JP2020037527A - Method for producing bisphenol and method for producing polycarbonate resin - Google Patents

Abstract

To provide a method for producing a bisphenol capable of producing a bisphenol excellent in color tone and polymerization activity and to provide a method for producing a polycarbonate resin capable of stably producing a polycarbonate resin having a good color tone.SOLUTION: There is provided a method for producing a bisphenol by the condensation of an aromatic alcohol and ketone or aldehyde in the presence of a catalyst and an organic solvent, wherein the catalyst contains a monoalkyl sulfate, the molar ratio of the aromatic alcohol to the ketone or aldehyde is set to 1.80 or more and 2.20 or less and the ketone or aldehyde and the aromatic alcohol are reacted. There is provided a method for producing a polycarbonate resin using a bisphenol produced by the method for producing a bisphenol.SELECTED DRAWING: None

Description

The present invention relates to a method for producing bisphenol. The present invention also relates to a method for producing a polycarbonate resin using bisphenol produced by the method for producing bisphenol.
The bisphenol produced by the bisphenol production method of the present invention is a resin material such as a polycarbonate resin, an epoxy resin, or an aromatic polyester resin, a curing agent, a color developer, an anti-fading agent, and other bactericides and fungicides. It is useful as an additive for the like.

  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.

  As a method for producing such a bisphenol, for example, a production method using hydrogen chloride gas as a catalyst (Patent Document 1), a production method using hydrochloric acid as a catalyst (Patent Document 2), a production method using a mixture of hydrochloric acid and sulfuric acid as a catalyst ( Patent Document 3) and a production method using sulfuric acid as a catalyst (Patent Document 4) are known.

JP-A-62-138443 JP 2008-214248 A JP 2014-40376 A JP 2015-51935 A

Journal of the Chemical Society of Japan 1982 (8) 1363-1370

However, a production method using hydrogen chloride gas as a catalyst (Patent Document 1) is known as a highly versatile production method of bisphenol. However, this hydrogen chloride gas is highly corrosive, and is not suitable for industrial practice. Special equipment is required.
The production method using hydrochloric acid as a catalyst (Patent Document 2) requires less handling of hydrogen chloride than the production method using hydrogen chloride gas as a catalyst, but concentrated hydrochloric acid is corrosive and is not easy to handle. Further, there is a problem that a reaction time is required.
Further, the production method using a mixture of hydrochloric acid and sulfuric acid as a catalyst (Patent Document 3) has a problem of corrosiveness because hydrochloric acid is used.
In the production method using sulfuric acid as a catalyst (Patent Document 4), a side reaction such as sulfonation of phenol easily occurs, and it is necessary to use a relatively large amount of various solvents to suppress the side reaction (Non-Patent Document 1). ). Further, when sulfuric acid is used, it is known that side reactions such as condensation (multimerization) of ketones and aldehydes as raw materials easily occur, and these become color components. Further, as a result of investigations by the present inventors, it has been found that a reaction solution of bisphenol is easily solidified and a problem that a reaction time is required occurs.

In the method for producing bisphenol, bisphenol can be obtained by reacting under the condition that the ratio of the amount of aromatic alcohol to ketone or aldehyde is higher than the theoretical ratio of the amount of theoretical alcohol, but unreacted aromatic alcohol is recovered. There are issues that must be addressed.
On the other hand, bisphenol can be obtained by reacting under the condition that the amount ratio of the aromatic alcohol to the ketone or aldehyde is lower than the theoretical amount ratio, but when the polymerization reaction is performed using the obtained bisphenol, the activity is poor and the polymerization is poor. , And the color tone of the obtained polycarbonate resin is deteriorated.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for producing a bisphenol capable of producing a bisphenol excellent in color tone and polymerization activity.
Another object of the present invention is to provide a method for producing a polycarbonate resin capable of stably producing a polycarbonate resin having an excellent color tone by using the obtained bisphenol.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, have found a method for producing bisphenol using a monoalkyl sulfate as a catalyst obtained by mixing sulfuric acid and an aliphatic alcohol, and have already filed an application. (Japanese Patent Application No. 2017-041829). In the method for producing bisphenol using a monoalkyl sulfate as a catalyst, the present inventors further set the molar ratio of the aromatic alcohol to the ketone or aldehyde used in the condensation to be in a specific range so that the unreacted aromatic alcohol can be obtained. Thus, the invention of a more efficient and industrially advantageous method for producing bisphenol has been completed.

That is, the present invention relates to the following inventions.
[1] A process for producing bisphenol by condensing an aromatic alcohol with a ketone or aldehyde in the presence of a catalyst and an organic solvent, wherein the catalyst comprises a monoalkyl sulfate and the ketone or aldehyde A method for producing a bisphenol, wherein the ketone or aldehyde is reacted with the aromatic alcohol at a molar ratio of the aromatic alcohol to 1.80 to 2.20.
[2] The method for producing bisphenol according to [1], wherein the catalyst includes sulfuric acid and monoalkyl sulfate, and the monoalkyl sulfate is generated from the sulfuric acid and an aliphatic alcohol.
[3] A method for producing bisphenol by condensing an aromatic alcohol with a ketone or aldehyde to obtain bisphenol, wherein the molar ratio of the aromatic alcohol to the ketone or aldehyde is from 1.80 to 2.20, A method for producing bisphenol, comprising reacting the ketone or aldehyde with the aromatic alcohol in the presence of sulfuric acid, an aliphatic alcohol and an organic solvent.
[4] The method for producing bisphenol according to any one of [1] to [3], wherein the ketone or aldehyde is acetone.
[5] The method for producing bisphenol according to any one of [1] to [4], wherein the aromatic alcohol is cresol.
[6] The method for producing bisphenol according to any one of [1] to [5], wherein the organic solvent is an aromatic hydrocarbon.
[7] A method for producing a polycarbonate resin using the bisphenol produced by the method for producing bisphenol according to any one of [1] to [6].

  According to the present invention, bisphenol having excellent color tone and polymerization activity can be produced. Further, a polycarbonate resin having an excellent color tone can be stably produced using the obtained bisphenol.

  Hereinafter, embodiments of the present invention will be described in detail. However, the description of constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is described below unless the gist is changed. It is not limited to the content of.

1. Bisphenol production method The present invention is a method for producing bisphenol in which an aromatic alcohol and a ketone or aldehyde are condensed in the presence of a catalyst and an organic solvent to obtain bisphenol, wherein the catalyst contains a monoalkyl sulfate. A molar ratio of the aromatic alcohol to the ketone or aldehyde of 1.80 to 2.20, and a method for producing bisphenol by reacting the ketone or aldehyde with the aromatic alcohol (hereinafter referred to as “the bisphenol of the present invention”). Manufacturing method (1) ”).

  Preferably, the present invention relates to a method for producing bisphenol, wherein the catalyst contains sulfuric acid and monoalkyl sulfate, and the monoalkyl sulfate is produced from the sulfuric acid and aliphatic alcohol.

The present invention also relates to a method for producing bisphenol by condensing an aromatic alcohol with a ketone or aldehyde to obtain a bisphenol, wherein the molar ratio of the aromatic alcohol to the ketone or aldehyde is from 1.80 to 2.20. Hereinafter, a method for producing a bisphenol in which the ketone or aldehyde is reacted with the aromatic alcohol in the presence of sulfuric acid, an aliphatic alcohol, and an organic solvent (hereinafter referred to as “the method (2) for producing a bisphenol of the present invention”) In some cases.)
In the bisphenol production method (2) of the present invention, monoalkyl sulfate is produced by a reaction between sulfuric acid and an aliphatic alcohol in the reaction system, and the produced monoalkyl sulfate also functions as a catalyst.

  The bisphenol production method (1) of the present invention and the bisphenol production method (2) of the present invention are common in that the reaction is carried out in the presence of monoalkyl sulfate. Hereinafter, the invention combining the method (1) for producing bisphenol of the present invention and the method (2) for producing bisphenol of the present invention is referred to as “the method for producing bisphenol of the present invention”.

The first feature of the method for producing bisphenol of the present invention is that in the reaction of condensing an aromatic alcohol with a ketone or aldehyde to obtain bisphenol, monoalkyl sulfate is included as an essential component of the catalyst.
The use of monoalkyl sulfate controls the acid strength of the catalyst, suppresses the condensation (multiplication) and coloration of the raw material ketone or aldehyde, and reduces the formation of by-products and the reduction of bisphenol coloration of the product. It is possible to manufacture easily and efficiently.

