method for producing an organic compound, which has a higher solubility in the organic phase of the liquid 3'.

In formula (I), X and Y are the same or different elements, and are elements selected from the group consisting of trivalent nitrogen, divalent oxygen, trivalent phosphorus, and divalent sulfur. The line connecting X and Y is a carbon chain.

According to the present invention, it is possible to produce bisphenol having good methanol dissolution color, melt color difference, thermal color tone stability, and thermal decomposition stability. According to the present invention, the obtained bisphenol can be used to produce a polycarbonate resin having a good color tone.

Embodiments of the present invention will be described in detail below. The description of the constituent elements described below is an example of the embodiment of the present invention, and the present invention is not limited to the following description contents as long as the gist thereof is not exceeded.
When the expression "-" is used in the present specification, it shall be used as an expression including numerical values or physical property values before and after the expression.

[Manufacturing method of bisphenol]
The method for producing bisphenol of the present invention is a mixed solution of an aqueous phase and an organic phase having a pH of 6 or less by mixing an organic phase 1 of a mixed solution 1 of an aqueous phase 1 and an organic phase 1 containing bisphenol with a chelating agent. A step of obtaining 2 (hereinafter, this step may be referred to as a "chelate treatment step") and a mixed solution of the obtained mixed solution 2 and a base are mixed to obtain a mixed solution of an aqueous phase and an organic phase having a pH of 8 or higher. The step of obtaining 3 and the step of removing the aqueous phase having a pH of 8 or more from the obtained mixed solution 3 to obtain the organic phase 3A (hereinafter, the step of mixing the bases to obtain the organic phase 3A is the "alkali treatment step". It is characterized in that the solubility of the chelating agent in the aqueous phase of the mixed solution 3 is higher than the solubility of the mixed solution 3 in the organic phase.

The feature of the method for producing bisphenol of the present invention is that a chelating agent is mixed with the organic phase 1 of the mixed solution 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol, and the aqueous phase and the organic phase having a pH of 6 or less are mixed. When liquid 2 is obtained and the mixed liquid 2 and the base are mixed to obtain a mixed liquid 3 of an aqueous phase having a pH of 8 or higher and an organic phase, the solubility of the mixed liquid 3 in the aqueous phase is the organic of the mixed liquid 3. The purpose is to remove the aqueous phase having a pH of 8 or higher from the mixed solution 3 by using a chelating agent having a higher solubility in the phase, and to efficiently recover the organic phase 3A containing bisphenol.

As described above, when hydrogen chloride gas or hydrochloric acid is conventionally used as a catalyst for the bisphenol production reaction, hydrogen chloride volatilizes, corrodes the equipment, and the corrosive components are mixed with the bisphenol, so that the quality of the bisphenol deteriorates. There was a problem. The corrosive component mixed in the bisphenol is mainly composed of a metal component such as iron, which is a constituent material of the equipment. In the present invention, a chelating agent is added and mixed under the specific pH acidic conditions, and then a basic aqueous solution is added to make the pH alkaline conditions to chelate metal components such as iron mixed in the bisphenol product. Efficiently remove. Then, the quality of bisphenol can be improved by removing the corrosive component.

In the present invention, the organic phase 1 to which the chelating agent is added is preferably the organic phase 1A obtained by removing the aqueous phase from the mixed solution 1. For that purpose, the aqueous phase 1 contained in the mixed solution 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol is preferably an aqueous phase having a pH of 6 or less.

In this case, as a method for obtaining the organic phase 1A by removing the aqueous phase from the mixed solution 1 of the aqueous phase 1 having a pH of 6 or less and the organic phase 1 containing bisphenol, for example, the following (1) and (2) ) Method can be mentioned.
(1) After the bisphenol production reaction, a method of adding an acidic solution to the reaction solution for phase separation (2) After the bisphenol production reaction, the reaction solution is neutralized, washed and crystallized, then the bisphenol is taken out and the taken out bisphenol is used. A method in which a bisphenol solution obtained by dissolving in a solvent is washed with an acidic solution and then phase-separated.

[Bisphenol production reaction]
The bisphenol production reaction to which the present invention is preferably applied will be described.

In the bisphenol production reaction, a ketone or aldehyde and an aromatic alcohol are condensed in the presence of a catalyst to obtain a reaction solution containing bisphenol.

The reaction of bisphenol is usually carried out according to the reaction formula (1) shown below.

For ^R 1 - ^{R 6} in the above reaction formula (1) are as described for ^R 1 - ^{R 6} in the general formula described below (2) - (3).

<Aromatic alcohol>.
The aromatic alcohol used as a raw material for bisphenol is usually a compound represented by the following general formula (2).

In the general formula (2), examples of R ¹ to R ⁴ include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group and the like independently of each other. Substituents such as the alkyl group, alkoxy group and aryl group may be substituted or unsubstituted. 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, cyclo Examples thereof include a heptyl group, a cyclooctyl group, a cyclododecyl group, a benzyl group, a phenyl group, a tolyl group, and a 2,6-dimethylphenyl group.

Of these, if R ² and R ³ are sterically bulky, the condensation reaction is unlikely to proceed. Therefore, as the aromatic alcohol, an aromatic alcohol in which R ² and R ³ are hydrogen atoms is preferable.
Further, as the aromatic alcohol, those in which R ¹ to R ⁴ are independently hydrogen atoms or alkyl groups are preferable, and more preferably, R ¹ and R ⁴ are independently hydrogen atoms or alkyl groups, respectively, and R ^An aromatic alcohol in which ² and R ³ are hydrogen atoms.

Specific examples of the aromatic alcohol represented by the general formula (2) include phenol, methylphenol (cresol), dimethylphenol (xylenol), ethylphenol, propylphenol, butylphenol, methoxyphenol, ethoxyphenol, and propoxyphenol. Examples thereof include butoxyphenol, aminophenol, benzylphenol and phenylphenol.

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

<Ketone or aldehyde>
The ketone or aldehyde used as a raw material for bisphenol is usually a compound represented by the following general formula (3).

In the general formula (3), examples of R ⁵ and R ⁶ include a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group, respectively. Substituents such as the alkyl group, alkoxy group and aryl group may be substituted or unsubstituted. Examples of R ⁵ and R ⁶ include hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, and 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, benzyl group, phenyl group, tolyl group, 2,6-dimethylphenyl group and the like can be mentioned.

R ⁵ and R ⁶ may be bonded or crosslinked with each other between the two groups. R ⁵ and R ⁶ may be bonded together with adjacent carbon atoms to form a cycloalkylidene group that may contain heteroatoms. The cycloalkylidene group is a divalent group obtained by removing two hydrogen atoms from one carbon atom of cycloalkane. When R ⁵ and R ⁶ are cycloalkylidene groups formed by bonding with adjacent carbons, the obtained bisphenol has a structure in which an aromatic alcohol is bonded via a cycloalkylidene group.

The cycloalkylidene group and R ⁵ and R ⁶ are attached form together with the adjacent carbon atoms, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3,3,5-trimethyl Cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclododecylidene, fluorenylidene, xantonilidene, thioxanthonilidene and the like can be mentioned.

Specific examples of the compound represented by the general formula (3) include formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde, undecylaldehyde, and dodecyl. Ketones such as aldehydes; ketones such as acetone, butanone, pentanon, hexanone, heptanone, octanon, nonanone, decanone, undecanone, dodecanone; benzaldehyde, phenylmethylketone, phenylethylketone, phenylpropylketone, cresylmethylketone, cleres Arylalkyl Ketones such as Zyrethyl Ketone, Cresylpropyl Ketone, Xylyl Methyl Ketone, Xylyl Ethyl Ketone, Xylylpropyl Ketone, Cyclopropanone, Cyclobutanone, Cyclopentanone, Cyclohexanone, Cycloheptanone, Cyclooctanone, Cyclononanone , Cyclic alcan ketones such as cyclodecanone, cycloundecanone, cyclododecanone; and the like. Of these, acetone is preferable.

<Bisphenol>
In the method for producing bisphenol of the present invention, bisphenol represented by the following general formula (4) is produced by condensation of a ketone or aldehyde with an aromatic alcohol according to the reaction formula (1).

In the general formula (4), R ¹ to R ⁶ are synonymous with those in the general formulas (2) and (3).

Specific examples of the bisphenol represented by the general formula (4) 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-hydroxyphenyl) ) Heptane, 2,2-bis (4-hydroxy-3-methylphenyl) heptane, 4,4-bis (4-hydroxyphenyl) heptane, 4,4-bis (4-hydroxy-3-methylphenyl) heptane, etc. However, it is not limited to these.

Among these, the method for producing bisphenol of the present invention is 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) dodecane, or 2,2-bis (4). It is suitable for the production of -hydroxy-3,5-dimethylphenyl) propane, and is particularly suitable for the production of 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C).

<Hydrogen chloride>
In the present invention, it is preferable to use hydrogen chloride as the catalyst because the effect of the present invention can be obtained more remarkably. Examples of hydrogen chloride include hydrogen chloride gas and hydrochloric acid. Of these, hydrogen chloride gas is preferable.

If the molar ratio of hydrogen chloride to the ketone or aldehyde used in the reaction ((number of moles of hydrogen chloride / number of moles of ketone) or (number of moles of hydrogen chloride / number of moles of aldehyde)) is small, water produced as a by-product during the condensation reaction Hydrogen chloride is diluted by this, which requires a long reaction time. If this molar ratio is large, the amount of ketones or aldehydes may increase. From these facts, the lower limit of the molar ratio of hydrogen chloride to ketones or aldehydes is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 10 or less, more preferably. It is 8 or less, more preferably 5 or less.

<Condensation reaction>
The method for condensing the aromatic alcohol with the ketone or aldehyde in order to obtain the reaction solution containing bisphenol is not particularly limited, and examples thereof include the following methods.
(I) A method in which a ketone or aldehyde is supplied to a mixed solution containing an aromatic alcohol and hydrogen chloride and then reacted for a predetermined time. (Ii) Hydrogen chloride is supplied to a mixed solution containing an aromatic alcohol and a ketone or aldehyde. After that, how to react for a predetermined time

Examples of the above-mentioned (i) supply of ketone or aldehyde and the above-mentioned (ii) supply of hydrogen chloride include a method of supplying all at once and a method of supplying hydrogen chloride separately. Since the reaction for producing bisphenol is an exothermic reaction, it is preferable to supply the bisphenol in divided amounts, such as by dropping it little by little. The method (i) above is preferable because the self-condensation of ketones or aldehydes can be further suppressed.

