JP2020037528A - Bisphenol production method and polycarbonate resin production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing bisphenol capable of efficiently producing bisphenol having excellent color tone and polymerization activity. Further, the present invention provides a method for producing a polycarbonate resin capable of stably producing a polycarbonate resin having an excellent color tone. SOLUTION: This is a method for producing bisphenol by condensing an aromatic alcohol with a ketone or an aldehyde in the presence of an acid catalyst and an organic solvent to obtain bisphenol, and the molar ratio of the aromatic alcohol to the ketone or aldehyde. 1.85 or more and 2.20 or less, and a method for producing bisphenol in which the ketone or aldehyde is reacted with the aromatic alcohol. A method for producing a polycarbonate resin for producing a polycarbonate resin using the bisphenol produced by the method for producing bisphenol. [Selection diagram] None

Description

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

  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.

Bisphenol is used for a wide variety of applications as a raw material for various resins such as polycarbonate resins, and its use is expected to expand in the future. Therefore, a bisphenol capable of stably performing a polymerization reaction for producing a polycarbonate resin or the like is required.
In addition, there is also a field where it is used as a raw material of an optical material such as an optical polycarbonate resin.In recent years, in order to obtain a polycarbonate resin having an excellent color tone, bisphenol capable of producing a polycarbonate resin having a good color tone has been required. ing.

  As a method for producing bisphenol, a method of condensing an aromatic alcohol with a ketone or aldehyde is known. Also, ketones and aldehydes are liable to self-condensation reaction.Therefore, if a condensation reaction is carried out at a low concentration of ketone or aldehyde during the production of bisphenol, the amount of by-product ketone or aldehyde condensate formed increases, Is known to decrease the reaction selectivity. Therefore, usually, a large excess of an aromatic alcohol is reacted with a ketone or an aldehyde to produce bisphenol, and 3 to 4 moles or more of the aromatic alcohol is used per 1 mole of the ketone or aldehyde. Is common.

  However, when a large excess of an aromatic alcohol is reacted with a ketone or an aldehyde, a large amount of the aromatic alcohol remains unreacted. In a state where a large amount of unreacted aromatic alcohol is present, recovery of bisphenol by crystallization or the like from the reaction solution becomes inefficient. Further, the unreacted aromatic alcohol can be recovered and reused, but equipment for recovering the unreacted aromatic alcohol or the like is required, or the unreacted aromatic alcohol is recovered. Heating and the like may cause decomposition and coloring of bisphenol.

  On the other hand, a method for producing bisphenol using a condition in which the amount ratio (molar ratio) of aromatic alcohol to ketone or aldehyde is lower than the theoretical substance ratio of 2 is also being studied.

For example, Patent Document 1 discloses a method for overcoming the problem of using chlorine gas or sulfuric acid alone as an acidic catalyst and producing a bisphenol safely and efficiently by mixing a phenol derivative, acetone, and hydrochloric acid. There is disclosed a method for producing a bisphenol compound which is reacted with sulfuric acid dropwise to obtain 2,2-bis (4-hydroxyphenyl) propane or a derivative thereof.
Further, Patent Document 2 discloses that a first mixture containing an acidic catalyst, a specific phenol compound, and a second mixture containing a specific ketone compound or aldehyde and a compound are used in order to suppress generation of a by-product. There is disclosed a method for producing a bisphenol compound in which an organic solvent is added to at least one of them, and the second mixture is added to the first mixture to cause a condensation reaction.

JP 2014-40376 A JP 2008-214248 A

  In the production of a polymer material such as a polycarbonate resin, there has been a problem that depending on the quality of bisphenol used as a raw material, polymerization becomes poor, and a polymer material such as a polycarbonate resin cannot be obtained stably. Similarly, depending on the quality of the bisphenol, there was a problem that a polymer material such as a polycarbonate resin having a good color tone could not be obtained.

Bisphenol produced by the production method described in Patent Documents 1 and 2 may not increase the degree of polymerization or take time to polymerize when used as a raw material of a polymer material such as a polycarbonate resin. It was found that the polymerization activity of bisphenols varied. Furthermore, even when the color tone of bisphenol was visually the same, it was found that when a polymer material such as a polycarbonate resin was produced using this as a raw material, the color tone of the obtained polymer material varied.
Further, bisphenols produced by the production methods described in Patent Documents 1 and 2 require a long time for the reaction, and there is room for improvement in terms of the reaction time.