  As the monoalkyl sulfate, monoalkyl sulfate can be used as it is, but since monoalkyl sulfate is difficult to isolate, preferably, sulfuric acid is used in combination, and sulfuric acid and an aliphatic alcohol are formed. It is more efficient to use monoalkyl sulfates.

  In the method for producing bisphenol of the present invention, unreacted sulfuric acid also works as a catalyst by producing monoalkyl sulfate from sulfuric acid and an aliphatic alcohol. Further, it is possible to dissolve the bisphenol generated from the remaining portion of the aliphatic alcohol used in generating the monoalkyl sulfate to suppress solidification of the reaction solution, improve the mixing state, and shorten the reaction time. .

Next, the second feature of the method for producing bisphenol of the present invention is that the molar ratio of aromatic alcohol to ketone or aldehyde used for the condensation ((mol number of aromatic alcohol / number of ketone)) or (mol number of aromatic alcohol) / Molar number of aldehyde)) in the range of 1.80 to 2.20.
As described above, by setting the molar ratio of the aromatic alcohol to the ketone or aldehyde used for the condensation within a specific range, the amount of the unreacted aromatic alcohol to be recovered is suppressed, and the condensation (multiplication) of the raw material ketone or aldehyde is performed. And coloring can be suppressed.
Further, bisphenol having high polymerization activity can be obtained. Using the obtained bisphenol, it is possible to efficiently produce a polymer material such as a polycarbonate resin having an excellent color tone.
In order to set the molar ratio of the aromatic alcohol to the ketone or aldehyde used for the condensation in the range of 1.80 to 2.20, the presence of an organic solvent is essential in the bisphenol production method of the present invention.

  Hereinafter, the used raw materials, processes, and the like will be described in detail.

[Aromatic alcohol]
The aromatic alcohol used in the bisphenol production method of the present invention is usually a compound represented by the following general formula (1).

R ^{1 to} R ⁴ each independently include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and the like. The alkyl group, alkoxy group, aryl group, and the like may be substituted or unsubstituted. For example, hydrogen atom, fluoro group, chloro group, bromo group, iodo group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n- Pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 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, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Heptyl group cyclopropyl, cyclooctyl group, cyclododecyl group, a benzyl group, a phenyl group, a tolyl group, 2,6-dimethylphenyl group.

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

  Specific examples of the compound represented by the general formula (1) include phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, methoxyphenol, ethoxyphenol, propoxyphenol, butoxyphenol, aminophenol, benzylphenyl, Phenylphenol and the like.

  Above all, it is preferably any one selected from the group consisting of phenol, cresol, and xylenol, more preferably cresol or xylenol, and even more preferably cresol.

[Ketone or aldehyde]
The ketone or aldehyde used in the method for producing bisphenol of the present invention is generally a compound represented by the following general formula (2).

R ⁵ and R ⁶ each independently include a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and the like. The alkyl group, alkoxy group, aryl group, and the like may be substituted or unsubstituted. For example, hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group , N-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, methoxy group, ethoxy group, n-propoxy group, i -Propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentyloxy group, i-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n -Nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group Cyclooctyl, cyclododecyl group, a benzyl group, a phenyl group, a tolyl group, 2,6-dimethylphenyl group.

R ⁵ and R ⁶ may be bonded or cross-linked to each other between the two groups, and R ⁵ and R ⁶ may be bonded together with adjacent carbon atoms to form a cycloalkylidene group. Note that the cycloalkylidene group is a divalent group obtained by removing two hydrogen atoms from one carbon atom of a cycloalkane.
Examples of the cycloalkylidene group formed by bonding R ⁵ and R ⁶ together with adjacent carbon atoms include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3,3,5-trimethyl Cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclododecylidene, fluorenylidene, xanthonylidene, thioxanthonylidene, and the like.

  Specific examples of the compound represented by the general formula (2) include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanealdehyde, hexanaldehyde, heptanealdehyde, octanealdehyde, nonanealdehyde, decanealdehyde, undecanealdehyde, dodecane Aldehydes such as aldehydes, ketones such as acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, benzaldehyde, phenylmethylketone, phenylethylketone, phenylpropylketone, cresylmethylketone, cretan Aryl such as zyl ethyl ketone, cresyl propyl ketone, xylyl methyl ketone, xylyl ethyl ketone, xylyl propyl ketone Rukiruketon, cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloalkyl undecanoic, cyclic alkanes ketones such as cyclododecanone, and the like. Among them, acetone is preferred.

The molar ratio of the aromatic alcohol to the ketone or aldehyde used for the condensation is from 1.80 to 2.20. That is, the aromatic alcohol used for the condensation is at least 1.80 mol and at most 2.20 mol for 1 mol of the ketone or aldehyde used for the condensation. If the molar ratio of the aromatic alcohol to the ketone or aldehyde used for the condensation is less than 1.80, bisphenol having high polymerization activity cannot be obtained or the color tone tends to deteriorate. If the molar ratio of the aromatic alcohol to the ketone or aldehyde used for the condensation is more than 2.20, it is difficult to efficiently recover the generated bisphenol, and the yield is likely to decrease. Further, the amount of unreacted aromatic alcohol increases, and an operation of recovering the unreacted aromatic alcohol is required, which is not economically preferable.
In order to produce bisphenol having high polymerization activity and good color tone in a short time, the molar ratio of aromatic alcohol to ketone or aldehyde used for condensation is preferably 1.85 or more, more preferably 1.90 or more. Further, the upper limit is preferably 2.15 or less, more preferably 2.10 or less.
The molar ratio of the aromatic alcohol to the ketone or the aldehyde is the molar ratio of the aromatic alcohol used when preparing the reaction solution to the ketone or the aldehyde, and is the molar ratio at the time of preparation.

[catalyst]
The catalyst used in the production method of the present invention contains a monoalkyl sulfate. The catalyst may be a monoalkyl sulfate alone, or a monoalkyl sulfate and another catalyst may be used in combination. Other catalysts that can be used in combination with the monoalkyl sulfate include sulfuric acid, hydrochloric acid, hydrogen chloride gas, phosphoric acid, aromatic sulfonic acids such as p-toluenesulfonic acid, and aliphatic sulfonic acids such as methanesulfonic acid. Among these, monoalkyl sulfate and sulfuric acid are preferably used as the catalyst because the acid strength of the catalyst is easily controlled.

  If the molar ratio of the catalyst to the ketone or aldehyde used for the condensation ((moles of catalyst / moles of ketone) or (moles of catalyst / moles of aldehyde)) is small, it is by-produced as the condensation reaction proceeds. The reaction is time-consuming because the catalyst is diluted with water. If the amount is large, the amount of ketone or aldehyde may increase. From these facts, the molar ratio of the catalyst to the ketone or aldehyde used for the condensation is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.1 or more. The upper limit is preferably 10 or less, more preferably 8 or less, and further preferably 5 or less.

  In the case of producing monoalkyl sulfate from sulfuric acid and an aliphatic alcohol, the catalyst is monoalkyl sulfate and sulfuric acid. In such a case, since the amount of monoalkyl sulfate produced is controlled by sulfuric acid, the molar ratio of catalyst (monoalkyl sulfate and sulfuric acid) to ketone or aldehyde can be controlled by controlling the molar ratio of sulfuric acid to ketone or aldehyde used for condensation. The ratio can be controlled.

[Monoalkyl sulfate]
In the present invention, the monoalkyl sulfate is a compound represented by the following general formula (3).

In the general formula (3), R ⁷ represents an alkyl group. The alkyl group may be linear or branched. Further, the alkyl group may be unsubstituted or may have a substituent.
Examples of the substituted alkyl group include a hydroxyalkyl group substituted with a hydroxyl group (OH group) and a hydroxyalkoxyalkyl group substituted with a hydroxyalkoxy group.

From the viewpoint of solubility in an organic solvent and water, R ⁷ is preferably an alkyl group having 12 or less carbon atoms. In the case of a substituted alkyl group, an alkyl group having 12 or less carbon atoms means an alkyl group having 12 or less carbon atoms including the number of carbon atoms of the substituent. For example, when R ⁷ is a 2-hydroxyethoxyethyl group, it has 4 carbon atoms. R ⁷ is more preferably an alkyl group having 8 or less carbon atoms since monoalkyl sulfate becomes more difficult to move between the organic phase and the aqueous phase as the amount of carbon increases and the lipophilicity increases.