In the reaction of condensing an aromatic alcohol with a ketone or an aldehyde, the molar ratio of the aromatic alcohol to the ketone or the aldehyde ((the number of moles of the aromatic alcohol / the number of moles of the ketone) or (the number of moles of the aromatic alcohol / the number of moles of the aldehyde) If the number of moles)) is small, the amount of ketones or aldehydes tends to increase. If this molar ratio is high, aromatic alcohol is lost unreacted. From these facts, the molar ratio of aromatic alcohol to ketone or aldehyde is preferably 1.5 or more, more preferably 1.6 or more, further preferably 1.7 or more, preferably 15 or less, more preferably 10. Below, it is more preferably 8 or less.

<Thiol>
In the present invention, thiol may be used as a cocatalyst in the reaction of condensing a ketone or aldehyde with an aromatic alcohol.

By using thiol as a cocatalyst, for example, in the production of 2,2-bis (4-hydroxy-3-methylphenyl) propane, the production of 24 bodies is suppressed, the selectivity of 44 bodies is increased, and the polycarbonate resin is produced. It is possible to obtain the effect of increasing the polymerization activity at the time and improving the color tone of the obtained polycarbonate resin.
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 produces an inhibitor for 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 formation of deteriorating substances as well as

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 the thiol cocatalyst to the ketone or aldehyde used for condensation ((the number of moles of the thiol cocatalyst / the number of moles of the ketone) or (the number of moles of the thiol cocatalyst / the number of moles of the aldehyde)) is small, the thiol cocatalyst is used. The effect of improving the reaction selectivity of bisphenol by using it cannot be obtained. If this molar ratio is large, it may be mixed with bisphenol and the quality may deteriorate. From these facts, the molar ratio of the thiol cocatalyst to the ketone and the aldehyde is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more, preferably 1 or less, more preferably 0. It is 5.5 or less, more preferably 0.1 or less.

The thiol is preferably premixed with a ketone or aldehyde before being subjected to the reaction. The method for mixing the thiol with the ketone or aldehyde may be a mixture of the thiol with the ketone or the aldehyde, or a ketone or the aldehyde with the thiol.
As a method of mixing the mixed solution of thiol and ketone or aldehyde and the aromatic alcohol, the aromatic alcohol may be mixed with the mixed solution of thiol and ketone or aldehyde, and the aromatic alcohol is mixed with thiol and ketone or aldehyde. The mixed solution of the above may be mixed. It is preferable to mix a mixed solution of thiol and a ketone or aldehyde with an aromatic alcohol.

<Organic solvent>
In the method for producing bisphenol of the present invention, 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 bisphenol production reaction, but aromatic hydrocarbons are usually used. Here, the aromatic alcohol as a substrate and the bisphenol as a product are removed from the organic solvent.

Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, and mesitylene. These 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.

If the mass ratio of the organic solvent to the ketone or aldehyde used for condensation ((mass of ketone / mass of organic solvent) or (mass of aldehyde / mass of organic solvent)) is too large, the ketone or aldehyde and the aromatic alcohol Is difficult to react and it takes a long time to react. If this mass ratio is too small, the increase in the amount of ketones or aldehydes may be promoted, or 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, more preferably 1 or more, while this mass ratio is preferably 100 or less, more preferably 50 or less.

A large amount of the raw material aromatic alcohol may be used instead of the organic solvent instead of the organic solvent. In this case, the unreacted aromatic alcohol is a loss, but the loss can be reduced by recovering, purifying and reusing it by distillation or the like.

<Reaction conditions>
The reaction time of the bisphenol production reaction is preferably 30 hours or less, more preferably 25 hours or less, still more preferably 20 hours or less because the produced bisphenol may be decomposed if it is too long. The lower limit of the reaction time is usually 2 hours or more.

The reaction time includes the mixing time at the time of preparing the reaction solution. For example, when a mixed solution in which an aromatic alcohol and an acid catalyst are mixed is supplied with a ketone or aldehyde over 1 hour and then reacted for 1 hour, the reaction time is 2 hours.

When the reaction temperature of the bisphenol production reaction is high, the amount of ketone or aldehyde tends to increase, and when the temperature is low, the time required for the reaction becomes long. From these facts, the reaction temperature is preferably -30 ° C or higher, more preferably -20 ° C or higher, further preferably -15 ° C or higher, preferably 80 ° C or lower, more preferably 70 ° C or lower, still more preferably 60 ° C. It is below ° C. The reaction temperature means the average temperature from the start to the end of the first step.

The reaction solution containing bisphenol is preferably obtained as a slurry-like solution in which the produced bisphenol is not completely dissolved in the reaction solution but dispersed. By appropriately adjusting the type of acid catalyst, the type and amount of organic solvent, the reaction time, etc., a slurry in which bisphenol is dispersed can be obtained.

[Chelating process]
The chelate treatment step in the present invention may be carried out before the crystallization step described later and after the bisphenol formation reaction step, or after the bisphenol formation reaction and after the water washing step described later, or the crystals described below. It may be performed after the analysis step.

When the chelate treatment step is performed after the bisphenol production reaction, water is added to and mixed with the reaction solution of the bisphenol production reaction, and if the pH of the aqueous phase obtained by phase separation is 6 or less, the aqueous phase is removed. A chelating agent can be added and mixed with the organic phase 1A as the organic phase 1 to obtain a mixed solution 2.

In the removal of the aqueous phase, the mixing ratio of the aqueous phase and the organic phase 1A after the removal of the aqueous phase is a weight ratio of aqueous phase: organic phase 1A = 1: 700 or less, particularly 1: 800 or less, especially 1: 900 or less. It is preferable to do so. If the amount of the aqueous phase is larger than this range, the amount of the basic aqueous solution required to bring the pH to 8 or higher in the alkali treatment step described later increases.

When the chelate treatment step is performed after the bisphenol production reaction step and the water washing step described later, if the pH of the aqueous phase obtained by phase separation after washing by adding or mixing water is 6 or less, this water A chelating agent is added and mixed with the organic phase after removing the phase as the organic phase 1 to obtain a mixed solution 2.
When the pH of the aqueous phase after washing exceeds 6, an acidic aqueous solution may be added and mixed with the organic phase after removing the aqueous phase to separate the aqueous phase having a pH of 6 or less.

When the chelating treatment step is performed after the crystallization step described later, an organic solvent is added to the solid bisphenol recovered by crystallization to obtain a bisphenol solution, and an acidic aqueous solution is added to and mixed with the bisphenol solution to obtain water having a pH of 6 or less. The phases may be separated from each other.

The above acidic aqueous solution is added and mixed, and water is added to the organic phase obtained by phase separation, and the phase is separated by mixing. If the phase-separated aqueous phase is pH 6 or less, this aqueous phase is used. The organic phase obtained by phase separation may be used as the first organic phase.

In either case, if the pH of the aqueous phase separated when obtaining the organic phase 1A exceeds 6, the corrosive components cannot be sufficiently removed by the chelating agent, and methanol dissolved color, molten color difference, thermal color stability, etc. It is not possible to obtain bisphenol with good thermal decomposition stability. The pH of this aqueous phase is particularly preferably 5 or less. If the pH of the aqueous phase is excessively low, the amount of the basic aqueous solution used in the next alkali treatment step becomes excessive, so the pH of the aqueous phase is preferably -1 or more.
In the present invention, the pH is a measured value at room temperature (20 to 30 ° C.).

As the acidic substance of the acidic aqueous solution for obtaining an aqueous phase having a pH of 6 or less as described above, hydrochloric acid, sulfuric acid, phosphoric acid, an inorganic acid of nitric acid and the like can be used.

The concentration of acidic substances in the acidic aqueous solution is appropriately adjusted according to the acidic substances and basic substances remaining in bisphenol. If the concentration of the acidic substance in the acidic aqueous solution is too high, bisphenol is decomposed, so that it is preferably 35% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less. If the concentration of the acidic substance in the acidic aqueous solution is too low, it is necessary to increase the amount of the acidic aqueous solution in order to obtain an aqueous phase having a pH of 6 or less. Therefore, the lower limit of the concentration of the acidic substance in the acidic aqueous solution is preferably 0.01 mass ppm or more. , 0.1 mass ppm or more is more preferable.

If the amount of the acidic aqueous solution used is too large, the amount of the aqueous phase will be too large with respect to the amount of the organic phase to be phase-separated after the addition of the acidic aqueous solution, and the phase separation will not be easy. Therefore, the mass ratio of the acidic aqueous solution to the amount of the organic phase to which the acidic aqueous solution is added (mass of the acidic aqueous solution / mass of the organic phase) is preferably 2 or less, more preferably 1 or less, still more preferably 0.5 or less. If the amount of the acidic aqueous solution to be added is too small, the amount of the organic phase is too large with respect to the amount of the aqueous phase, and phase separation is not easy. Therefore, the mass ratio of the acidic aqueous solution to the amount of the organic phase is preferably 0.05 or more, more preferably 0.1 or more.

The type of chelating agent to be added to the organic phase 1 after separating the aqueous phase having a pH of 6 or less is not limited as long as it is generally used as a chelating agent, but in the present invention, the alkali treatment step described later The solubility in the aqueous phase in the mixed solution 3 (hereinafter referred to as "solubility for the aqueous phase") obtained in 1) is higher than the solubility in the organic phase in the mixed solution 3 (hereinafter referred to as "solubility for the organic phase"). Also use a high chelating agent.

If the solubility of the chelating agent used in the aqueous phase is less than or equal to the solubility in the organic phase, the chelating agent used remains in the organic phase and remains in bisphenol, and the purity of bisphenol decreases. The chelating agent may have a higher solubility in the aqueous phase than the solubility in the organic phase, but the ratio of the solubility in the aqueous phase / the solubility in the organic phase is 1.5 times or more, preferably 2 times or more, more preferably more preferably. It is more than 10 times.

Examples of chelating agents include β-diketones such as acetylacetone and 3,5-heptandione; aminocarboxylic acids such as ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid and hydroxyethylethylenediaminetriacetic acid and salts thereof; pyruvate and acetoacetic acid. , Lebric acid, α-ketoglutaric acid, ketoic acid such as acetonedicarboxylic acid; hydroxy acids such as glycolic acid, glyceric acid, xylonic acid, gluconic acid, lactic acid, tartronic acid, tartrate acid, xylal acid, galactal acid, malic acid, citric acid; Polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid; amino acids such as aspartic acid and glutamic acid; polyphosphoric acids such as phytic acid, hydroxyethylidene diphosphate, nitrilotrismethylene phosphate and ethylenediaminetetramethylene phosphate; dimethyl Examples thereof include dioximes such as glyoxime, benzyl diglyoxime, and 1,2-cyclohexyl diglyoxime.

Among these, ethylenediaminetetraacetic acid, citric acid, oxalic acid, malonic acid, and succinic acid are examples of those that satisfy the above-mentioned solubility in aqueous phase and solubility in organic phase.

