Bisphenol composition containing aromatic alcohol sulfonate and method for producing same, polycarbonate resin and method for producing same, and method for producing bisphenol

Abstract

Provided are a bisphenol composition containing a specific amount of aromatic alcohol sulfonate and a simple method for producing the same. Also provided is a method for producing a polycarbonate resin, which uses the bisphenol composition containing the specific amount of aromatic alcohol sulfonate to efficiently proceed with a melt polymerization reaction and produce a polycarbonate resin with excellent color tone. A bisphenol composition containing 0.1 ppb or more by mass of aromatic alcohol sulfonate relative to bisphenol. Also provided is a method for producing the bisphenol composition by reacting a ketone or aldehyde with an aromatic alcohol in the presence of sulfuric acid. Also provided is a method for producing a polycarbonate resin using the bisphenol composition. Also provided is a polycarbonate resin containing a specific amount of aromatic alcohol sulfonate.

Description

[Technical Field]

[0001] The present invention relates to a bisphenol composition containing an aromatic alcohol sulfonate and a method for producing the same. It also relates to a method for producing a polycarbonate resin using the bisphenol composition. It also relates to a polycarbonate resin containing an aromatic alcohol sulfonate. It also relates to a method for producing bisphenol by reacting an aromatic alcohol with a ketone or an aldehyde to produce bisphenol. The bisphenol composition according to one embodiment of the present invention is useful as a raw material for resins such as polycarbonate resins, epoxy resins, and aromatic polyester resins, as well as an additive for curing agents, color developers, anti-fading agents, and other disinfectants, antibacterial and antifungal agents. [Background technology]

[0002] Bisphenols are useful as raw materials for polymeric materials such as polycarbonate resins, epoxy resins, aromatic polyester resins, etc. Known representative bisphenols include, for example, 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(4-hydroxy-3-methylphenyl)propane (Patent Document 1).

[0003] Known methods for producing bisphenol include a method using hydrogen chloride gas as a catalyst (Patent Document 2), a method using hydrochloric acid as a catalyst (Patent Document 1), a method using a mixture of hydrochloric acid and sulfuric acid as a catalyst (Patent Document 3), and a method using sulfuric acid as a catalyst (Patent Document 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-214248 [Patent Document 2] Japanese Patent Application Publication No. 62-138443 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-40376 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-51935 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when the present inventors produced 2,2-bis(4-hydroxy-3-methylphenyl)propane by the method described in Patent Document 1 and used the resulting 2,2-bis(4-hydroxy-3-methylphenyl)propane to produce a polycarbonate resin by melt polymerization, the melt polymerization did not proceed as expected. Furthermore, it was found that in order to produce the polycarbonate resin, it was necessary to increase the amount of catalyst used in the melt polymerization. Furthermore, the amount of catalyst added to promote the melt polymerization varied depending on the production lot of 2,2-bis(4-hydroxy-3-methylphenyl)propane, making it difficult to stably carry out the melt polymerization reaction and produce the desired polycarbonate resin.

[0006] The first object of the present invention, which has been made in view of the above circumstances, is to provide a bisphenol composition containing a specific amount of an aromatic alcohol sulfonate and a simple method for producing the same. It is also an object of the present invention to provide a method for producing a polycarbonate resin, which can efficiently proceed with a melt polymerization reaction by using the bisphenol composition containing the specific amount of the aromatic alcohol sulfonate to produce a polycarbonate resin. It is also an object of the present invention to provide a polycarbonate resin containing an aromatic alcohol sulfonate.

[0007] Furthermore, the production method using hydrogen chloride gas as a catalyst (Patent Document 2) is known as a versatile method for producing bisphenols, but the hydrogen chloride gas is highly corrosive and requires dedicated equipment for industrial implementation. The production method using hydrochloric acid as a catalyst (Patent Document 1) handles a smaller amount of hydrogen chloride than the production method using hydrogen chloride gas as a catalyst, but concentrated hydrochloric acid is corrosive and difficult to handle. Furthermore, there is a problem of the reaction time required. Furthermore, the production method using a mixture of hydrochloric acid and sulfuric acid as a catalyst (Patent Document 3) has the problem of corrosiveness due to the use of hydrochloric acid. The production method using sulfuric acid as a catalyst (Patent Document 4) is prone to side reactions such as sulfonation of phenol, and requires the use of relatively large amounts of various solvents to suppress this (Non-Patent Document 1). Furthermore, the need for sulfuric acid is known to cause side reactions such as condensation (polymerization) of the raw materials, ketones and aldehydes, resulting in colored components. Furthermore, as a result of investigations by the present inventors, it was found that the bisphenol reaction solution solidifies, resulting in a long reaction time.