Examples of the alkyl group for R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, and n -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, hydroxyethyl group, 2-hydroxyethoxyethyl group, 2- ( 2'-hydroxyethoxy) ethoxyethyl group and the like.

  Specifically, examples of the monoalkyl sulfate represented by the general formula (3) include, for example, monomethyl sulfate, monoethyl sulfate, monopropyl sulfate, monoisopropyl sulfate, monobutyl sulfate, monoisobutyl sulfate, monot-butyl sulfate, and mono-t-butyl sulfate. Pentyl, monoisopentyl sulfate, monohexyl sulfate, monoheptyl sulfate, monooctyl sulfate, monononyl sulfate, monodecyl sulfate, monoundecyl sulfate, monododecyl sulfate, mono (hydroxyethyl) sulfate, mono (2-hydroxyethoxyethyl) sulfate And monosulfate (2- (2'-hydroxyethoxy) ethoxyethyl).

The concentration of the monoalkyl sulfate in the bisphenol-forming reaction solution is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, from the viewpoint of producing sulfuric acid from the equilibrium reaction between the monoalkyl sulfate and water. In addition, from the viewpoint that the production efficiency of bisphenol decreases when the amount of the catalyst is large, it is preferably 50% by mass or less, more preferably 30% by mass or less. The concentration of monoalkyl sulfate in the bisphenol-forming reaction solution can be determined by ¹ H-NMR analysis.

As a method for preparing monoalkyl sulfate, a method of reacting sulfuric acid with an aliphatic alcohol to obtain monoalkyl sulfate, or a method of reacting a monoalkyl metal sulfate such as sodium monoalkyl sulfate (R ⁷ OSO ₂ ONa) with sulfuric acid. And the like to obtain a monoalkyl sulfate.
Among them, as described above, monoalkyl sulfate is preferably generated from sulfuric acid and an aliphatic alcohol. In addition, since heat is generated when an aliphatic alcohol and sulfuric acid are mixed, the mixing is preferably performed at a boiling point or lower of the aliphatic alcohol.

  In addition, monoalkyl sulfate is a deliquescent solid and is difficult to isolate. Therefore, in general, a monoalkyl sulfate synthesis solution prepared by synthesizing monoalkyl sulfate is used without isolation of monoalkyl sulfate. For example, a synthetic solution in which monoalkyl sulfate is generated from sulfuric acid and an aliphatic alcohol, a synthetic solution in which monoalkyl sulfate is generated from sulfuric acid and a metal salt of monoalkyl sulfate, or the like can be used. Further, the monoalkyl sulfate may be produced when preparing a reaction solution for the bisphenol production reaction.

[Sulfuric acid]
Sulfuric acid produces monoalkyl sulfate by reacting with an aliphatic alcohol or a monoalkyl sulfate metal salt. Unreacted sulfuric acid itself acts as a catalyst.
Sulfuric acid is an acidic liquid represented by the chemical formula H ₂ SO ₄ . Generally, sulfuric acid is used as a sulfuric acid aqueous solution diluted with water, and is called concentrated sulfuric acid or diluted sulfuric acid depending on its concentration. For example, dilute sulfuric acid is a sulfuric acid aqueous solution having a mass concentration of less than 90% by mass.
If the concentration of the sulfuric acid used (the concentration of H ₂ SO _{4 in} the aqueous sulfuric acid solution) is low, the amount of water increases, so that it is difficult to produce monoalkyl sulfate. In addition, the acidity of the entire catalyst also decreases, the reaction time for producing bisphenol increases, and it may be difficult to efficiently produce bisphenol. Therefore, the concentration of the sulfuric acid used is usually 80% by mass or more. In order to obtain bisphenol having higher polymerization activity, the content is preferably 90% by mass or more, more preferably 95% by mass or more. The upper limit of the concentration of sulfuric acid used can be 99.5% by mass or less or 99% by mass or less.
The concentration of sulfuric acid is the concentration of the aqueous sulfuric acid solution used when preparing the reaction solution, and is the concentration at the time of preparation.

[Aliphatic alcohol]
An aliphatic alcohol is an alkyl alcohol in which an alkyl group and a hydroxyl group are bonded. In the present invention, the aliphatic alcohol may be a monohydric alcohol in which an alkyl group and one hydroxyl group are bonded, or a polyhydric alcohol in which an alkyl group and two or more hydroxyl groups are bonded. Further, the alkyl group may be linear or branched, may be unsubstituted, or may have some of the carbon atoms of the alkyl group substituted by oxygen atoms.

  The aliphatic alcohol preferably has 12 or less carbon atoms, and more preferably 8 or less carbon atoms, because when the number of carbon atoms increases, the lipophilicity increases, it becomes difficult to mix with sulfuric acid, and it becomes difficult to obtain monoalkyl sulfate.

  In addition, the aliphatic alcohol is preferably an alcohol in which an alkyl group and one hydroxyl group are bonded, more preferably an alcohol in which an alkyl group having 1 to 12 carbon atoms and one hydroxyl group are bonded, More preferably, the alcohol is an alcohol in which an alkyl group having 1 to 8 carbon atoms and one hydroxyl group are bonded.

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

If the molar ratio of aliphatic alcohol to sulfuric acid (H ₂ SO ₄ ) (mol number of aliphatic alcohol / mol number of sulfuric acid) is small, the ratio of sulfuric acid in the catalyst increases, and condensation of ketone or aldehyde as a raw material ( Mass) and coloring may be significant. Also, at most, the concentration of the entire catalyst decreases, and the reaction slows down, requiring a long time for the reaction. From these facts, the lower limit of the molar ratio of the aliphatic alcohol to sulfuric acid is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.1 or more. The upper limit is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less.

[Organic solvent]
In the method for producing bisphenol of the present invention, the use of an organic solvent is essential for dissolving or dispersing the produced bisphenol. Further, the organic solvent used for the production of bisphenol can be recovered and purified by distillation or the like after completion of the reaction and reused. When the organic solvent is thus reused, a solvent having a low boiling point is preferable.
The organic solvent is not particularly limited as long as the formation reaction of the bisphenol is not hindered, but bisphenol is less likely to be decomposed when the generated bisphenol is dispersed without completely dissolving it in the organic solvent. Further, it is preferable to use a solvent having a low solubility of bisphenol from the viewpoint that the loss at the time of recovering bisphenol from the reaction solution after the completion of the reaction (for example, the loss to the filtrate during crystallization) can be reduced. As such an organic solvent, for example, an aromatic hydrocarbon or an aliphatic hydrocarbon can be used, and an aromatic hydrocarbon is preferable. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, and mesitylene. One of the preferred aromatic hydrocarbons is toluene because bisphenol is difficult to dissolve and has a low boiling point.

  If the mass ratio of the organic solvent to the ketone or aldehyde used for the condensation ((mass of organic solvent / mass of ketone) or (mass of organic solvent / mass of aldehyde)) is too large, ketone or aldehyde and aromatic It is difficult to react with alcohol, and the reaction requires a long time. If the amount is too small, the amount of ketone or aldehyde may be increased, or the precipitated bisphenol may be solidified. From these, the mass ratio of the organic solvent to the ketone or aldehyde used for the condensation is preferably 0.5 or more, more preferably 1 or more, and still more preferably 3 or more. The upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 10 or less.

[Thiol promoter]
In the reaction for condensing a ketone or aldehyde with an aromatic alcohol, a thiol promoter can be used as a promoter. Examples of the thiol promoter used as a cocatalyst include mercaptocarboxylic acids such as mercaptoacetic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and 4-mercaptobutyric acid, and methyl mercaptan, ethyl mercaptan, and propyl mercaptan. Butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan (decanethiol), undecyl mercaptan (undecanethiol), dodecyl mercaptan (dodecanethiol), tridecyl mercaptan, tetradecyl mercaptan And alkylthiols such as pentadecyl mercaptan and mercaptophenol.