Among these, a tetravalent carboxylic acid is preferable, and aminocarboxylic acids such as ethylenediaminetetraacetic acid and salts thereof are preferable from the viewpoint of easily chelating with various metals. In addition, a chelating agent composed of only carbon, hydrogen, and oxygen atoms is preferable because it has excellent solubility in an organic solvent and easily binds to a corrosive component. Examples thereof include acetylacetone and 3,5-heptandione. Β-diketones such as: pyruvate, acetoacetic acid, levulinic acid, α-ketoglutaric acid, acetone dicarboxylic acid and other keto acids; glycolic acid, glyceric acid, xylonic acid, gluconic acid, lactic acid, tartronic acid, tartrate acid, xylolic acid, galactal Hydroxy acids such as acids, malic acids and citric acids; polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid.

Only one of these chelating agents may be used, or two or more of these chelating agents may be used in combination.

The chelating agent is preferably added to the organic phase 1 as an aqueous solution of 0.1% by mass or more, particularly 0.5% by mass or more, and 15% by mass or less, particularly about 10% by mass or less. If the concentration of the chelating agent is too high, it may precipitate and the effect of the chelating agent may be reduced. If the concentration of the chelating agent is too low, there is a problem that the amount of wastewater generated after the chelating agent is supplied increases.

The amount of the aqueous chelating agent added to the organic phase 1 may be an amount that can sufficiently chelate and remove the corrosive components in the organic phase 1, the concentration of the chelating agent, and the organic phase 1 to be treated. It also depends on the amount of corrosive components in. If the amount of the aqueous chelating agent added to the organic phase 1 is too large, the production cost increases. If the amount of the aqueous chelating agent added to the organic phase 1 is too small, the corrosive components in the organic phase 1 cannot be sufficiently removed, and the effects of the present invention cannot be sufficiently obtained. Therefore, the mass ratio of the chelating agent aqueous solution to the organic phase 1 (mass of the chelating agent aqueous solution / mass of the organic phase 1) is 0.0001 or more, particularly 0.001 or more, and 10 or less, particularly 1 or less. It is preferable to have.

The pH of the aqueous phase of the mixed solution 2 after the addition and mixing of the aqueous chelating agent solution is also 6 or less, particularly 5 or less, preferably -1 or more.

[Alkaline treatment process]
In the alkali treatment step of the present invention, a base is preferably added and mixed as a basic aqueous solution to the mixed solution 2 obtained in the above chelate treatment step to obtain a mixed solution 3 of an aqueous phase having a pH of 8 or higher and an organic phase. This is a step of removing an aqueous phase having a pH of 8 or higher from the obtained mixed solution 3 to obtain an organic phase 3A.
Even if a basic aqueous solution is added to the organic phase from which the aqueous phase has been removed after the aqueous phase has been removed from the mixed solution 2 into the aqueous phase and the organic phase, the chelating effect of the chelating agent cannot be obtained. Therefore, it is important to add the basic aqueous solution to the mixed solution 2 before completely removing the aqueous phase. That is, the mixing ratio of the aqueous phase and the organic phase in the mixed solution 2 is preferably more than 0.001: 700 by weight, more preferably more than 0.01: 700, and 0. It is particularly preferable that there are more aqueous phases than .05: 700. On the other hand, the mixing ratio of the aqueous phase and the organic phase in the mixed solution 2 is preferably less than 1000: 700 mass ratio by weight, more preferably less than 500: 700, and 300: 700. It is particularly preferable that there is less aqueous phase. If it is out of this range, the chelating agent dissolved in the aqueous phase is also removed, so that the effect of the present invention is not exhibited.

The pH of the aqueous phase to be phase-separated here may be 8 or more, and may be 10 or more or 11 or more, but usually about 8 to 9 is adopted.

Sodium hydrogen carbonate, sodium carbonate, etc. can be used as the basic substance of the basic aqueous solution.

If the concentration of the basic substance in the basic aqueous solution used in this alkali treatment step is too low, the amount of the basic aqueous solution for obtaining an aqueous phase having a pH of 8 or higher increases, the total amount of the liquid increases, and the treatment efficiency deteriorates. .. Therefore, the concentration of the basic substance in the basic aqueous solution is preferably as high as possible, and is preferably a saturated aqueous solution of the basic substance.

If the amount of the basic aqueous solution to be added or mixed is too large, the amount of the aqueous phase will be too large with respect to the amount of the organic phase to be phase-separated after the addition or mixing of the basic aqueous solution, and the phase separation will not be easy. If the amount of the basic aqueous solution is too small, the amount of the organic phase is too large with respect to the amount of the aqueous phase, and phase separation is not easy. From these facts, the mass ratio of the basic aqueous solution to the amount of the mixed solution 2 in the alkali treatment step (mass of the basic aqueous solution / mass of the mixed solution 2) is 0.01 or more, particularly 0.1 or more, and 100 or less. , Especially preferably 10 or less.

It is preferable that the organic phase 3A obtained in the alkali treatment step is subjected to the following washing step as necessary and then purified in the crystallization step described later to recover the purified bisphenol.

[Washing process]
The method for producing bisphenol of the present invention may include a water washing step of washing the reaction solution containing bisphenol obtained in the bisphenol production reaction step and the organic phase 3A after the alkali treatment step with water. By performing such a washing step, the amount of impurities can be further reduced.

In the water washing step, for example, demineralized water is supplied to the reaction solution or the organic phase 3A, and the reaction solution or the organic phase 3A is washed with the demineralized water.
When the amount of water supplied here is large, the stirring efficiency tends to decrease due to the large amount of liquid, and the washing efficiency tends to decrease. When the amount of water to be supplied is small, the volume of the aqueous phase becomes small, the stirring efficiency tends to decrease, and the washing efficiency tends to decrease. Therefore, the mass ratio of water to the amount of the reaction solution or the organic phase 3A (mass of water / mass of reaction solution or organic phase 3A) is preferably 0.01 or more, more preferably 0.05 or more, and preferably 2 or less. 1, 1 or less is more preferable, and 0.5 or less is further preferable.

This water washing step is performed by supplying water to the reaction solution or the organic phase 3A for washing, then separating the organic phase and the aqueous phase, and removing the aqueous phase.
The washing step may be performed a plurality of times. In this case, the above water supply, washing, phase separation, and removal of the aqueous phase are repeated.

[Alkaline cleaning process]
The method for producing bisphenol of the present invention may include an alkali washing step of washing the obtained organic phase with a basic aqueous solution after the alkali treatment step or the washing step with water.

In this alkaline cleaning step, after the alkali treatment step or the water washing step, the separated organic phase and the basic aqueous solution are mixed, and then the organic phase and the aqueous phase having a pH of 9 or more are phase-separated to obtain the phase-separated aqueous phase. It is preferably a step of removing to obtain an organic phase.

By washing with a basic aqueous solution in this way, impurities that are easily dissolved under basic conditions can be removed.
The alkaline cleaning step may be performed a plurality of times.

The pH of the aqueous phase separated in the alkaline cleaning step may be 9 or more, and may be 10 or more or 11 or more. The upper limit of this pH may be 14 or less or 13 or less.

As the basic substance of the basic aqueous solution used in the alkaline cleaning step, sodium hydrogen carbonate, sodium carbonate or the like can be used.

The concentration of the basic substance in the basic aqueous solution used in the alkaline cleaning step is appropriately adjusted according to the type of the basic substance and the acid catalyst. If the concentration of the basic substance in the basic aqueous solution is too high, it will remain in the finally obtained bisphenol and deteriorate the quality. Therefore, it is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass. The following is more preferable. If the concentration of the basic substance in the basic aqueous solution is too low, it is necessary to increase the amount of the basic aqueous solution in order to obtain an aqueous phase having a pH of 9 or higher. Therefore, the concentration of the basic substance in the basic aqueous solution is 0.1% by mass. The above is preferable, and 0.5% by mass or more is more preferable.

If the amount of the basic aqueous solution supplied is too large, the amount of the aqueous phase will be too large with respect to the amount of the organic phase to be phase-separated after alkaline cleaning, and phase separation will not be easy. If the amount of the basic aqueous solution supplied is too small, the amount of the organic phase is too large with respect to the amount of the aqueous phase, and phase separation is not easy. From these facts, the mass ratio of the basic aqueous solution to the amount of the organic phase in the alkaline washing step (mass of the basic aqueous solution / mass of the organic phase) is preferably 2 or less, more preferably 1 or less, still more preferably 0.5 or less. , 0.05 or more, more preferably 0.1 or more.

[Temperature of chelate treatment process, alkali treatment process, water washing process, alkali washing process]
In the chelate treatment step, the alkali treatment step, the water washing step and the alkali washing step, in order to suppress the precipitation of bisphenol, the average temperature from the start to the end is preferably 50 ° C. or higher, preferably 55 ° C. or higher. Is more preferable. The average temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, in order to suppress the precipitation of bisphenol due to evaporation of the organic solvent. These steps can be performed, for example, at the same temperature.

[Crystalization process]
The method for producing bisphenol of the present invention preferably includes a crystallization step. The crystallization step is usually carried out after an alkali treatment step or an alkali treatment step, an alkali washing step and a subsequent washing step with water.

Crystallization can be performed according to a conventional method. For example, both a method of utilizing the difference in solubility of bisphenol due to a temperature difference and a method of precipitating a solid by supplying a poor solvent can be applied. Since the purity of the obtained bisphenol tends to decrease in the method of supplying the poor solvent, the method of utilizing the difference in the solubility of the bisphenol due to the temperature difference is preferable.
When the content of aromatic alcohol in the organic phase is high, excess aromatic alcohol may be distilled off before crystallization before crystallization.

For example, bisphenol is precipitated by cooling the organic phase at 60 to 90 ° C. to −10 to 30 ° C. The precipitated bisphenol can be separated into solid and liquid and recovered by drying or the like.

The organic phase used in this crystallization step preferably has an electrical conductivity of 10 μS / cm or less of the aqueous phase (hereinafter, may be referred to as “immediately preceding aqueous phase”) phase-separated in the immediately preceding step. .. When the electrical conductivity of the immediately preceding aqueous phase is 10 μS / cm or less, particularly 9 μS / cm or less, particularly 8 μS / cm or less, impurities such as by-products and residual catalyst in the product are highly removed, and the hue When used as a raw material bisphenol for a polycarbonate resin, bisphenol having high polymerization reaction efficiency and capable of producing a polycarbonate resin having an excellent hue can be obtained, which is preferable.

Here, the electric conductivity of the immediately preceding aqueous phase can be measured with an electric conductivity meter, for example, for the immediately preceding aqueous phase at room temperature (20 to 30 ° C.) separated from each other.

The bisphenol thus obtained may be further purified by a conventional method depending on its use. For example, it can be purified by simple means such as sprinkle washing, water washing, suspension washing, crystallization and column chromatography. Specifically, the obtained bisphenol can be further purified by dissolving it in an organic solvent such as an aromatic hydrocarbon, cooling it, and crystallizing it.