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 bisphenol that can efficiently produce bisphenol having excellent color tone and polymerization activity.
Another object of the present invention is to provide a method for producing a polycarbonate resin which can stably produce a polycarbonate resin having an excellent color tone using the bisphenol obtained by the above-mentioned method for producing bisphenol.

  Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the following inventions meet the above objects, and have accomplished the present invention.

That is, the present invention relates to the following inventions.
[1] A method for producing bisphenol by condensing an aromatic alcohol with a ketone or aldehyde in the presence of an acid catalyst and an organic solvent, wherein the molar ratio of the aromatic alcohol to the ketone or aldehyde is 1. A method for producing bisphenol, wherein the ketone or aldehyde is reacted with the aromatic alcohol to be 1.85 or more and 2.20 or less.
[2] The method for producing bisphenol according to [1], wherein the ketone or aldehyde is acetone.
[3] The method for producing bisphenol according to [1] or [2], wherein the aromatic alcohol is cresol.
[4] The method for producing bisphenol according to any one of [1] to [3], wherein the organic solvent contains an aromatic hydrocarbon.
[5] The method for producing bisphenol according to any one of [1] to [4], wherein the acid catalyst is sulfuric acid.
[6] A method for producing a polycarbonate resin using the bisphenol produced by the method for producing bisphenol according to any one of [1] to [5].

  According to the present invention, bisphenol excellent in color tone and polymerization activity can be efficiently 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. The present invention provides a method for producing bisphenol by condensing an aromatic alcohol and a ketone or aldehyde in the presence of an acid catalyst and an organic solvent to obtain a bisphenol, wherein the aromatic to the ketone or aldehyde is obtained. A method for producing a bisphenol by reacting the ketone or aldehyde with the aromatic alcohol by setting the molar ratio of the alcohol to 1.85 or more and 2.20 or less (hereinafter referred to as "the method for producing the bisphenol of the present invention") There is.)

  A feature of the method for producing bisphenol of the present invention is that the molar ratio of the aromatic alcohol to the ketone or aldehyde used for the condensation is controlled in the range of 1.85 or more and 2.20 or less. Therefore, in the method for producing bisphenol of the present invention, the presence of an organic solvent is essential.

  The present inventors have found that the molar ratio of aromatic alcohol to ketone or aldehyde used in the condensation is within a specific range, thereby suppressing the amount of unreacted aromatic alcohol to be recovered and industrially having excellent color tone and polymerization activity. It has been found that an advantageous bisphenol can be produced in a short time. Using the obtained bisphenol, it is possible to efficiently produce a polymer material such as a polycarbonate resin having an excellent color tone.

  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 bisphenol production method of the present invention is usually 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 ((moles of aromatic alcohol / moles of ketone) or (moles of aromatic alcohol / moles of aldehyde)) is 1.85 or more. .20 or less. If the molar ratio of aromatic alcohol to ketone or aldehyde used for the condensation is less than 1.85, bisphenol having high polymerization activity cannot be obtained, or a long time is required to obtain bisphenol having high polymerization activity. Further, the color tone of the obtained bisphenol tends to deteriorate. If the molar ratio of aromatic alcohol to ketone or aldehyde used for the condensation is more than 2.20, it is difficult to efficiently recover the produced bisphenol, and the yield tends 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 obtain bisphenol having higher polymerization activity, the molar ratio of aromatic alcohol to ketone or aldehyde used for the condensation is 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.

[Acid catalyst]
Examples of the acid catalyst used in the bisphenol production method of the present invention 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. Can be

  When the molar ratio of the acid catalyst to the ketone or aldehyde used for the condensation ((moles of the acid catalyst / moles of the ketone) or (moles of the acid catalyst / moles of the aldehyde)) is small, the molar ratio increases with the progress of the condensation reaction. The acid catalyst is diluted by the by-produced water, and the reaction takes time. If the amount is large, the amount of ketone or aldehyde may increase. From these facts, the molar ratio of the acid 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.

  The acid catalyst is preferably any one selected from the group consisting of sulfuric acid, hydrochloric acid, and hydrogen chloride gas, and more preferably sulfuric acid or hydrochloric acid. In addition, sulfuric acid is more preferable as the acid catalyst from the viewpoint that the reaction efficiency is excellent, the volatility of the acid catalyst is low, and the load on the equipment is small.