When the molar ratio of the thiol promoter to the ketone or aldehyde used in the condensation ((moles of thiol promoter / moles of ketone) or (moles of thiol promoter / moles of aldehyde)) is small, It is difficult to obtain the effect of improving the reaction selectivity of bisphenol by using phenol. In addition, the reaction selectivity of bisphenol is an index of the easiness of formation of the target bisphenol in the bisphenol formation reaction, and the higher the reaction selectivity of bisphenol, the larger the amount of bisphenol generated.
In addition, when the molar ratio of the thiol promoter to the ketone or aldehyde used in the condensation is large, it may be mixed with bisphenol to deteriorate the quality. From these facts, the lower limit of the molar ratio of the thiol promoter to ketone and aldehyde is preferably 0.001 or more, more preferably 0.005 or more, and further preferably 0.01 or more. The upper limit is preferably 1 or less, more preferably 0.5 or less, and further preferably 0.1 or less.

  As described below, the thiol promoter is preferably mixed with a ketone or an aldehyde before the reaction. In the method of mixing the thiol promoter with the ketone or aldehyde, the ketone or aldehyde may be supplied to the thiol promoter, or the thiol promoter may be supplied to the ketone or aldehyde. In addition, a mixed solution of a thiol co-catalyst and a ketone or an aldehyde, and the method of mixing the catalyst may be such that a catalyst may be supplied to a mixed solution of a thiol co-catalyst and a ketone or an aldehyde, and the thiol co-catalyst and the ketone or the A mixture with an aldehyde may be supplied. In order to suppress the self-condensation of the ketone or aldehyde, it is preferable to supply a mixed solution of the thiol promoter and the ketone or aldehyde to the catalyst. Furthermore, after supplying the catalyst and the aromatic alcohol to the reaction vessel, it is more preferable to supply the mixed solution of the thiol promoter and the ketone or aldehyde to the reaction vessel and mix them.

[Condensation reaction between ketone or aldehyde and aromatic alcohol]
In the method for producing bisphenol of the present invention, a bisphenol represented by the following general formula (5) is produced by condensation of a ketone or aldehyde with an aromatic alcohol according to the following reaction formula (4).

(In the formula, R ^{1 to} R ⁶ have the same meaning as those in the general formulas (1) and (2).)

(In the formula, R ^{1 to} R ⁶ have the same meaning as those in the general formulas (1) and (2).)

  As the compound represented by the general formula (5), specifically, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 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 and the like are mentioned. However, the present invention is not limited to this.

  Among them, in order to obtain bisphenol having higher polymerization activity, the method for producing bisphenol of the present invention requires 2,2-bis (4-hydroxy-3-methylphenyl) propane or 2,2-bis (4-hydroxy It is preferable to use a method for producing (-3,5-dimethylphenyl) propane.

  The method for preparing the reaction solution is not particularly limited, and in the method (1) for producing bisphenol of the present invention, a monoalkyl sulfate is supplied to a mixture obtained by mixing an aromatic alcohol, an organic solvent, and a ketone or an aldehyde. And a method of supplying a ketone or an aldehyde to a mixed liquid obtained by mixing a monoalkyl sulfate, an aromatic alcohol, and an organic solvent.

  In order to suppress the multiplication of ketones or aldehydes by self-condensation, it is preferable to mix a solution containing an aromatic alcohol, a monoalkyl sulfate, and an organic solvent with a solution containing a ketone or an aldehyde. In this case, the solution containing the ketone or the aldehyde may contain the ketone or the aldehyde alone, or may contain a thiol promoter or an organic solvent. Preferably, the solution containing a ketone or aldehyde contains a thiol promoter.

In addition, a mixture of a solution containing an aromatic alcohol, a monoalkyl sulfate, and an organic solvent and a solution containing a ketone or an aldehyde is usually mixed with a solution containing an aromatic alcohol, a monoalkyl sulfate, and an organic solvent. By supplying a solution containing a ketone or an aldehyde. Further, they may be supplied collectively or dividedly.
Since the reaction for producing bisphenol is an exothermic reaction, it is preferable to supply the solution containing the ketone or the aldehyde in a divided manner, for example, by supplying the solution dropwise.

A commercially available monoalkyl sulfate can be used as the catalyst, but it is usually difficult to isolate the monoalkyl sulfate. And make it exist in the reaction system. The monoalkyl sulfate is preferably produced by a reaction between sulfuric acid and an aliphatic alcohol.
As a method for producing a monoalkyl sulfate by the reaction of sulfuric acid and an aliphatic alcohol to obtain a solution containing an aromatic alcohol, a monoalkyl sulfate, and an organic solvent, for example, an organic solvent, an aliphatic alcohol and an aromatic alcohol may be used. There is a method in which sulfuric acid is supplied to the mixture to generate monoalkyl sulfate. Further, there is a method in which an aliphatic alcohol and sulfuric acid are mixed to generate monoalkyl sulfate, and then an organic solvent and an aromatic alcohol are supplied.

  In the method (2) for producing bisphenol of the present invention, a solution containing an aromatic alcohol, sulfuric acid, an aliphatic alcohol, and an organic solvent is used in order to suppress the multiplication of ketone or aldehyde by self-condensation. It is preferred to mix with a solution containing a ketone or aldehyde. In this case, the sulfuric acid reacts with the aliphatic alcohol to produce monoalkyl sulfate at the same time, and functions as a catalyst together with the sulfuric acid.

  A method for mixing a solution containing an aromatic alcohol, a sulfuric acid, an aliphatic alcohol, and an organic solvent with a solution containing a ketone or an aldehyde is not particularly limited, and examples thereof include an organic solvent, an aliphatic alcohol, and an aromatic alcohol. A solution containing an aromatic alcohol, a sulfuric acid, an aliphatic alcohol, and an organic solvent is prepared by adding sulfuric acid to the mixed solution of the above, and then a solution containing a ketone or an aldehyde is supplied. In addition, an organic solvent and an aromatic alcohol are added to a mixture of an aliphatic alcohol and sulfuric acid to prepare a solution containing an aromatic alcohol, sulfuric acid, an aliphatic alcohol, and an organic solvent, and then a ketone or an aldehyde is contained. And a method of supplying a solution to be used.

Further, the solution containing the ketone or the aldehyde may be supplied collectively or may be supplied separately.
Since the reaction for producing bisphenol is an exothermic reaction, it is preferable to supply the solution containing the ketone or the aldehyde in a divided manner, for example, by supplying the solution dropwise.

  In the bisphenol production method of the present invention, the bisphenol formation reaction is a condensation reaction between a ketone or aldehyde and an aromatic alcohol. When the reaction temperature of the condensation reaction is high, the amount of ketone or aldehyde increases easily. When the temperature is low, the time required for the reaction is prolonged. For these reasons, the lower limit of the reaction temperature can be -30 ° C or higher, -20 ° C or higher, or -15 ° C or higher. The lower limit of the reaction temperature is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and still more preferably 10 ° C. or higher. The upper limit of the reaction temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower. Further, the reaction temperature may be increased stepwise.

  In the method for producing bisphenol of the present invention, the reaction time of the condensation reaction is appropriately adjusted depending on the reaction conditions such as the production scale, the type of bisphenol to be produced, and the reaction temperature. The lower limit of the reaction time depends on the production scale and the like, but is usually 2 hours or more. By extending the reaction time, the self-condensate of the by-product ketone or aldehyde tends to decompose and the polymerization activity of the resulting bisphenol tends to be improved. Therefore, the lower limit of the reaction time is preferably 5 hours or more, and more preferably 10 hours or less. The time is more preferably not less than 15 hours, more preferably not less than 15 hours. When the reaction time is too long, the produced bisphenol is easily decomposed, so that the reaction time is preferably within 30 hours, more preferably within 25 hours, further preferably within 20 hours.

Note that the reaction time also includes the mixing time of the ketone or aldehyde with the aromatic alcohol (the time for preparing the reaction solution). For example, when a ketone or aldehyde is supplied to a mixed solution of an aromatic alcohol and a catalyst over 1 hour and then reacted for 1 hour, the reaction time is 2 hours.
The supply time (dropping time) of the solution containing the ketone or the aldehyde is appropriately adjusted according to the cooling capacity of the reaction tank, the production scale, the type of bisphenol to be produced, and the like, and depends on the cooling capacity of the reaction tank. It can be 0.3 hours or more or 0.5 hours or more. The upper limit can be, for example, 5 hours or less, 3 hours or less, 1 hour or less. By doing so, a reaction solution can be prepared while suppressing the generation of reaction heat.