[Process configuration of bisphenol production method]
The method for producing bisphenol of the present invention can be, for example, a production method having a chelate treatment step, an alkali treatment step, a washing step, and a crystallization step in this order. Further, the method for producing bisphenol of the present invention can be a production method having a water washing step, a chelate treatment step, an alkali treatment step, a water washing step, and a crystallization step in this order.

[Preferable physical properties of bisphenol]
Hereinafter, suitable physical properties of bisphenol produced by the method for producing bisphenol of the present invention (hereinafter, may be referred to as "bisphenol of the present invention") will be described.

<Methanol-dissolved color of bisphenol>
The methanol-dissolved color of bisphenol is used to evaluate the color tone of bisphenol at room temperature. The lower the number of Hazen colors of the methanol-dissolved color of bisphenol, the better the color tone of bisphenol (close to white). As a cause of deteriorating the methanol-dissolved color of bisphenol, there is an inclusion of an organic coloring component or a metal.

The methanol-dissolved color of bisphenol is measured at room temperature (about 20 ° C) after dissolving bisphenol in methanol to make a uniform solution. Examples of the measuring method include a method of visually comparing with a standard solution having a Hazen color number, or a method of measuring the Hazen color number using a color difference meter such as "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd. The mass ratio of the solvent methanol and bisphenol used here 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 bisphenol is preferably 20 or less, more preferably 10 or less, and particularly preferably 5 or less.

<Melted color difference of bisphenol>
The melt color difference of bisphenol is used to evaluate the color tone of bisphenol 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 bisphenol indicates that the lower the number of Hazen colors, the better the color tone of bisphenol (closer to white). Causes of exacerbating the melt color difference of bisphenol include components that are colored by heating, in addition to organic coloring components and metal contamination.

The melt color difference of bisphenol is measured in advance by melting bisphenol at a temperature close to the polymerization temperature and measuring the time when the temperature is stable. Examples of the measuring method include a method of visually comparing with a standard solution having a Hazen color number, or a method of measuring the Hazen color number using a color difference meter such as "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd.

The number of Hazen colors is preferably 40 or less, more preferably 30 or less, and particularly preferably 20 or less.

<Thermal color stability of bisphenol>
The thermal color stability of bisphenol is used to evaluate the thermal stability of bisphenol color tone by holding it at a temperature close to the polymerization temperature of polycarbonate for a predetermined time, similar to the melt color difference of bisphenol. The measurement temperature of the thermal color stability of bisphenol is the melting point of bisphenol + 50 ° C.

As for the thermal color stability of bisphenol, the lower the number of Hazen colors, the better the thermal color stability of bisphenol. In addition to the mixing of organic coloring components and metals, the causes of deteriorating the thermal color stability of bisphenol include components that are colored by heating and acidic substances and basic substances having a concentration of about several ppm.

The thermal color stability of bisphenol is measured in advance by melting bisphenol at a temperature close to the polymerization temperature and at a time when the temperature is stable. The retention time for thermal color stability of bisphenol is 4 hours. Examples of the measuring method include a method of visually comparing with a standard solution having a Hazen color number, or a method of measuring the Hazen color number using a color difference meter such as "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd.

The number of Hazen colors is preferably 50 or less, more preferably 45 or less, and particularly preferably 35 or less.

<Pyrolysis stability of bisphenol>
Similar to the thermal color stability of bisphenol, the thermal decomposition stability of bisphenol is used to evaluate the thermal stability of bisphenol by holding it at a temperature close to the polymerization temperature of polycarbonate for a predetermined time. The preferred measurement temperature for the thermal decomposition stability of bisphenol is the melting point of bisphenol + 50 ° C. The thermal decomposition stability of bisphenol indicates that the smaller the amount of decomposition product produced, the more stable the bisphenol is.

The decomposition product in the thermal decomposition stability of bisphenol includes an aromatic alcohol which is a raw material of the bisphenol, or an addition of a ketone or an aldehyde which is a raw material of the aromatic alcohol, although it depends on the type of the bisphenol. In addition to the mixing of organic coloring components and metals, the causes of deteriorating the thermal decomposition stability of bisphenol include components that are colored by heating and acidic substances and basic substances having a concentration of about several ppm.

Detection and quantification of bisphenol degradation products can be performed using standard reverse phase columns for fast analysis.
The amount of isopropenyl cresol produced as a decomposition product of bisphenol as measured in Examples described later is preferably 200 mass ppm or less.

The methanol-dissolved color of bisphenol is a method for evaluating the color tone of bisphenol itself. When bisphenol is the final product, bisphenol with good methanol dissolution color is important. Since the polycarbonate resin inherits the color tone of the raw material, bisphenol having a good color tone is important for the polycarbonate resin that is required to be colorless and transparent.

In the melt polymerization method, which is one of the methods for producing a polycarbonate resin, since the polymerization reaction is carried out at a high temperature, the color tone of bisphenol at the time of melting (melt color difference of bisphenol) and the color tone stability of bisphenol in the molten state (of bisphenol). Thermal color stability) is important.

Further, in the melt polymerization method, the bisphenol is kept melted at a high temperature until the start of the polymerization reaction. In the melt polymerization method, when bisphenol is decomposed at a high temperature, the substance amount ratio with diphenyl carbonate deviates from a predetermined substance amount ratio, and it becomes difficult to obtain a polycarbonate resin having polymerization reaction activity and a predetermined molecular weight. Therefore, resistance to thermal decomposition (thermal decomposition stability of bisphenol) is important.

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 bisphenol, the melt color difference of bisphenol, the thermal color stability of bisphenol, and the thermal decomposition stability of bisphenol are important.

[Use of bisphenol]
The bisphenol of the present invention is a polyether resin, polyester resin, polyarylate resin, polycarbonate resin, polyurethane resin, which is used for various purposes such as optical materials, recording materials, insulating materials, transparent materials, electronic materials, adhesive materials, and heat resistant materials. Components, curing agents, additives or precursors thereof such as various thermoplastic resins such as acrylic resin, various thermocurable resins such as epoxy resin, unsaturated polyester resin, phenol resin, polybenzoxazine resin and cyanate resin. It can be used as such. The bisphenol of the present invention is also useful as an additive such as a color developer such as a heat-sensitive recording material, a fading inhibitor, a bactericide, and an antibacterial and antifungal agent.

The bisphenol of the present invention is preferably used as a raw material (monomer) for a thermoplastic resin or a thermosetting resin, and more preferably as a raw material for a polycarbonate resin or an epoxy resin, because it can impart good mechanical properties. The bisphenol of the present invention is also preferably used as a color developer, and more preferably used in combination with a leuco dye and a discoloration temperature adjuster.

[Manufacturing method of polycarbonate resin]
The bisphenol of the present invention is used as a raw material for producing a polycarbonate resin.

The method for producing a polycarbonate resin using bisphenol of the present invention is a production in which a bisphenol produced by the above method and diphenyl carbonate or the like are subjected to a transesterification reaction in the presence of an alkali metal compound and / or an alkaline earth metal compound. The method.

As the bisphenol of the present invention, only one kind may be used, or two or more kinds may be used to produce a copolymerized polycarbonate resin. Dihydroxy compounds other than the bisphenol of the present invention can also be used in combination for the reaction.

The transesterification reaction can be carried out by appropriately selecting a known method. An example of using the bisphenol and diphenyl carbonate of the present invention as raw materials will be described below.

In the above method for producing a polycarbonate resin, it is preferable to use an excess amount of diphenyl carbonate with respect to the bisphenol 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. The amount of diphenyl carbonate used for bisphenol is preferably small in that the transesterification reaction rate is high and a polycarbonate resin having a desired molecular weight can be easily produced. From these facts, the amount of diphenyl carbonate used with respect to 1 mol of bisphenol is usually 1.001 mol or more, preferably 1.002 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less.

As a raw material supply method, the bisphenol and diphenyl carbonate of the present invention can be supplied in solid form, but it is preferable to supply one or both of them in a liquid state by melting them.

When producing a polycarbonate resin by 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 combination of two or more in any combination and ratio. 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, more preferably 0.10 μmol or more, and usually 100 μmol or less, preferably 50 μmol, based on 1 mol of bisphenol or diphenyl carbonate. Below, it is more preferably 20 μmol or less.
When the amount of the catalyst used is within the above range, the polymerization activity required for producing a polycarbonate resin having a desired molecular weight can be easily obtained, 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, both raw materials supplied to the raw material mixing tank are usually stirred uniformly and then supplied to a polymerization tank to which a transesterification catalyst is added to produce a polymer.

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

According to the bisphenol of the present invention, a polycarbonate resin having excellent hue and transparency can be produced. For example, a polycarbonate resin having a viscosity average molecular weight (Mv) of 10,000 or more, preferably 15,000 or more, 100,000 or less, preferably 35,000 or less, and a pellet YI of 10 or less and excellent hue and transparency can be produced in a short time.

[Method for producing organic compounds]
Similar to the method for producing bisphenol of the present invention, by undergoing the above-mentioned chelate treatment step and alkali treatment step, not only the bisphenol but also the partial structure represented by the following formula (I) in the molecule (hereinafter, "partial structure (hereinafter," partial structure (hereinafter, "partial structure") A metal-coordinating organic compound (hereinafter, may be referred to as “organic compound (I)”) including (may be referred to as “I)” is also mixed in the organic compound (I). It is possible to produce a high-purity and high-quality organic compound (I) by removing impurities such as metals.

Here, "metal coordination" refers to a compound that can be bonded to a metal ion by a coordination bond to form a complex, and the organic compound (I) has a partial structure (I) to form a metal ion. Functions as a ligand for.

Each of X and Y in the formula (I) may further have a substituent containing an element selected from the group consisting of trivalent nitrogen, divalent oxygen, trivalent phosphorus, and divalent sulfur. ..
The "carbon chain" refers to a link in which carbon atoms are connected by a single bond, a double bond, or a triple bond, and is not limited to a chain such as a linear or branched bond, but includes a cyclic structure. It may be a combination of these.

The organic compound (I) is a metal-coordinating compound in which the partial structure (I) functions as a ligand for a metal ion. Therefore, the organic compound (I) may be present in the reaction product as a metal compound used as a catalyst in the production process or as a complex compound coordinated to the metal due to impurities mixed in the production process. There are many.
In the use of the organic compound (I), the product incorporating the metal causes problems such as coloring, decomposition, and alteration due to the contained metal.

By applying the above-mentioned production procedure of the method for producing bisphenol of the present invention to the production of the organic compound (I), the metal is efficiently removed from the organic compound (I) to obtain a high-purity and high-quality organic compound ( I) can be manufactured.