(Sulfuric acid)
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 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 the reaction for producing bisphenol hardly proceeds, the reaction time for producing bisphenol increases, and the efficiency increases. It can be difficult to produce bisphenol. Therefore, the concentration of the sulfuric acid used is preferably 70% by mass or more, more preferably 75% by mass or more, and further preferably 80% by mass or more. Further, it can be 90% by mass or more or 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.

[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. Further, the mixing method of the mixed solution of the thiol promoter and the ketone or aldehyde with the acid catalyst may be such that the acid catalyst may be supplied to the mixed solution of the thiol promoter and the ketone or aldehyde, And a mixture of ketone and aldehyde. 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 acid catalyst. Further, a method is more preferable in which after the acid catalyst and the aromatic alcohol are supplied to the reaction vessel, a mixed solution of the thiol promoter and the ketone or aldehyde is supplied to the reaction vessel and mixed.

[Organic solvent]
In the method for producing bisphenol of the present invention, the use of an organic solvent is essential for dissolving and dispersing the produced bisphenol.
The organic solvent is not particularly limited as long as it does not inhibit the reaction for producing bisphenol, and examples thereof include aromatic hydrocarbons, aliphatic alcohols, and aliphatic hydrocarbons. May be used in combination.

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

  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.

  Further, the aliphatic alcohol is preferably an alcohol in which an alkyl group and one hydroxyl group are bonded, and from the viewpoint of compatibility with an acid catalyst, an alkyl group having 1 to 12 carbon atoms and one hydroxyl group are preferable. The alcohol is more preferably an alcohol having a group bonded thereto, and even more preferably an alcohol having an alkyl group having 1 to 8 carbon atoms and one hydroxyl group bonded thereto.

  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 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 alcohol Are difficult to react, and the reaction takes 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.

  The bisphenol that is produced is more difficult to decompose if it is dispersed without completely dissolving it in an 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. Examples of the solvent having low solubility of bisphenol include aromatic hydrocarbons. Therefore, the organic solvent preferably contains an aromatic hydrocarbon, preferably contains 55% by mass or more of the aromatic hydrocarbon in the organic solvent, more preferably contains 70% by mass or more, and contains 80% by mass or more. Is more preferred. One of the preferred aromatic hydrocarbons is toluene because bisphenol is difficult to dissolve and has a low boiling point.

When the acid catalyst contains sulfuric acid, the organic solvent is preferably an organic solvent containing an aliphatic alcohol. In addition, since the aliphatic alcohol increases in lipophilicity and becomes difficult to mix with sulfuric acid when the number of carbon atoms increases, an alkyl alcohol having 12 or less carbon atoms is preferable, and an alkyl alcohol having 8 or less carbon atoms is more preferable.
As described above, by using sulfuric acid and an aliphatic alcohol in combination, the acid strength of sulfuric acid can be controlled, and the condensation (multimerization) and coloring of the raw material ketone or aldehyde can be further suppressed. In addition, it is considered that monoalkyl sulfate generated by the reaction between sulfuric acid and an aliphatic alcohol also has a catalytic effect, so that the formation reaction of bisphenol is easily caused. For this reason, it is possible to easily and efficiently produce bisphenol in which the generation of by-products is suppressed and the coloring of the products is reduced.

  When sulfuric acid and an aliphatic alcohol are used in combination, if the molar ratio of the aliphatic alcohol to sulfuric acid (the number of moles of the aliphatic alcohol / the number of moles of sulfuric acid) is small, the effect of the aliphatic alcohol is low, and the condensation of the raw material ketone or aldehyde is performed. (Multimerization) and coloring may be significant. On the other hand, when the amount is large, the sulfuric acid concentration decreases, and the reaction slows down. 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.

  For example, the organic solvent may include an aromatic hydrocarbon and an aliphatic alcohol, and the organic solvent includes 90 to 99.9% by mass of the aromatic hydrocarbon and 0.1 to 10% by mass of the aliphatic alcohol. Can be included.

[Condensation reaction between ketone or aldehyde and aromatic alcohol]
In the method for producing a bisphenol of the present invention, a bisphenol represented by the following general formula (4) is produced by condensation of a ketone or aldehyde with an aromatic alcohol according to the following reaction formula (3).

(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).)

  Specific examples of the compound represented by the general formula (4) include 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, bisphenol having more excellent color tone and polymerization activity is easily obtained. Therefore, the method for producing bisphenol of the present invention employs 2,2-bis (4-hydroxy-3-methylphenyl) propane or 2,2-bis (4 (Hydroxy-3,5-dimethylphenyl) propane is preferred.