  Further, the reaction can be stopped by adding water or a base in an amount equal to or more than that of the catalyst used to lower the catalyst concentration.

[Purification method]
In the method for producing bisphenol of the present invention, the bisphenol obtained by the condensation reaction can be purified by a conventional method. For example, it can be purified by a simple means such as crystallization or column chromatography.
Specifically, after the condensation reaction, the organic phase obtained by separating the reaction solution is washed with water or a saline solution and, if necessary, further washed with an aqueous solution of sodium bicarbonate. Next, the washed organic phase is cooled and crystallized. Washing with water, sodium bicarbonate water, crystallization, etc. may be performed plural times.
When a large amount of the aromatic alcohol is used, the crystallization can be performed after removing the excess aromatic alcohol by distillation before crystallization.

2. Use of bisphenol Bisphenol obtained by the method for producing bisphenol of the present invention (hereinafter sometimes referred to as “bisphenol of the present invention”) is an optical material, a recording material, an insulating material, a transparent material, an electronic material, an adhesive material, Various thermoplastic resins such as polyether resin, polyester resin, polyarylate resin, polycarbonate resin, polyurethane resin, acrylic resin, epoxy resin, unsaturated polyester resin, phenol resin, polybenzo used for various applications such as heat-resistant materials It can be used as a component such as various thermosetting resins such as oxazine resin and cyanate resin, a curing agent, an additive, or a precursor thereof. Further, it is also useful as an additive such as a developer for heat-sensitive recording materials and the like, an anti-fading agent, a bactericide, a fungicide and a fungicide.

  Among these, it is preferable to use it as a raw material (monomer) of a thermoplastic resin or a thermosetting resin because it can impart good mechanical properties, and it is more preferable to use it as a raw material of a polycarbonate resin or an epoxy resin. It is also preferable to use it as a color developer, and it is particularly preferable to use it in combination with a leuco dye and a color change temperature regulator.

3. Next, a method for producing a polycarbonate resin using the bisphenol of the present invention as a raw material will be described.
The method for producing a polycarbonate resin using the bisphenol of the present invention as a raw material includes a transesterification reaction between the bisphenol of the present invention and a diester carbonate such as diphenyl carbonate in the presence of, for example, an alkali metal compound and / or an alkaline earth metal compound. It is a method of manufacturing by a method such as The transesterification reaction can be carried out by appropriately selecting a known method. Hereinafter, an example using the bisphenol and diphenyl carbonate of the present invention as raw materials will be described.

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

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

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

  The amount of the transesterification catalyst used per 1 mol of bisphenol or diphenyl carbonate is usually 0.05 μmol or more, preferably 0.08 μmol or more, more preferably 0.10 μmol or more. Further, it is usually 100 μmol or less, preferably 50 μmol or less, more preferably 20 μmol or less.

  When the amount of the transesterification catalyst is within the above range, it is easy to obtain polymerization activity suitable for producing a polycarbonate resin having a desired molecular weight, and it is excellent in polymer hue, and excessive polymer branching proceeds. First, it is easy to obtain a polycarbonate resin having excellent fluidity during molding.

In order to produce a polycarbonate resin by the above method, it is preferable that both the above-mentioned raw materials are continuously supplied to a raw material mixing tank, and the obtained mixture and the transesterification catalyst are continuously supplied to a polymerization tank.
In the production of a polycarbonate resin by a transesterification method, usually, both raw materials supplied to a raw material mixing tank are uniformly stirred 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, the polymerization time is appropriately adjusted depending on the production scale, the ratio of the raw materials, the desired molecular weight of the polycarbonate resin, and the like. If the polymerization time is long, deterioration in quality such as deterioration in color tone becomes apparent, so that the polymerization time is preferably 10 hours or less, and more preferably 8 hours or less. The lower limit of the polymerization time can be 0.1 hours or more or 0.3 hours or more.

  In addition, when a polycarbonate resin is produced by a melt polymerization method using bisphenol as a raw material, it tends to be difficult to obtain a high-molecular-weight polycarbonate resin. However, the bisphenol of the present invention has excellent polymerization activity (high polymerization activity). And a polycarbonate resin having a large molecular weight can be efficiently produced. In the method for producing a polycarbonate resin of the present invention, by using the bisphenol of the present invention, such a high molecular weight (for example, a viscosity average molecular weight of 10,000 to 100,000 or a viscosity average molecular weight of 24,000 to 50,000) is obtained. A polycarbonate resin can be produced in a short polymerization time (for example, 3 hours or less). In the method for producing a polycarbonate resin of the present invention, a polycarbonate resin having an excellent color tone can be obtained by using the bisphenol of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless the gist is changed.

[Raw materials and reagents]
Orthocresol, toluene, sodium hydroxide, sulfuric acid, dodecanethiol, methanol, acetone, sodium hydrogen carbonate, and cesium carbonate used reagents manufactured by Wako Pure Chemical Industries, Ltd.
As the diphenyl carbonate, a product manufactured by Mitsubishi Chemical Corporation was used.

[analysis]
(Quantitative analysis of bisphenol C, etc.)
Quantitative analysis of the dimer of bisphenol C, orthocresol, and isopenylcresol was performed by high performance liquid chromatography according to the following procedure and conditions.
-Apparatus: LC-2010A manufactured by Shimadzu Corporation, Imtakt Scherzo SM-C18 3 µm 150 mm x 4.6 mm ID
・ Low pressure gradient method ・ Analysis temperature: 40 ℃
・ Eluent composition:
Solution A Ammonium acetate: acetic acid: demineralized water = 3.000 g: 1 mL: 1 L solution Solution B Ammonium acetate: acetic acid: acetonitrile = 1.500 g: 1 mL: 900 mL solution-Solution A: Solution B = 60 at 0 min analysis time : 40 (volume ratio, the same applies hereinafter)
During the analysis time from 0 to 25 minutes, the eluent composition was gradually changed to A: B: 90: 10.
For the analysis time of 25 to 30 minutes, the solution A: solution B is maintained at 90:10,
The analysis was performed at a flow rate of 0.8 mL / min and a detection wavelength of 280 nm.

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

(Terminal hydroxyl group concentration of polycarbonate resin)
The terminal hydroxyl group concentration (OH concentration) of the polycarbonate resin was measured by performing colorimetric quantification in accordance with the titanium tetrachloride / acetic acid method (see Makromol. Chem. 88, 215 (1965)).

(Polycarbonate resin pellet YI)
The pellet YI of the polycarbonate resin (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.
The apparatus used was a spectrophotometer CM-5 manufactured by Konica Minolta, and the measurement conditions were a measurement diameter of 30 mm and SCE.
The calibration glass CM-A212 for petri dish measurement was inserted into the measuring section, and a zero calibration box CM-A124 was placed over the measurement glass to perform zero calibration, and then white calibration was performed using a built-in white calibration plate. Next, measurement was performed using a white calibration plate CM-A210, and L * was 99.40 ± 0.05, a * was 0.03 ± 0.01, b * was −0.43 ± 0.01, and YI was measured. Was -0.58 ± 0.01.
The measurement of the pellet was performed by packing the pellet in a cylindrical glass container having an inner diameter of 30 mm and a height of 50 mm to a depth of about 40 mm. The operation of taking out the pellets from the glass container and performing the measurement again was repeated twice, and the average value of the measured values of three times in total was used.

[Example 1-1]
(1) Production of bisphenol C (first step)
Under a nitrogen atmosphere, 278 g of toluene, 5 g of methanol, and 230 g (2.13 mol) of ortho-cresol were placed in a 1.5-L separable flask equipped with a thermometer, a dropping funnel, a jacket, and a squid-type stirring blade. It was as follows. Then, while stirring a mixed solution of toluene, methanol and ortho-cresol, 250 g of 80% by mass sulfuric acid was slowly added thereto, and sulfuric acid and methanol were reacted to generate monomethyl sulfate. Toluene, methanol, ortho-cresol, and sulfuric acid , A mixed solution (a1-1) of monomethyl sulfate was obtained. The production of monomethyl sulfate was confirmed by H ¹ -NMR.