In the method for producing an organic compound of the present invention, the organic phase 1'of the mixed solution 1'of the aqueous phase 1'and the organic phase 1'containing the organic compound (I) and the chelating agent are mixed and pH 6 The following steps of obtaining a mixed solution 2'of an aqueous phase and an organic phase, and a step of mixing the obtained mixed solution 2'and a base to obtain a mixed solution 3'of an aqueous phase having a pH of 8 or more and an organic phase. , The step of removing the aqueous phase having a pH of 8 or more from the obtained mixed solution 3'to obtain the organic phase 3A', and the solubility of the mixed solution 3'of the organic compound (I) in the organic phase of the mixed solution 3 is included. It is characterized in that the solubility of the chelating agent mixture 3'in the aqueous phase is higher than that of the mixture 3'in the organic phase.
In the above-mentioned method for producing bisphenol, "bisphenol" is changed to "organic compound (I)", "organic phase 1" is changed to "organic phase 1'", "mixed solution 2" is changed to "mixed solution 2'", and "organic". "Phase 3A" can be read as "organic phase 3A'", respectively, and can be carried out in the same manner as the above-mentioned method for producing bisphenol.

As the organic compound (I) to which the method for producing an organic compound of the present invention is applied, as the partial structure (I), an amide group, a hydrazide group, an imide group, an amidin group in which X and / or Y are nitrogen elements, Examples thereof include those having a nitrile group, an alcohol group which is an oxygen element, a phenol group, an ether group, a thiol group which is a sulfur element, and a sulfide group.

When the organic compound (I) is the chelating agent, the chelating agent different from the organic compound (I) is selected. For example, the following combinations can be mentioned.
When the organic compound (I) is the carboxylic acid, the β-diketones or the dioxime are selected as the chelating agent.
When the organic compound (I) is the β-diketones, the carboxylic acids or the dioximes are selected as the chelating agent.
When the organic compound (I) is the dioxime, the carboxylic acid or β-diketone is selected as the chelating agent.

Examples of the organic compound (I) include the following, but the organic compound (I) to which the method for producing an organic compound of the present invention is applied is not limited to any of the following.

<Organic compound (I) with the same X and Y>
Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. Oxamide, malonic acid diamide, succinate diamide, glutaru Diamides such as acid diamide, adiponic acid diamide, pimelliate diamide, suberic acid diamide, azelaic acid diamide, sebacic acid diamide, phthalic acid diamide, isophthalic acid diamide, and terephthalic acid diamide.

Dihydrazide oxalate, dihydrazide malonic acid, dihydrazide succinate, dihydrazide glutarate, dihydrazide adipate, dihydrazide pimelliate, dihydrazide suberic acid, dihydrazide azelaine, dihydrazide sevacinate, dihydrazide phthalate, dihydrazide phthalate, dihydrazide phthalate Acids Dinitriles such as butanedinitrile, pentandinitrile, hexanedinitrile, heptanedinitrile, octanedinitrile, nonandinitrile, decandinitrile Dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene Diisocyanides such as diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, etc. ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclo Propanediol, cyclopropanedimethanol, cyclobutanediol, city cyclobutanedimethanol, cyclopentanediol, cyclopentanedimethanol, cyclohexanediol, cyclohexanedimethanol, cycloheptanediol, cycloheptanedimethanol, cyclooctanediol, cyclooctanedimethanol, Dialcohols such as cyclononanediol, cyclononandimethanol, cyclodecanediol, cyclodecanedimethanol

Biphenols such as biphenol, dimethylbiphenol, tetramethylbiphenol Diamines such as ethylenediamine, propylenediamine, butenediamine, pentendiamine, hexenediamine, heptenediamine, octenediamine, nonenediamine, decenediamine, benzenediamine, etc. Diamines such as pentanediamine, hexanediamine, heptanediamine, octanediamine, nonandidiimin, decanediamine

Dihydrazines such as ethylenedihydrazine, propylene dihydrazine, butenedihydrazine, pentendihydrazine, hexenedihydrazine, heptendihydrazine, octendihydrazine, nonanedihydrazine, decenedihydrazine, benzenedihydrazine, dimethoxymethane, dimethoxyethane, Dimethoxypropane, dimethoxybutane, dimethoxypentane, dimethoxyhexane, dimethoxyheptane, dimethoxyoctane, dimethoxynonane, dimethoxydecane, dimethoxybenzene, diethoxymethane, diethoxyethane, diethoxypropane, diethoxybutane, diethoxypentane, diethoxyhexane , Diethoxyheptane, diethoxyoctane, diethoxynonane, diethoxydecane, diethoxybenzene, dipropoxymethane, dipropoxyetane, dipropoxypropane, dipropoxybutane, dipropoxypentane, dipropoxyhexane, dipropoxyheptan, dipropoxyheptan Diethers such as propoxyoctane, dipropoxynonane, dipropoxydecane, dipropoxybenzene

Dimethylthiomethane, dimethylthioethane, dimethylthiopropane, dimethylthiobutane, dimethylthiopentane, dimethylthiohexane, dimethylthioheptan, dimethylthiooctane, dimethylthiononane, dimethylthiodecane, dimethylthiobenzene, diethylthiomethane, diethylthio Etan, diethylthiopropane, diethylthiobutane, diethylthiopentane, diethylthiohexane, diethylthioheptane, diethylthiooctane, diethylthiononane, diethylthiodecane, diethylthiobenzene, dipropylthiomethane, dipropylthioethane, dipropyl Disulfides such as thiopropane, dipropylthiobutane, dipropylthiopentane, dipropylthiohexane, dipropylthioheptan, dipropylthiooctane, dipropylthiononane, dipropylthiodecane, dipropylthiobenzene

<Organic compound (I) with different X and Y>
Nitrile isocyanates such as methine nitrile isocyanate, ethylene nitrile isocyanate, propylene nitrile isocyanate, butene nitrile isocyanate, penten nitrile isocyanate, hexene nitrile isocyanate, heptene nitrile isocyanate, octene nitrile isocyanate, nonen nitrile isocyanate, decene nitrile isocyanate, and benzene nitrile isocyanate.

Hydroxynitriles such as hydroxymethylnitrile, hydroxyethylnitrile, hydroxypropylnitrile, hydroxybutylnitrile, hydroxypentylnitrile, hydroxyhexylnitrile, hydroxyheptylnitrile, hydroxyoctylnitrile, hydroxynonylnitrile, hydroxydecylnitrile, and hydroxyphenylnitrile

Hydroxyphenylmethylnitrile, hydroxyphenylethylnitrile, hydroxyphenylpropylnitrile, hydroxyphenylbutylnitrile, hydroxyphenylpentylnitrile, hydroxyphenylhexylnitrile, hydroxyphenylheptylnitrile, hydroxyphenyloctylnitrile, hydroxyphenylnonylnitrile, hydroxyphenyldecylnitrile , Hydroxyphenylnitriles such as hydroxyphenylphenylnitriles

Aminonitriles such as aminomethylnitrile, aminoethylnitrile, aminopropylnitrile, aminobutylnitrile, aminopentylnitrile, aminohexylnitrile, aminoheptylnitrile, aminooctylnitrile, aminononylnitrile, aminodecylnitrile, aminophenylnitrile

Iminonitriles such as iminomethylnitrile, iminoethylnitrile, iminopropylnitrile, iminobutylnitrile, iminopentylnitrile, iminohexylnitrile, iminoheptylnitrile, iminooctylnitrile, iminononylnitrile, iminodecylnitrile, iminophenylnitrile

Nitrile hydrazines such as methinenitrile hydrazine, ethylenenitrile hydrazine, propylenenitrile hydrazine, butenenitrile hydrazine, pentennitrile hydrazine, hexenenitrile hydrazine, heptenenitrile hydrazine, octenenitrile hydrazine, nonennitrile hydrazine, decenenitrile hydrazine, benzenenitrile hydrazine.

Methoxymethylnitrile, methoxyethylnitrile, methoxypropylnitrile, methoxybutylnitrile, methoxypentylnitrile, methoxyhexylnitrile, methoxyheptylnitrile, methoxyoctylnitrile, methoxynonylnitrile, methoxydecylnitrile, methoxyphenylnitrile, ethoxymethylnitrile, ethoxy Ethylnitrile, ethoxypropylnitrile, ethoxybutylnitrile, ethoxypentylnitrile, ethoxyhexylnitrile, ethoxyheptylnitrile, ethoxyoctylnitrile, ethoxynonylnitrile, ethoxydecylnitrile, ethoxyphenylnitrile, propoxymethylnitrile, propoxyethylnitrile, propoxypropyl Alkoxynitriles such as nitriles, propoxybutyl nitriles, propoxypentyl nitriles, propoxyhexyl nitriles, propoxyheptyl nitriles, propoxyoctyl nitriles, propoxynonyl nitriles, propoxydecyl nitriles, propoxyphenyl nitriles.

Nitrile sulfides such as methine nitrile sulfide, ethylene nitrile sulfide, propylene nitrile sulfide, butene nitrile sulfide, penten nitrile sulfide, hexene nitrile sulfide, heptene nitrile sulfide, octene nitrile sulfide, nonen nitrile sulfide, decene nitrile sulfide, and benzene nitrile sulfide.

Hydroxy isocyanates such as hydroxymethyl isocyanate, hydroxyethyl isocyanate, hydroxypropyl isocyanate, hydroxybutyl isocyanate, hydroxypentyl isocyanate, hydroxyhexyl isocyanate, hydroxyheptyl isocyanate, hydroxyoctyl isocyanate, hydroxynonyl isocyanate, hydroxydecyl isocyanate, hydroxyphenyl isocyanate, etc.

Hydroxyphenylmethyl isocyanate, hydroxyphenylethyl isocyanate, hydroxyphenylpropyl isocyanate, hydroxyphenylbutyl isocyanate, hydroxyphenylpentyl isocyanate, hydroxyphenylhexyl isocyanate, hydroxyphenyl heptyl isocyanate, hydroxyphenyloctyl isocyanate, hydroxyphenylnonyl isocyanate, hydroxyphenyldecyl isocyanate , Hydroxyphenyl isocyanates such as hydroxyphenyl phenyl isocyanate

Amino isocyanates such as aminomethyl isocyanate, aminoethyl isocyanate, aminopropyl isocyanate, aminobutyl isocyanate, aminopentyl isocyanate, aminohexyl isocyanate, aminoheptyl isocyanate, aminooctyl isocyanate, aminononyl isocyanate, aminodecyl isocyanate, aminophenylisocyanate, etc.

Iminomethyl isocyanate, iminoethyl isocyanate, iminopropyl isocyanate, iminobutyl isocyanate, iminopentyl isocyanate, iminohexyl isocyanate, iminoheptyl isocyanate, iminooctyl isocyanate, iminononyl isocyanate, iminodecyl isocyanate, iminophenyl isocyanate and other iminoisocyanates

Ethine isocyanate hydrazine, ethylene isocyanate hydrazine, propylene isocyanate hydrazine, butene isocyanate hydrazine, penten isocyanate hydrazine, hexene isocyanate hydrazine, heptene isocyanate hydrazine, octene isocyanate hydrazine, nonen isocyanate hydrazine, decene isocyanate hydrazine, benzeneisocyanide hydrazine and other isocyanate hydrazines.