  The method for preparing the reaction solution is not particularly limited, and a method of mixing a solution containing an aromatic alcohol, an organic solvent, and a ketone or an aldehyde with a solution containing an acid catalyst, an acid catalyst, an aromatic alcohol, And a method of mixing a solution containing an organic solvent and a solution containing a ketone or an aldehyde.

  It is preferable to mix a solution containing an acid catalyst, an aromatic alcohol, and an organic solvent with a solution containing a ketone or an aldehyde, in order to suppress the multiplication of the ketone or the aldehyde due to self-condensation. 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.

The acid catalyst, aromatic alcohol, and a solution containing an organic solvent, and a mixture of a solution containing a ketone or an aldehyde, usually, an acid catalyst, an aromatic alcohol, and a solution containing an organic solvent, It can be performed by supplying a solution containing a ketone or an aldehyde. The solution containing the ketone or the aldehyde may be supplied in a lump or in a divided manner.
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.

  The bisphenol formation reaction in the bisphenol production method of the present invention 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 according to the reaction conditions such as the production scale, the type of bisphenol to be produced, and the reaction temperature. When the reaction time is 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. The lower limit of the reaction time is usually 2 hours or longer, and may be 5 hours or longer or 10 hours or longer.

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 solution in which an aromatic alcohol and an acid catalyst are mixed 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.
In the method for producing a polycarbonate resin using the bisphenol of the present invention as a raw material, a transesterification reaction between the bisphenol of the present invention and a diester carbonate such as diphenyl carbonate is carried out, for example, in the presence of 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 relative 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, the polymerization activity required for producing a polycarbonate resin having a desired molecular weight can be easily obtained, and the polymer hue is excellent, and excessive polymer branching is promoted. 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, a high molecular weight polycarbonate resin tends to be difficult to obtain, but the bisphenol of the present invention has excellent polymerization activity (high polymerization activity). And a polycarbonate having a large molecular weight can be efficiently produced. In the method for producing a polycarbonate resin of the present invention, a polycarbonate resin having such a high molecular weight (for example, a viscosity average molecular weight of 10,000 to 100,000 or 24,000 to 50,000) can be obtained by using the bisphenol of the present invention. It 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)
The quantitative analysis of bisphenol C 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: dechlorinated water = 3.000 g: 1 mL: 1 L solution Solution B Ammonium acetate: acetic acid: acetonitrile = 1.500 g: 1 mL: 900 mL solution • At analysis time 0 minutes, solution A: solution B = 60:40 (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.
Solution A: Solution B = 90: 10 for an analysis time of 25 to 30 minutes,
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 and 230 g (2.13 mol) of ortho-cresol were placed in a 3 L separable flask equipped with a thermometer, a dropping funnel, a jacket, and an squid-type stirring blade, and the internal temperature was adjusted to 30 ° C. or lower. . Next, 650 g of 35% by mass hydrochloric acid was slowly added thereto while stirring the mixed solution of toluene and ortho-cresol to obtain a mixed solution (a1-1) of toluene, ortho-cresol, and hydrochloric acid.

(2nd process)
A 500 mL Erlenmeyer flask was mixed with 50 g of toluene, 66.8 g (1.15 mol) of acetone, and 7.5 g of dodecanethiol to prepare a mixed solution (a2-1), which was placed in the dropping funnel. The amount ratio of ortho-cresol to acetone was 2.13 mol ÷ 1.15 mol = 1.85.
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 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 1 hour 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 liquid (A1), 500 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 192 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, 192 g of bisphenol C cake (c1-1) and 315 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 (b4-1) was obtained, the homogeneous solution (b4-1) was sufficiently washed with 600 g of demineralized water in three portions, and the aqueous phase was removed to remove the organic phase (b5-1). I got
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 177 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. Time of this polymerization step (time from the time when the external temperature of the reactor is raised to 280 ° C. and the absolute pressure of the reactor is started to be reduced to 30 Pa, until the stirrer of the reactor has a predetermined stirring power) Was 140 minutes.

  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 25,300, and the pellet YI was 9.2.

[Example 1-2]
(1) Production of bisphenol C The amount of acetone was changed from 66.8 g (1.15 mol) to 56.2 g (0.968 mol; the ratio of ortho-cresol to acetone was 2.13 mol ÷ 0.968 mol = Except having changed into 2.20), 183 g of bisphenol cake (c1-2) was obtained after the first crystallization in the same manner as (1) of Example 1-1. 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, 154 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 26,100, and the pellet YI was 10.5.