(2nd process)
In a 500 mL Erlenmeyer flask, 50 g of toluene, 61.0 g (1.05 mol) of acetone, and 7.5 g of dodecanethiol were mixed to prepare a mixed solution (a2-1), which was placed in the dropping funnel. The ratio of ortho-cresol to acetone was 2.13 mol２．１1.05 mol = 2.03.
The mixed solution (a2-1) was added dropwise over 1 hour (dropping time) to the mixed solution (a1-1) such that the temperature of the liquid in the separable flask did not exceed 30 ° C.
After the completion of the dropwise addition, the mixture was stirred for 1 hour while maintaining the internal temperature at 30 ° C, and then heated to 45 ° C over 0.5 hours to obtain a slurry reaction liquid (A1).

After 200 g of demineralized water and 59 g of toluene were added to the obtained slurry reaction solution (A1), 233 g of a 28% aqueous sodium hydroxide solution was added, and the temperature was raised to 80 ° C. After reaching 80 ° C., the organic phase and the aqueous phase were separated by standing, and the lower aqueous phase was extracted to obtain an organic phase (b1-1).
400 g of demineralized water was added to the organic phase (b1-1), mixed, and allowed to stand to separate into an organic phase and an aqueous phase. The aqueous phase was removed to obtain an organic phase (b2-1).
Further, 240 g of a 1.5% by mass aqueous solution of sodium bicarbonate was supplied to the organic phase (b2-1) in two portions, mixed and washed, and the aqueous phase was removed to obtain an organic phase (b3-1).
The obtained organic phase (b3-1) was cooled from 80 ° C to 20 ° C and maintained at 20 ° C to precipitate bisphenol C. Thereafter, the mixture was cooled to 10 ° C., and stirred for 1 hour at 10 ° C. to perform first crystallization to obtain a crystallization slurry liquid (B1).
The obtained crystallization slurry liquid (B1) was subjected to solid-liquid separation using a centrifugal separator to obtain 218 g of a cake (c1-1).
A part of the obtained cake (c1-1) was taken out, and the composition was confirmed by high performance liquid chromatography, thereby confirming that the cake (c1-1) was bisphenol C.

Under a nitrogen atmosphere, 218 g of bisphenol C cake (c1-1) and 373 g of toluene were supplied to a 1 L separable flask equipped with a thermometer, a jacket, and an squirrel-type stirring blade, and the temperature was raised to 80 ° C. After confirming that a homogeneous solution (b4-1) was obtained, the homogeneous solution (b4-1) was sufficiently washed with 600 g of demineralized water in three portions to remove the aqueous phase, and the organic phase (b5-1) was removed. Obtained.
The obtained organic phase (b5-1) was cooled from 80 ° C to 10 ° C, and second crystallization was performed. Thereafter, solid-liquid separation was performed using a centrifuge to obtain wet bisphenol C (c2-1).
Using an evaporator equipped with an oil bath, light boiling components were distilled off under reduced pressure at an oil bath temperature of 100 ° C. to obtain 195 g of white bisphenol C (c3-1).

(2) Production of Polycarbonate Resin 100.00 g (0.39 mol) of the obtained bisphenol C (c3-1) and diphenyl carbonate 86.sup.2 were placed in a 150-mL glass reactor equipped with a stirrer and a distillation tube. 49 g (0.4 mol) and 479 μL of 400 mass ppm cesium carbonate aqueous solution were charged. The operation of reducing the pressure of the glass reactor to about 100 Pa and then returning the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reactor with nitrogen. Thereafter, the reaction vessel was immersed in an oil bath at 200 ° C. to dissolve the contents.

  The rotation speed of the stirrer was set to 100 times per minute, and while the phenol by-produced by the oligomerization reaction of bisphenol C and diphenyl carbonate in the reaction tank was distilled off, the pressure in the reaction tank was changed to an absolute pressure over 40 minutes. The pressure was reduced from 101.3 kPa to 13.3 kPa.

  Subsequently, the pressure in the reaction tank was maintained at 13.3 kPa, and a transesterification reaction was performed for 80 minutes while further distilling off phenol.

  Thereafter, the temperature inside the reaction tank was raised to 250 ° C., and the pressure inside the reaction tank was reduced from 13.3 kPa to 399 Pa in absolute pressure over 40 minutes to remove phenol distilled out of the system.

  Thereafter, the external temperature of the reaction vessel was raised to 280 ° C., the absolute pressure of the reaction vessel was reduced to 30 Pa, and a polycondensation reaction was performed. The polycondensation reaction was terminated when the stirrer in the reaction tank had a predetermined stirring power. The time required for this polymerization step (step until the external temperature of the reaction vessel is raised to 280 ° C., the absolute pressure of the reaction vessel is reduced to 30 Pa, and the stirrer of the reaction vessel has a predetermined stirring power) is 180 minutes. Met.

  Next, after the pressure in the reaction tank was restored to 101.3 kPa with nitrogen, the pressure was increased to 0.2 MPa with a gauge pressure, and the polycarbonate was extracted in a strand form from the bottom of the reaction tank to obtain a strand-like polycarbonate resin.

  Then, the strand was pelletized using a rotary cutter to obtain a pellet-like polycarbonate resin.

  The viscosity average molecular weight (Mv) of the polycarbonate was 24,800, and the pellet YI was 7.6.

[Example 1-2]
(1) Production of bisphenol C The amount of acetone was changed from 61.0 g to 58.0 g (0.999 mol; the ratio of ortho-cresol to acetone was 2.13 mol ÷ 0.999 mol = 2.13). After the first crystallization, 203 g of a bisphenol cake (c1-2) was obtained in the same manner as in Example 1-1 (1), except that this was performed. Further, the second crystallization and distillation of light boiling components were carried out in the same manner as in Example 1-1 (1) except that the cake (c1-1) was replaced with the cake (c1-2). Then, 180 g of white bisphenol C (c3-2) was obtained.

(2) Production of polycarbonate resin A polycarbonate resin was produced in the same manner as (2) of Example 1-1, except that bisphenol C (c3-2) obtained in place of bisphenol C (c3-1) was used. did. The time of the polymerization step was 193 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 253,00, and the pellet YI was 8.5.

[Comparative Example 1]
(1) Production of Bisphenol C In a 1.5 L separable flask equipped with a thermometer, a dropping funnel, a jacket, and a squid-type stirring blade, 278 g of toluene, 5 g of methanol, and 230 g (2.13 mol) of orthocresol were placed under a nitrogen atmosphere. After the internal temperature was lowered to 30 ° C. or lower, 250 g of 80% by mass sulfuric acid was slowly added with stirring.

A 500 mL Erlenmeyer flask was mixed with 50 g of toluene, 71.0 g (1.22 mol) of acetone, and 7.5 g of dodecanethiol to prepare a dropping solution, which was placed in the dropping funnel. The mass ratio of the ortho-cresol to the acetone was 2.13 mol ÷ 1.22 mol = 1.75.
The dropping solution was slowly dropped over 1 hour (dropping time) so that the temperature of the solution in the separable flask did not exceed 30 ° C.
After completion of the dropwise addition, the mixture was stirred for 1 hour while maintaining the internal temperature at 30 ° C., and then heated to 45 ° C. over 0.5 hour and stirred for 3 hours to obtain a slurry reaction liquid.

  The obtained slurry reaction solution was purified in the same manner as in Example 1-1 (1) to obtain 235 g of bisphenol C cake (c1-3) after the first crystallization. Further, the second crystallization and the distillation of light boiling components were carried out in the same manner as in Example 1-1 (1) except that the cake (c1-1) was replaced with the cake (c1-3). Then, 215 g of white bisphenol C (c3-3) was obtained.

(2) Production of polycarbonate resin A polycarbonate resin was produced in the same manner as in (2) of Example 1-1, except that bisphenol C (c3-3) obtained in place of bisphenol C (c3-1) was used. did. The time of the polymerization step was 240 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 23,300, and the pellet YI was 47.3.

[Comparative Example 2]
(1) Production of bisphenol C The amount of acetone was changed from 61.0 g to 30.9 g (0.532 mol; the ratio of orthocresol to acetone was 2.13 mol ÷ 0.532 mol = 4.00). Except having performed, similarly to (1-1) of Example 1-1, 14 g of a bisphenol cake (c1-4) was obtained after the first crystallization. Since the yield of the cake (c1-4) was low, further experiments were abandoned.