[0008] The second object of the present invention has been made in view of the above circumstances, and is to provide a simple, efficient, and industrially advantageous method for producing bisphenol, which does not impair the hue even when used as a resin raw material or a color developer, produces few by-products, and is therefore advantageous. [Means for solving the problem]

[0009] As a result of intensive research into solving the first problem, the present inventors have found that polycarbonate resins can be produced efficiently by using a bisphenol composition containing a specific amount of an aromatic alcohol sulfonate, and have completed the present invention.

[0010] That is, the gist of the present invention for solving the first problem lies in the following [1] to [9]. [1] A bisphenol composition containing an aromatic alcohol sulfonate in an amount of 0.1 ppb by mass or more relative to the bisphenol. [2] The bisphenol composition according to [1], wherein a phenol production rate in a reaction liquid obtained by heating a mixture of the bisphenol and the diphenyl carbonate, in which the molar ratio of diphenyl carbonate to the bisphenol is 1.1, in an aluminum block heater heated to 194°C for 90 minutes, is 0.3 area % or more. [3] The bisphenol composition according to [1] or [2], wherein the aromatic alcohol sulfonate comprises a compound represented by general formula (1) and / or general formula (2). [ka] (In the formula, R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. ,gold indicates a group atom.) [ka] (In the formula, R 5 ~R 8 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. ,gold indicates a group atom.) [4] The bisphenol composition according to [3], wherein X in the general formula (1) and / or the general formula (2) is a sodium atom or a potassium atom. [5] The bisphenol composition according to any one of [1] to [4], wherein the content of the aromatic alcohol sulfonate relative to the bisphenol is 1.0 mass % or less. [6] The bisphenol composition according to any one of [1] to [5], wherein the content of bisphenol in the composition is 95.0% by mass or more. [7] A method for producing a bisphenol composition, comprising reacting a ketone or an aldehyde with an aromatic alcohol in the presence of sulfuric acid to produce the bisphenol composition according to any one of [1] to [6]. [8] A method for producing a polycarbonate resin, comprising reacting the bisphenol composition according to any one of [1] to [6] to produce a polycarbonate resin. [9] Polycarbonate resin containing 1 ppb or more of aromatic alcohol sulfonate in the resin.

[0011] As a result of intensive research to achieve the second object, the present inventors have discovered a method for producing bisphenol using a monoalkyl sulfate obtained by mixing sulfuric acid with an aliphatic alcohol as a catalyst, and have completed the invention of a simple, efficient, and industrially advantageous method for producing bisphenol.

[0012] That is, the gist of the present invention lies in the following

[10] to

[16] .

[10] A method for producing bisphenol, comprising a step of producing bisphenol by reacting an aromatic alcohol with a ketone or an aldehyde, wherein the reaction liquid used in the reaction is separated into an organic phase and an aqueous phase, and the aqueous phase contains a monoalkyl sulfate.

[11] The method for producing bisphenol according to

[10] , wherein the monoalkyl sulfate is produced by reacting sulfuric acid with a fatty acid alcohol.

[12] The method for producing bisphenol according to

[11] , wherein the sulfuric acid and the fatty acid alcohol are mixed to produce the monoalkyl sulfate, and then the monoalkyl sulfate is mixed with a reaction liquid containing an aromatic alcohol.

[13] The method for producing bisphenol according to any one of

[10] to

[12] , wherein the concentration of the monoalkyl sulfate in the aqueous phase is 0.0001% by mass or more and 50% by mass or less.

[14] The method for producing bisphenol according to any one of

[10] to

[13] , wherein the step of producing bisphenol is carried out in the presence of a thiol.

[15] The method for producing bisphenol according to

[14] , wherein the thiol and the ketone or the aldehyde are mixed together, and then the monoalkyl sulfate is added.

[16] A method for producing a polycarbonate resin, comprising producing bisphenol by the method for producing bisphenol according to any one of

[10] to

[15] , and reacting the resulting bisphenol to produce a polycarbonate resin. [Effects of the Invention]

[0013] According to one aspect of the present invention, there are provided a bisphenol composition containing a specific amount of an aromatic alcohol sulfonate and a simple method for producing the same. That is, according to the present invention, it is possible to provide a bisphenol composition containing a specific amount of an aromatic alcohol sulfonate, which can efficiently proceed with a melt polymerization reaction in the production of a polycarbonate resin from bisphenol and can produce a polycarbonate resin with excellent color tone. Furthermore, by using a bisphenol crystallization composition containing a specific amount of aromatic alcohol sulfonate, the time required for bubbles to disappear from the oil-water interface during washing can be shortened, and a bisphenol composition containing an appropriate amount of aromatic alcohol sulfonate can be easily and productively prepared, thereby providing a method for producing the bisphenol composition. Furthermore, it is possible to provide a method for producing a polycarbonate resin in which the melt polymerization reaction is efficient and the polycarbonate resin produced has an excellent color tone, and a polycarbonate having an excellent color tone.