[Comparative Example 1-1]
(1) Production of bisphenol C The amount of acetone was changed from 66.8 g (1.15 mol) to 71.4 g (1.23 mol; the ratio of orthocresol to acetone was 2.13 mol ÷ 1.23 mol = After the first crystallization, 223 g of a bisphenol cake (c1-3) was obtained in the same manner as (1) of Example 1-1, except that the composition was changed to 1.73). 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, 192 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 21,100, and the pellet YI was 65.2.

About Example 1-1, Example 1-2, and Comparative Example 1-1, the molar ratio of orthocresol to acetone (substance amount ratio) in the production of bisphenol C, and the viscosity average molecular weight (Mv) of the obtained polycarbonate resin. Table 1 summarizes the pellets YI of the obtained polycarbonate resin.
According to Table 1, when the molar ratio of orthocresol to acetone (substance amount ratio) is lower than 1.85 in the production of bisphenol, the pellet YI of the polycarbonate resin obtained in the production of the polycarbonate resin using the obtained bisphenol is high. It can be seen that a polycarbonate resin having a good color tone cannot be obtained.
Further, when the molar ratio of orthocresol to acetone (substance amount ratio) is 1.73, the polymerization time until a predetermined stirring power is obtained when a polycarbonate resin is produced using the obtained bisphenol C is increased. Also, the molecular weight of the obtained polycarbonate resin was low. This indicates that when the molar ratio (substance amount ratio) of ortho-cresol to acetone is 1.73, the polymerization activity of bisphenol C obtained decreases. This can be presumed to be due to the fact that the polymerization time required for obtaining the predetermined stirring power is long, so that the polymer chain is branched.

[Example 2-1]
(1) Production of bisphenol C (first step)
Under a nitrogen atmosphere, 278 g of toluene and 230 g (2.13 mol) of ortho-cresol were placed in a 3 L separable flask equipped with a thermometer, a dropping funnel, a jacket, and an squid-type stirring blade, and the internal temperature was adjusted to 30 ° C. or lower. . Next, while stirring the mixed solution of toluene and ortho-cresol, 80 g of 98% by mass sulfuric acid was slowly added thereto to obtain a mixed solution (a1-4) of toluene, ortho-cresol, and sulfuric acid.

(2nd process)
A 500 mL Erlenmeyer flask was mixed with 50 g of toluene, 65.0 g (1.12 mol) of acetone, and 10.5 g of dodecanethiol to prepare a mixed solution (a2-4), which was placed in the dropping funnel. The ratio of the amount of ortho-cresol to acetone was 2.13 mol ÷ 1.12 mol = 1.90.
The mixed liquid (a2-4) was added dropwise to the mixed liquid (a1-4) over 1 hour (dropping time) such that the temperature of the liquid 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. Thereafter, 60 g of toluene was added, and the temperature was raised to 45 ° C. over 1 hour to obtain a slurry reaction liquid (A4).

After 200 g of demineralized water was added to the obtained slurry reaction liquid (A4), 200 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 (b1-4).
400 g of demineralized water was added to the organic phase (b1-4), 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 (b2-4).
Further, 240 g of a 1.5 mass% aqueous solution of sodium bicarbonate was supplied to the organic phase (b2-4) in two portions, mixed and washed, and the aqueous phase was removed to obtain an organic phase (b3-4).
The obtained organic phase (b3-4) 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 to obtain a crystallization slurry liquid (B4).
The obtained crystallization slurry liquid (B4) was subjected to solid-liquid separation using a centrifuge to obtain 152 g of a cake (c1-4).
A part of the obtained cake (c1-4) was taken out, and the composition was confirmed by high performance liquid chromatography, thereby confirming that the cake (c1-4) was bisphenol C.

Under a nitrogen atmosphere, 152 g of bisphenol C cake (c1-4) and 315 g of toluene were supplied to a 1-L separable flask equipped with a thermometer, a jacket, and a squirrel-type stirring blade, and the temperature was raised to 80 ° C. After confirming that a homogeneous solution (b4-4) was obtained, the homogeneous solution (b4-4) was thoroughly washed three times with 600 g of demineralized water to remove the aqueous phase, and the organic phase (b5-4). I got
The obtained organic phase (b5-4) 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 (c2-4).
Using an evaporator equipped with an oil bath, light-boiling components were distilled off at an oil bath temperature of 100 ° C. under reduced pressure to obtain 132 g of white bisphenol C (c3-4).