For Example 1-1, Example 1-2, Comparative Example 1, and Comparative Example 2, the molar ratio of orthocresol to acetone (substance ratio) in the production of bisphenol C, the polymerization time in the production of the polycarbonate resin, and the like were obtained. The viscosity average molecular weight (Mv) of the obtained polycarbonate resin and the pellet YI of the obtained polycarbonate resin are summarized in Table 1.
From Table 1, when the molar ratio of orthocresol to acetone (substance amount ratio) is 1.75 (Comparative Example 1) in the production of bisphenol C, the polymerization time is increased when producing the polycarbonate resin using the obtained bisphenol C. Even when the length was increased, the viscosity average molecular weight of the obtained polycarbonate resin was low. From these results, it was found that bisphenol C produced at a molar ratio of orthocresol to acetone (substance amount ratio) of 1.75 or less has a long polymerization time until a predetermined stirring power is obtained in the production of a polycarbonate resin, and the obtained polycarbonate The molecular weight of the resin has not reached the predetermined viscosity average molecular weight. Since the viscosity average molecular weight cannot be reached even if the polymerization time is lengthened, it can be seen that the polymerization activity decreases. In Comparative Example 1, it can be estimated that since the polymerization time until the predetermined stirring power is obtained is long, the polymer chain is branched and the viscosity average molecular weight is low.
The polycarbonate resin pellets YI obtained in Comparative Example 1 also showed high results. From this result, when the molar ratio of orthocresol to acetone (substance ratio) is set to 1.75 or less in the production of bisphenol C, the pellet YI of the polycarbonate resin produced using the obtained bisphenol C as a raw material is high. It can be seen that the raw material bisphenol C is a factor that deteriorates the color tone of the polycarbonate resin. The reason for this is that if the molar ratio of orthocresol to acetone (the ratio of the amounts of substances) to acetone is low, the self-condensation of acetone is promoted, and the sulfuric acid produces a sulfonate of a self-condensed product of acetone as a by-product. It is presumed to be the cause.
On the other hand, it can be seen that in the production of bisphenol C, when the ratio of the amount of ortho-cresol to acetone increases, the amount of cake obtained in the first crystallization decreases.

[Example 2-1]
(1) Production of bisphenol C Under a nitrogen atmosphere, 320 g of toluene, 12 g of methanol, and 230 g (2.13 mol) of orthocresol were placed in a 1.5 L separable flask equipped with a thermometer, a dropping funnel, a jacket, and a squirrel-type stirring blade under a nitrogen atmosphere. And the internal temperature was adjusted to 10 ° C. or lower. Next, while stirring a mixture of toluene, methanol and ortho-cresol, 95 g of 98% by mass sulfuric acid was slowly added thereto, and sulfuric acid was reacted with methanol to produce monomethyl sulfate. Toluene, methanol, ortho-cresol and sulfuric acid , A mixed solution of monomethyl sulfate (a1-5) was obtained.

In a 500 mL Erlenmeyer flask, 50 g of toluene, 68.5 g (1.18 mol) of acetone, and 5.4 g of dodecanethiol were mixed to prepare a mixed solution (a2-5), which was placed in the dropping funnel. The substance ratio of ortho-cresol to acetone was 2.13 mol ÷ 1.18 mol = 1.81.
The mixed solution (a2-5) was slowly added dropwise over 1 hour (dropping time) to the mixed solution (a1-5) such that the temperature of the internal solution in the separable flask did not exceed 10 ° C.
After completion of the dropwise addition, the mixture was stirred for 5 hours while maintaining the internal temperature at 10 ° C. to obtain a slurry reaction liquid (A5).

190 g of a 25% aqueous sodium hydroxide solution was added to the obtained slurry reaction solution (A5), and the temperature was raised to 80 ° C. After the temperature reached 80 ° C., the organic phase and the aqueous phase were separated by standing, and the lower aqueous phase was extracted to obtain an organic phase (b1-5).
400 g of demineralized water was added to the organic phase (b1-5), mixed and allowed to stand to separate into an organic phase and an aqueous phase, and the aqueous phase was removed to obtain an organic phase (b2-5).
Further, 240 g of a 1.5% by mass aqueous solution of sodium bicarbonate was supplied to the organic phase (b2-5) in two portions, mixed and washed, and the aqueous phase was removed to obtain an organic phase (b3-5).

  A part of the obtained organic phase (b3-5) was taken out, and the composition of the organic phase (b3-5) was confirmed by high performance liquid chromatography. As a result, 5.7% by mass of cresol and 32.3% by mass of bisphenol C were obtained. % And isopropenyl cresol dimer was 0.6% by mass.

The obtained organic phase (b3-5) was cooled from 80 ° C to 20 ° C and maintained at 20 ° C to precipitate bisphenol C. Thereafter, the mixture was cooled to 10 ° C. and stirred at 10 ° C. for 1 hour to perform first crystallization, thereby obtaining a crystallization slurry liquid (B5).
The obtained crystallization slurry liquid (B5) was subjected to solid-liquid separation using a centrifuge to obtain 276 g of a cake (c1-5).
A part of the obtained cake (c1-5) was taken out, and the composition was confirmed by high performance liquid chromatography, thereby confirming that the cake (c1-5) was bisphenol C.

Under a nitrogen atmosphere, 276 g of bisphenol C cake (c1-5) and 373 g of toluene were supplied to a 1 L separable flask equipped with a thermometer, a jacket, and an squid-type stirring blade, and the temperature was raised to 80 ° C. After confirming that a homogeneous solution (b4-5) was obtained, the homogeneous solution (b4-5) was sufficiently washed three times with 600 g of demineralized water to remove the aqueous phase, and the organic phase (b5-5) I got
The obtained organic phase (b5-5) was cooled from 80 ° C to 10 ° C, and second crystallization was performed. Thereafter, solid-liquid separation was performed using a centrifuge to obtain wet bisphenol C (c2-5).
Using an evaporator equipped with an oil bath, light-boiling components were distilled off under reduced pressure at an oil bath temperature of 100 ° C. to obtain 189 g of white bisphenol C (c3-5).

(2) Production of polycarbonate resin A polycarbonate resin was produced in the same manner as (2) of Example 1-1, except that bisphenol C (c3-5) obtained in place of bisphenol C (c3-1) was used. did. The time of the polymerization step was 170 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,600, and the pellet YI was 7.4.

[Example 2-2]
Under a nitrogen atmosphere, 320 g of toluene, 15 g of methanol, and 230 g (2.13 mol) of ortho-cresol were put into a 1.5 L separable flask equipped with a thermometer, a dropping funnel, a jacket, and a squid-type stirring blade. It was as follows. Next, while stirring a mixture of toluene, methanol and ortho-cresol, 95 g of 98% by mass sulfuric acid was slowly added thereto, and sulfuric acid was reacted with methanol to produce monomethyl sulfate. Toluene, methanol, ortho-cresol and sulfuric acid , A mixed solution of monomethyl sulfate (a1-6) was obtained.

In a 500 mL Erlenmeyer flask, 50 g of toluene, 65.0 g (1.12 mol) of acetone, and 5.4 g of dodecanethiol were mixed to prepare a mixed solution (a2-6), which was placed in the dropping funnel. The mass ratio of the ortho-cresol to the acetone was 2.13 mol ÷ 1.12 mol = 1.90.
The mixed solution (a2-6) was slowly added dropwise over 1 hour (dropping time) to the mixed solution (a1-6) such that the temperature of the internal solution in the separable flask did not exceed 10 ° C.
After the completion of the dropwise addition, the mixture was stirred for 2.5 hours while maintaining the internal temperature at 10 ° C. to obtain a slurry reaction liquid (A6).

  The obtained slurry reaction solution (A6) was purified in the same manner as the slurry reaction solution (A5) of Example 2-1 (1), and after the first crystallization, 274 g of bisphenol C cake (c1-6) I got Further, the second crystallization and distillation of light boiling components were carried out in the same manner as (1) of Example 2-1 except that the cake (c1-5) was replaced with the cake (c1-6). Then, 193 g of white bisphenol C (c3-6) was obtained.