Methoxymethyl isocyanate, methoxyethyl isocyanate, methoxypropyl isocyanate, methoxybutyl isocyanate, methoxypentyl isocyanate, methoxyhexyl isocyanate, methoxyheptyl isocyanate, methoxyoctyl isocyanate, methoxynonyl isocyanate, methoxydecyl isocyanate, methoxyphenyl isocyanate, ethoxymethylisocyanate, ethoxy Ethyl isocyanate, ethoxypropyl isocyanate, ethoxybutyl isocyanate, ethoxypentyl isocyanate, ethoxyhexyl isocyanate, ethoxyheptyl isocyanate, ethoxyoctyl isocyanate, ethoxynonyl isocyanate, ethoxydecyl isocyanate, ethoxyphenyl isocyanate, propoxymethyl isocyanate, propoxyethyl isocyanate, propoxypropyl Alkoxy isocyanates such as isocyanate, propoxybutyl isocyanate, propoxypentyl isocyanate, propoxyhexyl isocyanate, propoxyheptyl isocyanate, propoxyoctyl isocyanate, propoxynonyl isocyanate, propoxydecyl isocyanate, propoxyphenyl isocyanate

Silica sulfides such as methine isocyanate sulfide, ethylene isocyanate sulfide, propylene isocyanate sulfide, butene isocyanate sulfide, penten isocyanate sulfide, hexene isocyanate sulfide, heptene isocyanate sulfide, octene isocyanate sulfide, nonene isocyanate sulfide, decene isocyanate sulfide, and benzene isocyanate sulfide.

Hydroxyalkylphenols such as hydroxymethylphenol, hydroxyethylphenol, hydroxypropylphenol, hydroxybutylphenol, hydroxypentylphenol, hydroxyhexylphenol, hydroxyheptylphenol, hydroxyoctylphenol, hydroxynonylphenol, hydroxydecylphenol

Hydroxyalkylamines such as hydroxymethylamine, hydroxyethylamine, hydroxypropylamine, hydroxybutylamine, hydroxypentylamine, hydroxyhexylamine, hydroxyheptylamine, hydroxyoctylamine, hydroxynonylamine, hydroxydecylamine, etc.

Hydroxyalkylimines such as hydroxymethylimine, hydroxyethylimine, hydroxypropylimine, hydroxybutylimine, hydroxypentylimine, hydroxyhexyluimine, hydroxyheptylimine, hydroxyoctylimine, hydroxynonylimine, hydroxydecylimine, etc.

Hydroxyalkyl hydrazines such as hydroxymethyl hydrazine, hydroxyethyl hydrazine, hydroxypropyl hydrazine, hydroxybutyl hydrazine, hydroxypentyl hydrazine, hydroxyhexyl hydrazine, hydroxyheptyl hydrazine, hydroxyoctyl hydrazine, hydroxynonyl hydrazine, hydroxydecyl hydrazine

Methoxymethyl alcohol, methoxyethyl alcohol, methoxypropyl alcohol, methoxybutyl alcohol, methoxypentyl alcohol, methoxyhexyl alcohol, methoxyheptyl alcohol, methoxyoctyl alcohol, methoxynonyl alcohol, methoxydecyl alcohol, methoxyphenyl alcohol, ethoxymethyl alcohol, ethoxy Ethyl alcohol, ethoxypropyl alcohol, ethoxybutyl alcohol, ethoxypentyl alcohol, ethoxyhexyl alcohol, ethoxyheptyl alcohol, ethoxyoctyl alcohol, ethoxynonyl alcohol, ethoxydecyl alcohol, ethoxyphenyl alcohol, propoxymethyl alcohol, propoxyethyl alcohol, propoxypropyl Alcohols such as alcohol, propoxybutyl alcohol, propoxypentyl alcohol, propoxyhexyl alcohol, propoxyheptyl alcohol, propoxyoctyl alcohol, propoxynonyl alcohol, propoxydecyl alcohol, propoxyphenyl alcohol

Hydroxyalkyl sulfides such as hydroxymethyl sulfide, hydroxyethyl sulfide, hydroxypropyl sulfide, hydroxybutyl sulfide, hydroxypentyl sulfide, hydroxyhexyl sulfide, hydroxyheptyl sulfide, hydroxyoctyl sulfide, hydroxynonyl sulfide, and hydroxydecyl sulfide.

Hydroxyphenylmethylamine, hydroxyphenylethylamine, hydroxyphenylpropylamine, hydroxyphenylbutylamine, hydroxyphenylpentylamine, hydroxyphenylhexylamine, hydroxyphenylheptylamine, hydroxyphenyloctylamine, hydroxyphenylnonylamine, hydroxyphenyldecylamine, hydroxyphenylphenyl Hydroxyphenylamines such as amines

Hydroxyphenylmethylimine, hydroxyphenylethylimine, hydroxyphenylpropylimine, hydroxyphenylbutylimine, hydroxyphenylpentylimine, hydroxyphenylhexyluimine, hydroxyphenylheptylimine, hydroxyphenyloctylimine, hydroxyphenylnonylimine, hydroxyphenyldecylimine, Hydroxyphenylimines such as hydroxyphenylphenylimines

Hydroxyphenylmethylhydrazine, hydroxyphenylethylhydrazine, hydroxyphenylpropylhydrazine, hydroxyphenylbutylhydrazine, hydroxyphenylpentylhydrazine, hydroxyphenylhexylhydrazine, hydroxyphenylheptylhydrazine, hydroxyphenyloctylhydrazine, hydroxyphenylnonylhydrazine, hydroxyphenyldecylhydrazine , Hydroxyphenylhydrazines such as hydroxyphenylphenylhydrazine

Methoxymethylphenol, methoxyethylphenol, methoxypropylphenol, methoxybutylphenol, methoxypentylphenol, methoxyhexylphenol, methoxyheptylphenol, methoxyoctylphenol, methoxynonylphenol, methoxydecylphenol, methoxyphenylphenol, ethoxymethylphenol, ethoxyethylphenol, Ethoxypropylphenol, ethoxybutylphenol, ethoxypentylphenol, ethoxyhexylphenol, ethoxyheptylphenol, ethoxyoctylphenol, ethoxynonylphenol, ethoxydecylphenol, ethoxyphenylphenol, propoxymethylphenol, propoxyethylphenol, propoxypropylphenol, propoxybutylphenol, propoxy Alkoxyphenols such as pentylphenol, propoxyhexylphenol, propoxyheptylphenol, propoxyoctylphenol, propoxynonylphenol, propoxydecylphenol, propoxyphenylphenol

Hydroxyphenyl methyl sulfide, hydroxyphenyl ethyl sulfide, hydroxyphenyl propyl sulfide, hydroxyphenyl butyl sulfide, hydroxyphenyl pentyl sulfide, hydroxyphenyl hexyl sulfide, hydroxyphenyl heptyl sulfide, hydroxyphenyl octyl sulfide, hydroxyphenyl nonyl sulfide, hydroxyphenyl decyl sulfide. , Hydroxyphenyl sulfides such as hydroxyphenyl phenyl sulfide

Methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, methoxypentylamine, methoxyhexylamine, methoxyheptylamine, methoxyoctylamine, methoxynonylamine, methoxydecylamine, methoxyphenylamine, ethoxymethylamine, ethoxyethylamine, ethoxy Propylamine, ethoxybutylamine, ethoxypentylamine, ethoxyhexylamine, ethoxyheptylamine, ethoxyoctylamine, ethoxynonylamine, ethoxydecylamine, ethoxyphenylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, propoxypentyl Alkoxyamines such as amines, propoxyhexylamines, propoxyheptylamines, propoxyoctylamines, propoxynonylamines, propoxydecylamines, and propoxyphenylamines.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. 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, dodecanethiol, acetone, sodium hydrogen carbonate, cesium carbonate, citric acid, malonic acid, oxalic acid, succinic acid, tartaric acid, disodium ethylenediamine tetraacetate, For dodecanal and heptane, reagents manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. were used.
As the hydrogen chloride gas, a product of Sumitomo Seika Chemical Co., Ltd. was used.
As diphenyl carbonate, a product manufactured by Mitsubishi Chemical Corporation was used.

[analysis]
<Composition of bisphenol C production reaction solution>
The composition analysis of the bisphenol C production reaction solution was carried out by high performance liquid chromatography under the following procedure and conditions.
・ 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 ・ Elution at 0 minutes of analysis time 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 solution A: solution B = 10:90.
Analysis time 41.67 to 50 minutes is maintained at solution A: solution B = 10:90,
The analysis was performed at a flow rate of 0.34 mL / min.

<Identification of isopropenyl cresol>
Identification of isopropenyl cresol was performed using a gas chromatograph by the following procedure and conditions.
-Device: "Agilent 6890" manufactured by Agilent Technologies
-Column: "DB-1MS" manufactured by Agilent Technologies (inner diameter 0.25 mm x 30 m x 0.25 μm)
・ Carrier gas: Helium Flow rate: 1 cm / min ³
-Inlet temperature: 280 ° C
・ Transfer temperature: 250 ℃
・ Ion source temperature: 250 ℃
-Column temperature rise pattern: First, hold at 50 ° C for 3 minutes, then raise the temperature to 320 ° C at 10 ° C per minute, and hold at 280 ° C for 5 minutes.

<Measurement of iron concentration in bisphenol C or 1,1-bis (4-hydroxyphenyl) dodecane>
A sample was prepared by ashing 1 g of bisphenol C or 1,1-bis (4-hydroxyphenyl) dodecane and dissolving it in an acid. The following equipment was used for the analysis.
apparatus:
ICP-MS: "ELEMENT2" manufactured by Thermo Fisher Scientific
ICP-OES: "ICP VISTA-PRO" made by Agilent (VARIAN)

<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 electric conductivity was measured 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>
For the methanol-dissolved color of bisphenol C, put 10 g of bisphenol C and 10 g of methanol in 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 ° C), Japan. The number of Hazen colors was measured and evaluated using "SE6000" manufactured by Denshoku Kogyo Co., Ltd.

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

<Thermal color stability of bisphenol C>
For the thermal color stability of bisphenol C, put 20 g of bisphenol C in a test tube "P-24" (24 mmφ x 200 mm) manufactured by Nichiden Rika Glass Co., Ltd. and melt it at 190 ° C. for 4 hours to obtain "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd. Was used to measure and evaluate the number of Hazen colors.

<Pyrolysis stability of bisphenol C>
For the thermal decomposition stability of bisphenol C, 20 g of bisphenol C was placed in a test tube "P-24" (24 mmφ x 200 mm) manufactured by Nichiden Rika Glass Co., Ltd. and melted at 190 ° C. for 2 hours to analyze the composition of the bisphenol C production reaction solution. The same procedure as above was carried out, and the amount of isopropenyl cresol produced was measured and evaluated.