[0014] According to another aspect of the present invention, by using a monoalkyl sulfate as a catalyst, the acid strength of the catalyst can be controlled, and the condensation (polymerization) and coloration of the raw material ketones and aldehydes can be suppressed, thereby enabling simple, efficient, and high-yield production of bisphenol with reduced by-products and reduced coloration of the product. Furthermore, the bisphenol can be used to produce polymeric materials such as polycarbonates with reduced coloration.

[0015] As described above, the present invention provides a simple, efficient, and industrially advantageous method for producing various bisphenols. Furthermore, by using the bisphenols produced by the production method of the present invention as raw materials for polymeric materials such as polycarbonate resins, epoxy resins, and aromatic polyester resins, these resins can be produced efficiently, and polymeric materials such as polycarbonate resins with excellent physical properties can be produced while suppressing deterioration in hue due to coloration. DETAILED DESCRIPTION OF THE INVENTION

[0016] The following describes in detail an embodiment of the present invention. However, the description of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not go beyond the gist of the present invention. In this specification, when the expression "to" is used, it is intended to be used as an expression that includes the numerical values ​​or physical property values ​​before and after it.

[0017] [Bisphenol composition] A bisphenol composition according to one embodiment of the present invention contains an aromatic alcohol sulfonate in an amount of 0.1 ppb by mass or more relative to bisphenol. Such a bisphenol composition is suitable as a raw material for polymers such as polycarbonate resins, and has the effect of efficiently promoting a polymerization reaction to produce a polymer.

[0018] The bisphenol composition contains bisphenol and an aromatic alcohol sulfonate at a concentration of 0.1 mass ppb or more relative to the bisphenol, and therefore may be simply referred to as a "bisphenol composition," but may also be referred to as a "bisphenol composition containing an aromatic alcohol sulfonate."

[0019] Each component of the bisphenol composition will now be described.

[0020] <Aromatic alcohol sulfonate> The "aromatic alcohol sulfonate" is a salt of aromatic alcohol sulfonic acid, and examples thereof include sodium salts, potassium salts, and lithium salts of aromatic alcohol sulfonic acid. An "aromatic alcohol sulfonic acid" is a compound in which one hydrogen atom of an aromatic hydrocarbon is replaced with a hydroxyl group (OH group) and another hydrogen atom of the aromatic ring is replaced with a sulfonic acid group (SOOH group). Furthermore, the aromatic alcohol sulfonic acid may be a structure having a substituent (that is, a structure having a substituent other than an OH group and an SO2OH group) or an unsubstituted structure.

[0021] The aromatic hydrocarbon that is the main skeleton of the aromatic alcohol sulfonate may be a monocyclic ring (a benzene ring) or a polycyclic ring (a naphthalene ring, an anthracene ring, or the like). The aromatic alcohol sulfonate is preferably hydroxybenzenesulfonic acid, which may have a substituent. Among these, 4-hydroxybenzenesulfonate and / or 2-hydroxybenzenesulfonate, which may have a substituent, are more preferred. Specifically, the aromatic alcohol sulfonate is more preferably a compound represented by the following general formula (1) and / or general formula (2): The following general formulas (1) and (2) will be explained below.

[0022] Examples of 4-hydroxybenzenesulfonate include 4-hydroxybenzenesulfonate represented by the following general formula (1), which may contain a substituent.

[0023] [ka]

[0024] In general formula (1), R 1 ~R 4are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, etc. The alkyl group, alkoxy group, aryl group, etc. may be substituted or unsubstituted. Examples thereof include a hydrogen atom, a halogen atom such as a fluoro group, a chloro group, a bromo group, or an iodo group, a linear or branched alkyl group having 1 to 12 carbon atoms such as 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, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, or an n-dodecyl group, and a cyclic alkyl group having 3 to 12 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclododecyl group. linear or branched alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, n-pentyloxy, i-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, and n-dodecyloxy; alkyl groups having an aryl group as a substituent such as benzyl; and aryl groups which may have an alkyl group as a substituent such as phenyl, tolyl, and xylyl.