(2) Production of polycarbonate resin A polycarbonate resin was produced in the same manner as (2) of Example 1-1, except that bisphenol C (c3-6) obtained in place of bisphenol C (c3-1) was used. did. The time of the polymerization step was 170 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,700, and the pellet YI was 10.6.

[Example 2-3]
(1) Production of bisphenol C The amount of acetone was changed from 65.0 g to 61.0 g (1.05 mol; the ratio of the amount of ortho-cresol to acetone was 2.13 mol ÷ 1.05 mol = 2.03). Except having performed, similarly to (1) of Example 2-2, after the first crystallization, 256 g of a bisphenol cake (c1-7) was obtained. Further, the second crystallization and light-boiling distillation were performed in the same manner as in Example 2-2, except that the cake (c1-6) was replaced with the cake (c1-7). 197 g of bisphenol C (c3-7) was obtained.

(2) Production of polycarbonate resin A polycarbonate resin was produced in the same manner as (2) of Example 1-1, except that bisphenol C (c3-7) obtained in place of bisphenol C (c3-1) was used. did. The time of the polymerization step was 140 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,900, and the pellet YI was 12.2.

[Comparative Example 3]
Example 2-2 except that the amount of acetone was changed from 65.0 g to 49.4 g of acetone (0.850 mol; the ratio of the amount of ortho-cresol to acetone was 2.13 mol ÷ 0.850 mol = 2.51). In the same manner as (1), after the first crystallization, 194 g of a bisphenol cake (c1-8) was obtained.

For Examples 2-1 to 2-3 and Comparative Examples 1 to 3, the molar ratio of orthocresol to acetone (substance amount ratio) in the production of bisphenol C, the polymerization time in the production of the polycarbonate resin, and the molecular weight of the obtained polycarbonate resin Table 2 summarizes the pellets YI of the obtained polycarbonate resin.
From Table 2, it can be seen that bisphenol C produced under the condition that the molar ratio of ortho-cresol to acetone (substance amount ratio) is higher than 1.75 has a short polymerization time in the production of polycarbonate resin, and pellets YI of the obtained polycarbonate resin are obtained. It can be seen that the temperature can also be kept low.
On the other hand, from the results of Comparative Example 2 and Comparative Example 3, in the production of bisphenol C, when the ratio of the amount of ortho-cresol to acetone increased, the amount of residual cresol increased, and the production of bisphenol C by the first crystallization and filtration was started. It can be seen that loss increases and the amount of bisphenol C cake obtained decreases.

[Comparative Example 4]
Example 2-1 was carried out in the same manner as in Example 2-1, except that supply of 12 g of methanol was omitted, to obtain 148 g of slightly yellow bisphenol C (c3-9).
A part of the organic phase (b3-9) after washing with an aqueous sodium bicarbonate solution was taken out, and the composition of the organic phase (b3-9) was confirmed by high performance liquid chromatography. C was 27.3% by mass, and a dimer of isopropenyl cresol was 2.6% by mass.

For Example 2-1 and Comparative Example 4, the presence or absence of monomethyl sulfate in the production of bisphenol C, the concentration of the dimer of isopenylcresol contained in the obtained organic phase (b3), and the second crystallization were used. Table 3 summarizes the yield and color tone of the obtained bisphenol C.
From Table 3, in the production of bisphenol C, the reaction solution contains monoalkyl sulfate, thereby suppressing the production of dimer of isopenylcresol, increasing the yield of bisphenol C and improving the color tone of bisphenol C. You can see that

[Example 3-1]
A full-jacketed 1 L separable flask equipped with a thermometer, a stirrer, and a 100 mL dropping funnel was charged with 21.2 g of methanol under a nitrogen atmosphere, and 46.5 g of 92% by weight sulfuric acid was slowly added. The solution generated monomethyl. Thereafter, 122.4 g of ortho-xylene, 137.7 g (1.27 mol) of ortho-cresol and 4.4 g of dodecanethiol were added, the temperature in the separable flask was set at 40 ° C., and ortho-xylene, methanol, ortho-cresol, sulfuric acid, and sulfuric acid were added. A mixed solution of monomethyl (a1-10) was obtained. 34.3 g (0.590 mol) of acetone was put into the dropping funnel and slowly dropped into the separable flask over 30 minutes and supplied. The substance ratio of ortho-cresol to acetone was 1.27 mol７0.590 mol = 2.15.

After the completion of the dropwise addition of acetone, the reaction was carried out at 40 ° C. for 2 hours to obtain a slurry reaction liquid (A10).
After completion of the reaction, 100.0 g of ortho-xylene and 100.0 g of dechlorinated water were supplied to the slurry reaction solution (A10), and the temperature was raised to 80 ° C. After reaching 80 ° C., it was allowed to stand, and after confirming that the substance precipitated during the reaction was dissolved in the organic phase and the aqueous phase, the lower aqueous phase was extracted to obtain an organic phase (b1-10). Was.
Thereafter, a saturated sodium hydrogen carbonate solution was added to the obtained organic phase (b1-10), and after confirming that the lower aqueous phase pH became 9 or more, the lower aqueous phase was extracted, and the organic phase was extracted. Phase (b2-10) was obtained.
Dechlorinated water was added to the obtained organic phase (b2-10), and the mixture was stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was extracted to obtain an organic phase (b3-10).

  A part of the obtained organic phase (b3-10) was taken out, and the composition of the organic phase (b3-10) was confirmed by high performance liquid chromatography to confirm the formation of bisphenol C. The reaction yield of bisphenol C based on acetone (mol amount of bisphenol / mol amount of raw material acetone × 100%) was 88 mol%.

[Reference Example 1]
0.2 g of methanol was placed in a 50 mL eggplant-shaped flask, and 0.5 g of 92% by weight sulfuric acid was slowly added thereto, followed by shaking for 1 minute. This solution was placed in a 5 mmφ NMR sample tube, and a heavy chloroform tube for locking (2 mmφ sealed tube) was inserted into the sample to measure proton nuclear magnetic resonance ( ¹ H-NMR). ^{On the 1} H-NMR spectrum, a signal was observed at δ 4.0 ppm. When 9.7 mg of monomethyl sodium sulfate as a reagent was added to the NMR sample tube, the peak at δ 4.0 ppm was increased. Thus, it was confirmed that the peak was a signal of a proton of monomethyl sulfate. From this result, it was confirmed that when sulfuric acid and methanol were mixed, monomethyl sulfate was generated.
Incidentally, proton nuclear magnetic resonance ⁽¹ H-NMR) measurements were performed using a JNM = ECS400 type manufactured by JEOL Corporation.

  ADVANTAGE OF THE INVENTION According to this invention, about a various bisphenol, bisphenol can be manufactured simply, efficiently, and industrially advantageously. The bisphenol produced by the method for producing bisphenol of the present invention is useful as a raw material for a polymer material such as a polycarbonate resin because of its excellent polymerization activity.

Claims (7)

In the presence of a catalyst and an organic solvent, an aromatic alcohol, a ketone or an aldehyde is condensed to obtain a bisphenol, a method for producing bisphenol,
The catalyst comprises a monoalkyl sulfate,
A method for producing bisphenol, wherein the molar ratio of the aromatic alcohol to the ketone or aldehyde is 1.80 or more and 2.20 or less, and the ketone or aldehyde is reacted with the aromatic alcohol. The catalyst comprises sulfuric acid and monoalkyl sulfate,
The method for producing bisphenol according to claim 1, wherein the monoalkyl sulfate is generated from the sulfuric acid and an aliphatic alcohol. A method for producing bisphenol by condensing an aromatic alcohol and a ketone or aldehyde to obtain a bisphenol,
The molar ratio of the aromatic alcohol to the ketone or aldehyde is 1.80 or more and 2.20 or less,
A method for producing bisphenol, comprising reacting the ketone or aldehyde with the aromatic alcohol in the presence of sulfuric acid, an aliphatic alcohol and an organic solvent.   The method for producing bisphenol according to any one of claims 1 to 3, wherein the ketone or aldehyde is acetone.   The method for producing bisphenol according to any one of claims 1 to 4, wherein the aromatic alcohol is cresol.   The method for producing bisphenol according to any one of claims 1 to 5, wherein the organic solvent is an aromatic hydrocarbon.   A method for producing a polycarbonate resin, comprising producing a polycarbonate resin using the bisphenol produced by the method for producing a bisphenol according to any one of claims 1 to 6.