(2) Production of polycarbonate resin A polycarbonate resin was produced in the same manner as in Example 1-1 (2) except that bisphenol C (c3-4) obtained in place of bisphenol C (c3-1) was used. did. The time of the polymerization step was 200 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,900, and the pellet YI was 11.2.

[Comparative Example 2-1]
(1) Production of bisphenol C The amount of acetone was changed from 66.8 g (1.15 mol) to 70.2 g (1.21 mol; the ratio of orthocresol to acetone was 2.13 mol ÷ 1.21 mol = Except having changed into 1.76), 212 g of bisphenol cake (c1-5) was obtained after the first crystallization in the same manner as in (2-1) of Example 2-1. Further, the second crystallization and light-boiling distillation were carried out in the same manner as (1) of Example 2-1 except that the cake (c1-4) was replaced with the cake (c1-5). Then, 182 g of white bisphenol C (c3-5) 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 (c3-5) 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 20,100, and the pellet YI was 58.2.

[Example 3-1]
(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. Next, 250 g of 80% by mass sulfuric acid was slowly added thereto while stirring the mixed solution of toluene, methanol and ortho-cresol to obtain a mixed solution (a1-6) of toluene, methanol, ortho-cresol and sulfuric acid.

(2nd process)
A 500 mL Erlenmeyer flask was mixed with 50 g of toluene, 66.8 g (1.15 mol) of acetone, and 7.5 g of dodecanethiol to prepare a mixed solution (a2-6), which was placed in the dropping funnel. The amount ratio of ortho-cresol to acetone was 2.13 mol ÷ 1.15 mol = 1.85.
The mixture (a2-6) was added dropwise to the mixture (a1-6) over 1 hour (dropping time) such that the temperature of the liquid 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 hours to obtain a slurry reaction liquid (A6).

After 200 g of demineralized water and 59 g of toluene were added to the obtained slurry reaction solution (A6), 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 (b1-6).
400 g of demineralized water was added to the organic phase (b1-6), 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 (b2-6).
Further, 240 g of a 1.5% by mass aqueous solution of sodium bicarbonate was supplied to the organic phase (b2-6) in two portions, mixed and washed, and the aqueous phase was removed to obtain an organic phase (b3-6).
The obtained organic phase (b3-6) 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 (B6).
The obtained crystallization slurry liquid (B6) was subjected to solid-liquid separation using a centrifuge to obtain 230 g of a cake (c1-6).
A part of the obtained cake (c1-6) was taken out, and the composition was confirmed by high performance liquid chromatography, thereby confirming that the cake (c1-6) was bisphenol C.

Under a nitrogen atmosphere, 230 g of bisphenol C cake (c1-6) and 373 g of toluene were supplied to a 1 L separable flask equipped with a thermometer, a jacket, and a squirrel-type stirring blade, and the temperature was raised to 80 ° C. After confirming that a homogeneous solution (b4-6) was obtained, the homogeneous solution (b4-6) was sufficiently washed three times with 600 g of demineralized water to remove the aqueous phase and remove the organic phase (b5-6). I got
The obtained organic phase (b5-6) 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 (c2-6).
Using an evaporator equipped with an oil bath, light-boiling components were distilled off at an oil bath temperature of 100 ° C. under reduced pressure to obtain 205 g of white bisphenol C (c3-6).

(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 150 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 25,700, and the pellet YI was 12.0.

[Example 3-2]
(1) Production of Bisphenol C The amount of acetone was changed from 66.8 g (1.15 mol) to 65.1 g (1.12 mol; the ratio of orthocresol to acetone was 2.13 mol ÷ 1.12 mol = Except having changed to 1.90), 228 g of bisphenol C cake (c1-7) was obtained after the first crystallization in the same manner as (1) of Example 3-1. Further, the second crystallization and the distillation of light boiling components were performed in the same manner as in (1) of Example 3-1 except that the cake (c1-6) was replaced with the cake (c1-7). Then, 201 g of white 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 120 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,700, and the pellet YI was 9.7.