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

<Pellet YI>
The pellet YI (transparency of the polycarbonate resin) 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.

[Reference example 1]
85 g of bisphenol C and 4.5 g of sodium hydroxide were placed in a 500 mL eggplant-shaped flask equipped with a stirrer, a thermometer, and a distillation apparatus, and immersed in an oil bath heated to 195 ° C. After confirming that the bisphenol C in the eggplant-shaped flask was melted, the inside of the flask was gradually depressurized using a vacuum pump to obtain a full vacuum. After a while, evaporation started, and vacuum distillation was carried out until the distillation subsided. The resulting fraction was found by gas chromatography equipped with a massimeter detector to be a mixture of cresol and isopropenyl cresol produced by thermal decomposition of bisphenol C. Using the obtained fraction, the retention time of isopropenyl cresol under the composition analysis conditions of the bisphenol C production reaction solution was confirmed.

[Reference example 2]
(1) Preparation of mixed solution In a separable flask equipped with a hydrogen chloride blowing tube, a thermometer, a jacket and an anchor-type stirring blade, 510 g (4.7 mol) of orthocresol and 104 g (1.8 mol) of acetone under a nitrogen atmosphere. ), 100 g of toluene and 10 g of dodecanethiol were added, and the internal temperature was adjusted to 30 ° C. to prepare a mixed solution.

(2) Reaction The mixed solution was slowly bubbled with hydrogen chloride gas and then reacted for 10 hours to obtain a reaction solution.

(3) Crude Purification After adding 720 g of toluene and 900 g of desalinated water to the obtained reaction solution, the internal temperature was raised to 80 ° C. with stirring. After the internal temperature reached 80 ° C., the mixture was allowed to stand and separated into a first organic phase and a first aqueous phase to obtain a first organic phase.
250 g of desalted water was added to the obtained first organic phase, and after the internal temperature reached 80 ° C., the mixture was allowed to stand and separated into a second organic phase and a second aqueous phase, and the second aqueous phase was separated. A second organic phase was obtained by extracting.
To 1400 g of the obtained second organic phase, 300 g of a 5 mass% sodium hydrogen carbonate aqueous solution was added, and after the internal temperature reached 80 ° C. while mixing, the mixture was allowed to stand, and the pH of the lower phase became 9 or more. It was confirmed. Then, the third organic phase and the aqueous sodium hydrogen carbonate solution were phase-separated, and the lower phase was extracted to obtain a third organic phase.

(4) Purification The obtained third organic phase is cooled from 80 ° C. to 10 ° C., and after reaching 10 ° C., solid-liquid separation is performed using centrifugation (2,500 rpm for 10 minutes), and the first I got a wet cake. The obtained first wet cake was transferred to a beaker, 500 g of toluene was added thereto, and suspension washing was performed. The obtained slurry liquid was subjected to solid-liquid separation again using centrifugation (2,500 rpm for 10 minutes) to obtain 415 g of a second wet cake.
The iron concentration of bisphenol C contained in the obtained second wet cake was 4.7 mass ppm.

[Example 1]
A part of 300 g of the second wet cake of Reference Example 2 and 420 g of toluene were placed in a full-jacket type separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ° C. After confirming that the solution was uniform, a fourth organic phase was obtained. To 700 g of the obtained fourth organic phase, 200 g of 5% by mass hydrochloric acid was added and mixed for 30 minutes to remove the third aqueous phase of the lower phase to obtain a fifth organic phase. 200 g of desalinated water was added to the obtained fifth organic phase and mixed for 30 minutes to remove the fourth aqueous phase of the lower phase to obtain a sixth organic phase.
When the pH of the fourth aqueous phase (the pH of the aqueous phase before supplying disodium ethylenediaminetetraacetate) was confirmed, it was pH 2.

To 700 g of the obtained sixth organic phase, 1 g of a 5% by mass aqueous solution of disodium ethylenediaminetetraacetate was added, mixed for 30 minutes, and the liquid property was confirmed with pH test paper to confirm that the aqueous phase was pH 2. did. A saturated aqueous solution of sodium carbonate (18% by mass) was added thereto until the aqueous phase showed basicity, and the mixture was mixed for 30 minutes to extract the fifth aqueous phase to obtain a seventh organic phase.
When the pH of the fifth aqueous phase (the pH of the aqueous phase from which disodium ethylenediaminetetraacetate was extracted) was confirmed, it was pH 9.
The obtained seventh organic phase was repeatedly washed with desalinated water until the electrical conductivity of the lower aqueous phase became 3.0 μS / cm or less to obtain an eighth organic phase.

The obtained eighth organic phase was cooled from 80 ° C. to 10 ° C. Then, filtration was performed using a centrifuge (3000 rpm for 10 minutes) to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, a light boiling point was distilled off at an oil bath temperature of 80 ° C. under reduced pressure to obtain 210 g of white bisphenol C.

The iron concentration of the obtained bisphenol C was 16 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 36. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 100 mass ppm.

[Example 2]
In Example 1, the same procedure as in Example 1 was carried out except that 10 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added instead of 1 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution.
The aqueous phase before supplying disodium ethylenediaminetetraacetate was pH 2, and the aqueous phase from which disodium ethylenediaminetetraacetate was extracted was pH 9.

The iron concentration of the obtained bisphenol C was 20 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 34. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 95 mass ppm.

[Example 3]
In Example 1, the same procedure as in Example 1 was carried out except that 100 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added instead of 1 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution.
The aqueous phase before supplying disodium ethylenediaminetetraacetate was pH 2, and the aqueous phase from which disodium ethylenediaminetetraacetate was extracted was pH 9.

The iron concentration of the obtained bisphenol C was 18 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 33. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 91 parts by mass ppm.

[Example 4]
A part of 300 g of the second wet cake of Reference Example 2 and 420 g of toluene were placed in a full-jacket type separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ° C. After confirming that the solution was uniform, a fourth organic phase was obtained. To 700 g of the obtained fourth organic phase, 300 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, mixed for 30 minutes, and the liquid property was confirmed with pH test paper, and it was confirmed that the aqueous phase was pH 5. did.
A saturated aqueous solution of sodium carbonate (18% by mass) was added thereto until the aqueous phase showed basicity, and the mixture was mixed for 30 minutes to extract the fourth aqueous phase to obtain a fifth organic phase.
When the pH of the fourth aqueous phase (the pH of the aqueous phase from which disodium ethylenediaminetetraacetate was extracted) was confirmed, it was pH 9.
The obtained fifth organic phase was repeatedly washed with desalinated water until the electrical conductivity of the lower aqueous phase became 3.0 μS / cm or less to obtain a sixth organic phase.

The obtained sixth organic phase was cooled from 80 ° C. to 10 ° C. Then, filtration was performed using a centrifuge (3000 rpm for 10 minutes) to obtain wet purified bisphenol C. 209 g of white bisphenol C was obtained by distilling off a light boiling point at an oil bath temperature of 80 ° C. under reduced pressure using an evaporator equipped with an oil bath.

The iron concentration of the obtained bisphenol C was 54 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 19. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 38. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 127 mass ppm.

[Comparative Example 1]
A part of 300 g of the second wet cake of Reference Example 2 and 420 g of toluene were placed in a full-jacket type separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ° C. After confirming that the solution was uniform, a fourth organic phase was obtained. 200 g of desalinated water was added to the obtained fourth organic phase and mixed for 30 minutes to remove the third aqueous phase of the lower phase to obtain a fifth organic phase.
When the liquid property was confirmed with pH test paper, the third aqueous phase (pH of the aqueous phase before supplying disodium ethylenediaminetetraacetate) was pH 9.
To the obtained fifth organic phase, 10 g of a 5% by mass aqueous solution of disodium ethylenediaminetetraacetate was added and mixed for 30 minutes, and the fourth aqueous phase was extracted to obtain a sixth organic phase.
The fourth aqueous phase (pH of the aqueous phase from which disodium ethylenediaminetetraacetate was extracted) was pH 9.
The obtained sixth organic phase was repeatedly washed with desalinated water until the electrical conductivity of the lower aqueous phase became 3.0 μS / cm or less to obtain a seventh organic phase.

The obtained seventh organic phase was cooled from 80 ° C. to 10 ° C. Then, filtration was performed using a centrifuge (3000 rpm for 10 minutes) to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, a light boiling point was distilled off at an oil bath temperature of 80 ° C. under reduced pressure to obtain 212 g of white bisphenol C.

The iron concentration of the obtained bisphenol C was 102 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 12. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 42. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 65. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 250 mass ppm.

[Comparative Example 2]
A part of 300 g of the second wet cake of Reference Example 2 and 420 g of toluene were placed in a full-jacket type separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ° C. After confirming that the solution was uniform, a fourth organic phase was obtained. To the obtained fourth organic phase, 200 g of 5% by mass hydrochloric acid was added and mixed for 30 minutes to remove the third aqueous phase of the lower phase to obtain a fifth organic phase. 200 g of desalinated water was added to the obtained fifth organic phase and mixed for 30 minutes to remove the fourth aqueous phase of the lower phase to obtain a sixth organic phase.
The fourth aqueous phase (pH of the aqueous phase before supplying disodium ethylenediaminetetraacetate) was pH 2.
To the obtained sixth organic phase, 10 g of a 5% by mass aqueous solution of disodium ethylenediaminetetraacetate was added and mixed for 30 minutes to remove the fifth aqueous phase to obtain a seventh organic phase.
The fifth aqueous phase had a pH of 2.
A saturated aqueous sodium carbonate solution was added to the obtained seventh organic phase until the aqueous phase showed basicity, and the mixture was mixed for 30 minutes to extract the sixth aqueous phase to obtain an eighth organic phase. The obtained eighth organic phase was repeatedly washed with desalinated water until the electrical conductivity of the lower aqueous phase became 3.0 μS / cm or less to obtain a ninth organic phase.

The obtained ninth organic phase was cooled from 80 ° C. to 10 ° C. Then, filtration was performed using a centrifuge (3000 rpm for 10 minutes) to obtain wet purified bisphenol C. 209 g of white bisphenol C was obtained by distilling off a light boiling point at an oil bath temperature of 80 ° C. under reduced pressure using an evaporator equipped with an oil bath.

The iron concentration of the obtained bisphenol C was 89 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 5. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 41. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 80. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 210 mass ppm.

The pH of the aqueous phase before supplying disodium ethylenediaminetetraacetate, the pH of the aqueous phase from which disodium ethylenediaminetetraacetate was extracted, and the iron concentration of bisphenol C obtained in Examples 1 to 4 and Comparative Examples 1 and 2. Table 1 summarizes the dissolved color of methanol, the difference in molten color, the stability of thermal color tone, and the stability of thermal decomposition.