[0025] Of these, R 1 ~R 4 If the carbon number of R is large, when the hydroxybenzenesulfonate is produced as a by-product in the reaction system during the production of bisphenol (described below), the lipophilicity of the hydroxybenzenesulfonate increases, the effect of the surfactant decreases, the amount of benzenesulfonate remaining relative to the bisphenol increases, and the color tone of the polycarbonate tends to deteriorate. 1 ~R 4 When the number of carbon atoms is small, it becomes possible to control the amount of benzenesulfonate remaining in bisphenol to a low level, and the polymerization stability of polycarbonate improves, so it is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

[0026] In general formula (1), R1 ~R 4 Specific examples of the aryl group that is a 4-hydroxyphenyl group having the formula: 1 ~R 4 is a hydrogen atom), 4-hydroxytolyl group (e.g., R 1 is a methyl group and R 2 ~R 4 is a hydrogen atom), 4-hydroxyxylyl group (e.g., R 1 ,R 4 is a methyl group and R 2 ,R 3 is a hydrogen atom), but is not limited to these.

[0027] In the general formula (1), X is ,gold Examples of metal atoms include elements of Group 1 of the periodic table, such as lithium, sodium, potassium, and cesium. Of these, sodium and potassium atoms are preferred because they are industrially inexpensive, and sodium atoms are more preferred, but the metal atoms are not limited thereto.

[0028] Furthermore, examples of 2-hydroxybenzenesulfonates include 2-hydroxybenzenesulfonates represented by the following general formula (2), which may have a substituent.

[0029] [ka]

[0030] In general formula (2), R 5 ~R 8are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, etc. The alkyl group, alkoxy group, aryl group, etc. may be substituted or unsubstituted. Examples thereof include a hydrogen atom, a halogen atom such as a fluoro group, a chloro group, a bromo group, or an iodo group, a linear or branched alkyl group having 1 to 12 carbon atoms such as 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, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, or an n-dodecyl group, and a cyclic alkyl group having 3 to 12 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclododecyl group. linear or branched alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, n-pentyloxy, i-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, and n-dodecyloxy; alkyl groups having an aryl group as a substituent such as benzyl; and aryl groups which may have an alkyl group as a substituent such as phenyl, tolyl, and xylyl.

[0031] Of these, R 5 ~R 8 If the carbon number of R is large, when the hydroxybenzenesulfonate is produced as a by-product in the reaction system during the production of bisphenol (described below), the lipophilicity of the hydroxybenzenesulfonate increases, the effect of the surfactant decreases, the amount of benzenesulfonate remaining relative to the bisphenol increases, and the color tone of the polycarbonate tends to deteriorate. 1 ~R 4 When the number of carbon atoms is small, it becomes possible to control the amount of benzenesulfonate remaining in bisphenol to a low level, and the polymerization stability of polycarbonate improves, so it is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

[0032] In general formula (2), R5 ~R 8 Specific examples of the aryl group that is a 2-hydroxyphenyl group having the formula: 5 ~R 8 is a hydrogen atom), 2-hydroxytolyl group (e.g., R 7 is a methyl group, and R 5 , R 6 , R 8 is a hydrogen atom), but is not limited to these.

[0033] In the general formula (2), X is ,gold Examples of metal atoms include elements of Group 1 of the periodic table, such as lithium, sodium, potassium, and cesium. Of these, sodium and potassium atoms are preferred because they are industrially inexpensive, and sodium atoms are more preferred, but the metal atoms are not limited thereto.

[0034] Specific examples of the hydroxybenzenesulfonate salts represented by the above general formula (1) or general formula (2) include sodium 4-hydroxybenzenesulfonate, sodium 2-hydroxybenzenesulfonate, sodium 4-hydroxy-3-methylbenzenesulfonate, sodium 2-hydroxy-3-methylbenzenesulfonate, and sodium 4-hydroxy-3,5-dimethylbenzenesulfonate, but are not limited to these.

[0035] Of the above, sodium 4-hydroxy-3-methylbenzenesulfonate and sodium 2-hydroxy-3-methylbenzenesulfonate are particularly preferred in that they can be produced as by-products in the reaction system during the production of bisphenol, which will be described later, and thereby can be contained in the bisphenol product.

[0036] The bisphenol composition may contain only one type of aromatic alcohol sulfonate, or may contain two or more types.

[0037] For example, the bisphenol composition contains a predetermined amount of aromatic alcohol sulfonate, but may also be a bisphenol composition containing 4-hydroxybenzenesulfonate and 2-hydroxybenzenesulfonate in a total amount of 1 ppb by mass or more and 100 ppm by mass or less relative to the bisphenol.