[Example 3-3]
(1) Production of bisphenol C The amount of acetone was changed from 66.8 g (1.15 mol) to 60.8 g (1.05 mol; the ratio of ortho-cresol to acetone was 2.13 mol ÷ 1.05 mol = Except having changed to 2.03), 218 g of bisphenol C cake (c1-8) was obtained after the first crystallization in the same manner as (1) of Example 3-1. Further, the second crystallization and light-boiling distillation were carried out in the same manner as (1) of Example 3-1 except that the cake (c1-6) was replaced with the cake (c1-8). Then, 195 g of white bisphenol C (c3-8) was obtained.

(2) Production of polycarbonate A polycarbonate resin was produced in the same manner as (2) of Example 1-1, except that bisphenol C (c3-8) obtained in place of bisphenol C (c3-1) was used. . The time of the polymerization step was 180 minutes.
The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,900, and the pellet YI was 7.6.

[Example 3-4]
(1) Production of Bisphenol C The amount of acetone was changed from 66.8 g (1.15 mol) to 58.0 g (0.999 mol; the ratio of orthocresol to acetone was 2.13 mol ÷ 1.00 mol = Except having changed to 2.13), it carried out similarly to (1) of Example 3-1 to obtain 203 g of a bisphenol cake (c1-9) after the first crystallization. Further, the second crystallization and the distillation of light boiling components were carried out in the same manner as in (1) of Example 3-1 except that the cake (c1-6) was replaced with the cake (c1-9). Then, 180 g of white bisphenol C (c3-9) was obtained.

(2) Production of polycarbonate A polycarbonate resin was produced in the same manner as in (2) of Example 1-1, except that bisphenol C (c3-9) obtained in place of bisphenol C (c3-1) was used. . 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 3-1]
(1) Production of bisphenol C The amount of acetone was changed from 66.8 (1.15 mol) g to 70.5 g (1.21 mol; the ratio of orthocresol to acetone was 2.13 mol ÷ 1.21 mol). = 1.76), and 235 g of bisphenol cake (c1-10) was obtained after the first crystallization in the same manner as (1) in Example 3-1. Further, the second crystallization and light-boiling distillation were carried out in the same manner as (1) of Example 3-1 except that the cake (c1-6) was replaced with the cake (c1-10). Then, 215 g of white bisphenol C (c3-10) was obtained.

(2) Production of polycarbonate A polycarbonate resin was produced in the same manner as (2) of Example 1-1, except that bisphenol C (c3-10) obtained in place of bisphenol C (c3-1) was used. . 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 3-2]
(1) Production of Bisphenol C The amount of acetone was changed from 66.8 g (1.15 mol) to 30.9 g (0.532 mol; the ratio of ortho-cresol to acetone was 2.13 mol ÷ 0.532 mol = After the first crystallization, 14 g of a bisphenol cake (c1-11) was obtained in the same manner as (1) of Example 3-1 except that the composition was changed to 4.00). Since the yield of the cake (c1-11) was low, further experiments were abandoned.

For Examples 3-1 to 3-4, Comparative Example 3-1 and Comparative Example 3-2, the ratio of the amount of ortho-cresol to acetone in the production of bisphenol C, the cake of bisphenol C obtained in the first crystallization Table 2 summarizes the amount, the polymerization time in the production of the polycarbonate resin, the viscosity average molecular weight (Mv) of the obtained polycarbonate resin, and the pellet YI of the obtained polycarbonate resin.
From Table 2, it can be seen that, in the production of bisphenol C, when the ratio of the amount of ortho-cresol to acetone is 1.85 or more, the polymerization time is short in the production of the polycarbonate resin using the obtained bisphenol C, and the obtained polycarbonate is obtained. It can be seen that the resin pellet YI can also be kept low.
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.

  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 (6)

A method for producing bisphenol by condensing an aromatic alcohol with a ketone or aldehyde in the presence of an acid catalyst and an organic solvent to obtain bisphenol,
A method for producing bisphenol, wherein a molar ratio of the aromatic alcohol to the ketone or aldehyde is 1.85 to 2.20, and the ketone or aldehyde is reacted with the aromatic alcohol.   The method for producing bisphenol according to claim 1, wherein the ketone or aldehyde is acetone.   3. The method according to claim 1, wherein the aromatic alcohol is cresol.   The method for producing bisphenol according to any one of claims 1 to 3, wherein the organic solvent contains an aromatic hydrocarbon.   The method for producing bisphenol according to any one of claims 1 to 4, wherein the acid catalyst is sulfuric acid.   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 5.