From Table 1, the iron of bisphenol C obtained is obtained when the liquidity of the aqueous phase before supplying disodium ethylenediaminetetraacetic acid is acidic and the liquidity of the aqueous phase extracted from disodium ethylenediaminetetraacetic acid is basic. It can be seen that the concentration, methanol-dissolved color, melt color difference, thermal color stability, and thermal decomposition stability are improved.
In Comparative Example 2, since the saturated aqueous sodium carbonate solution was added to the organic phase from which the aqueous phase had been removed after the addition of disodium ethylenediaminetetraacetate, the effect of removing iron by the chelating agent was not obtained.

[Example 5]
In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5 mass% aqueous citric acid solution was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate.

The iron concentration of the obtained bisphenol C was 22 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 32. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 99 mass ppm.

[Example 6]
In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5 mass% aqueous solution of oxalic acid was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate.

The iron concentration of the obtained bisphenol C was 32 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 35. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 98 mass ppm.

[Example 7]
In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5% by mass aqueous solution of malonic acid was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate.

The iron concentration of the obtained bisphenol C was 35 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 33. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 95 mass ppm.

[Example 8]
In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5 mass% aqueous solution of succinic acid was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate.

The iron concentration of the obtained bisphenol C was 23 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 32. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 90 mass ppm.

[Example 9]
In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5 mass% aqueous solution of tartaric acid was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate.
The iron concentration of the obtained bisphenol C was 21 mass ppb.

When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 0. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 31. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 85 mass ppm.

[Comparative Example 3]
In Comparative Example 2, the same procedure as in Comparative Example 2 was carried out except that 10 g of a 5 mass% aqueous citric acid solution was added instead of 10 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution.

The iron concentration of the obtained bisphenol C was 102 mass ppb.
When the methanol-dissolved color of the obtained bisphenol C was measured, the number of Hazen colors was 10. When the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 39. When the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 77. When the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 310 mass ppm.

Table 2 summarizes the chelating agent used, the iron concentration of the obtained bisphenol C, the methanol-dissolved color, the melt color difference, the thermal color tone stability, and the thermal decomposition stability in Examples 5 to 9 and Comparative Example 3.

From Table 2, when other chelating agents are used as in the case of disodium ethylenediaminetetraacetate, the iron concentration of the obtained bisphenol C, methanol dissolution color, melt color difference, thermal color stability, and thermal decomposition stability are improved. I understand.

[Example 10]
100.00 g (0.39 mol) of bisphenol C, 86.49 g (0.4 mol) and 400 of diphenyl carbonate obtained in Example 2 in a glass reaction tank having an internal volume of 150 mL equipped with a stirrer and a distillate. 479 μL of a mass ppm cesium carbonate aqueous solution was 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 dissolve the contents.

The rotation speed of the stirrer is set to 100 times per minute, and the pressure in the reaction vessel is adjusted to absolute pressure over 40 minutes while distilling off the phenol produced by the oligomerization reaction of 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.

After that, the temperature outside the reaction vessel was raised to 280 ° C., the absolute pressure in 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 210 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 24700, and the pellet YI was 7.7, so that a polycarbonate resin having a good hue could be obtained.

[Reference example 3]
237 g (2.5 mol) of phenol was heated to 40 ° C. in a full-jacket separable flask equipped with a thermometer and a stirrer, and 3.2 g of hydrochloric acid was added. A mixed solution of 92.0 g (0.5 mol) of dodecanal and 55.2 g of toluene was added dropwise thereto over 4 hours. After the dropping, the mixture was stirred at 40 ° C. for 1 hour, and then a 5 mass% aqueous sodium hydrogen carbonate solution was added. Then, under reduced pressure, toluene and phenol were distilled off to obtain a residue. 450 g of toluene was added to this residue and dissolved to obtain an organic phase. This organic phase was washed 4 times with 230 g of desalinated water. Then, toluene was distilled off to obtain a residue. 330 g of toluene and 330 g of heptane were added to the obtained residue, and the mixture was heated to 70 ° C. to dissolve it. Then, the temperature was lowered to 5 ° C. to precipitate a solid to obtain a slurry liquid. The obtained slurry liquid was filtered to obtain a solid. The obtained solid was placed in an eggplant flask and dried using a rotary evaporator at 70 ° C. and 20 Torr for 1 hour to obtain 45 g of 1,1-bis (4-hydroxyphenyl) dodecane. The iron concentration of the obtained 1,1-bis (4-hydroxyphenyl) dodecane was 570 mass ppb.

[Example 11]
10 g of 1,1-bis (4-hydroxyphenyl) dodecane and 14 g of toluene obtained in Reference Example 3 were placed in an eggplant-shaped flask equipped with a magnetic rotor and dissolved at 80 ° C. to obtain a toluene solution. 7 g of 5% by mass hydrochloric acid was added thereto, and the mixture was stirred. After allowing the obtained mixed solution to stand for 30 minutes, the aqueous phase was removed to obtain a first organic phase. The pH of the removed aqueous phase was less than 1.

After adding 7 g of desalinated water to the obtained first organic phase, the mixture was shaken with a separating funnel for 10 minutes, allowed to stand for 30 minutes, and then the aqueous phase was removed to obtain a second organic phase. .. To the obtained organic phase, 0.3 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added and shaken for 10 minutes, and further 2 g of a 5 mass% sodium hydrogen carbonate aqueous solution was added and shaken for 10 minutes. After standing for 30 minutes, the aqueous phase was removed to obtain a third organic phase. The pH of the removed aqueous phase was 9.

The obtained third organic phase was washed repeatedly with 7 g of desalinated water three times to obtain a fourth organic phase. The obtained fourth organic phase was cooled to 10 ° C. to obtain a slurry liquid. The obtained slurry liquid was filtered, and the obtained cake was dried at 70 ° C. under reduced pressure to obtain 7.5 g of 1,1-bis (4-hydroxyphenyl) dodecane. The iron concentration of the obtained 1,1-bis (4-hydroxyphenyl) dodecane was 100 mass ppb.

[Comparative Example 4]
10 g of 1,1-bis (4-hydroxyphenyl) dodecane and 14 g of toluene obtained in Reference Example 3 were placed in an eggplant-shaped flask equipped with a nuclear magnetic rotor and dissolved at 80 ° C. to obtain a toluene solution. To the obtained toluene solution, 0.3 g of a 5% by mass aqueous solution of disodium ethylenediaminetetraacetate was added, and the mixture was shaken for 10 minutes. After allowing the obtained mixed solution to stand for 30 minutes, the aqueous phase was removed to obtain a first organic phase. The obtained first organic phase was washed repeatedly with 7 g of desalinated water three times to obtain a second organic phase. The obtained second organic phase was cooled to 10 ° C. to obtain a slurry liquid. The obtained slurry liquid was filtered, and the obtained cake was dried at 70 ° C. under reduced pressure to obtain 7.5 g of 1,1-bis (4-hydroxyphenyl) dodecane. The iron concentration of the obtained 1,1-bis (4-hydroxyphenyl) dodecane was 400 mass ppb.

Table 3 shows the presence or absence of a pH change before and after the addition of a 5% by mass aqueous solution of disodium ethylenediaminetetraacetate and the iron concentration of the obtained 1,1-bis (4-hydroxyphenyl) dodecane in Example 11 and Comparative Example 4. I summarized it in.

From Table 3, it can be seen that the iron concentration of 1,1-bis (4-hydroxyphenyl) dodecane can be reduced by changing the pH before and after the addition of the 5% by mass aqueous solution of disodium ethylenediaminetetraacetate.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention.
This application is based on Japanese Patent Application 2019-049991 filed on March 18, 2019 and Japanese Patent Application 2019-238265 filed on December 27, 2019, which are incorporated by reference in their entirety. ..

Claims

A step of mixing the organic phase 1 of the mixed solution 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol with a chelating agent to obtain a mixed solution 2 of the aqueous phase and the organic phase having a pH of 6 or less.
A step of mixing the obtained mixed solution 2 with a base to obtain a mixed solution 3 of an aqueous phase having a pH of 8 or higher and an organic phase, and
Including a step of removing an aqueous phase having a pH of 8 or more from the obtained mixed solution 3 to obtain an organic phase 3A.
A method for producing bisphenol in which the solubility of the chelating agent in the aqueous phase of the mixed solution 3 is higher than the solubility of the mixed solution 3 in the organic phase.
The method for producing bisphenol according to claim 1, wherein the organic phase 1 is an organic phase 1A obtained by removing the aqueous phase from the mixed solution 1.
The method for producing bisphenol according to claim 2, wherein the aqueous phase is removed from the mixed solution 1 so that the mixing ratio of the aqueous phase and the organic phase 1A after removing the aqueous phase is 1: 700 or less by weight. ..
The method for producing bisphenol according to any one of claims 1 to 3, wherein the mixing ratio of the aqueous phase and the organic phase in the mixed solution 2 is 0.001: 100 to 1000: 700 in weight ratio.
The production of bisphenol according to any one of claims 1 to 4, which comprises a step of removing the aqueous phase from the mixed solution 4 obtained by mixing the organic phase 3A and desalinated water to obtain the organic phase 4. Method.
The method for producing bisphenol according to any one of claims 1 to 5, wherein the bisphenol is a bisphenol obtained by condensing a ketone or aldehyde and an aromatic alcohol in the presence of hydrogen chloride.
The bisphenols are 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) dodecane, and 2,2-bis (4-hydroxy-3,5-dimethyl). The method for producing bisphenol according to any one of claims 1 to 6, which is any one of the group consisting of phenyl) methane.
A method for producing a polycarbonate resin using bisphenol produced by the method for producing bisphenol according to any one of claims 1 to 7.
A method for producing a metal-coordinating organic compound containing a partial structure represented by the following formula (I) in the molecule.
The organic phase 1'of the mixed solution 1'of the aqueous phase 1'and the organic phase 1'containing the organic compound and the chelating agent are mixed, and the mixed solution 2'of the aqueous phase and the organic phase having a pH of 6 or less is mixed. And the process of obtaining
A step of mixing the obtained mixed solution 2'and a base to obtain a mixed solution 3'of an aqueous phase having a pH of 8 or higher and an organic phase.
Including a step of removing an aqueous phase having a pH of 8 or higher from the obtained mixed solution 3'to obtain an organic phase 3A'.
The solubility of the organic compound in the organic phase of the mixed solution 3'is higher than the solubility of the mixed solution 3'in the aqueous phase.
A method for producing an organic compound, wherein the solubility of the chelating agent in the aqueous phase of the mixed solution 3'is higher than the solubility of the mixed solution 3'in the organic phase.

In formula (I), X and Y are the same or different elements, and are elements selected from the group consisting of trivalent nitrogen, divalent oxygen, trivalent phosphorus, and divalent sulfur. The line connecting X and Y is a carbon chain.