[0038] Generally, sodium element is detected in the order of several tens of ppb in compositions that have not undergone any special treatment. Whether or not the sodium element forms a salt with sulfonic acid can be clearly determined by whether or not it reacts with diphenyl carbonate. In other words, if a sulfonate salt is present, the reaction with diphenyl carbonate will proceed. phenol is produced, whereas in the absence of sulfonate, phenol does not generate. In the present invention, if a mixture of bisphenol and diphenyl carbonate, in which the molar ratio of diphenyl carbonate to bisphenol is 1.1, is heated in an aluminum block heater heated to 194°C for 90 minutes, and the phenol production rate in the resulting reaction solution is 0.3 area % or more, it can be determined that the sulfonate required in the present invention has been produced.

[0039] <Bisphenol> The bisphenol contained in the bisphenol composition is usually a compound represented by the following general formula (3).

[0040] [ka]

[0041] In the above general formula (3), R 11 ,R 12 ,R 13 ,R 14 may be the same or different. In addition, when there are two R 11 ,R 12 ,R 13 ,R 14Although the two R 11 ,R 12 ,R 13 ,R 14 Preferably, R 11 ~R 14 As the R in the general formula (1), 1 ~R 4 and R in general formula (2) 5 ~R 8 Examples include the same as those exemplified above (R 1 and R 7 R 11 To, R 2 and R 8 R 12 To, R 3 and R 6 R 13 To, R 4 R 14 ), and the same goes for the preferred ones.

[0042] R 15 ,R 16are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, etc. The alkyl group, alkoxy group, aryl group, etc. may be substituted or unsubstituted. For example, a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms such as 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, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, or an n-dodecyl group, a cyclic alkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclododecyl group, a methoxy group, an ethoxy group, Examples of the alkoxy group include linear or branched alkoxy groups having 1 to 20 carbon atoms, such as n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, n-pentyloxy, i-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, and n-dodecyloxy; alkyl groups having an aryl group as a substituent, such as benzyl; and aryl groups which may have an alkyl group as a substituent, such as phenyl, tolyl, and 2,6-dimethylphenyl.

[0043] In general formula (3), R 15 and R 16 may be bonded or bridged to each other between two groups, and such R 15 ,R 16 Examples of linking groups include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclododecylidene, fluorenylidene, xanthonylidene, and thioxanthonylidene.

[0044] Examples of bisphenols contained in the bisphenol composition include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 3,3-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxy-3-methylphenyl)pentane, and 2,2-bis(4-hydroxyphenyl)pentane. Examples of the hydroxyphenyl ether include, but are not limited to, 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, and 4,4-bis(4-hydroxy-3-methylphenyl)heptane. Among these, one of the preferred bisphenols is 2,2-bis(4-hydroxy-3-methylphenyl)propane.

[0045] In order for the aromatic alcohol sulfonate contained in the bisphenol composition to fully exert its effect as a polymerization catalyst in the production of polymers such as polycarbonate resins, the content of the aromatic alcohol sulfonate relative to the bisphenol is 0.1 mass ppb or more, preferably 1 mass ppb or more, more preferably 5 mass ppb or more, even more preferably 8 mass ppb or more, and particularly preferably 10 mass ppb or more. On the other hand, if the content of aromatic alcohol sulfonate relative to bisphenol is high, the color tone of the polycarbonate using the bisphenol composition will deteriorate, so the content is usually 1.0 mass% or less, preferably 100 mass ppm or less, more preferably 80 mass ppm or less, and even more preferably 50 mass ppm or less.

[0046] The bisphenol composition contains bisphenol as a main component and typically contains 95.0% by mass or more of bisphenol in the bisphenol composition. The content of bisphenol in the bisphenol composition is preferably 97.0% by mass or more, more preferably 98.0% by mass or more, even more preferably 98.5% by mass or more, and most preferably 99.0% by mass or more. In addition, the bisphenol composition preferably contains a small amount of components other than bisphenol and aromatic alcohol sulfonate. In particular, when used as a raw material for polycarbonate resin, a bisphenol composition with a low content of components that inhibit polymerization with a carbonate diester is preferred. In the method for producing a bisphenol composition (Method 4) described below, components that inhibit polymerization with a carbonate diester can be efficiently removed, and a bisphenol composition with an extremely low content of components that inhibit polymerization with a carbonate diester can be obtained. Therefore, the bisphenol composition obtained by the method for producing a bisphenol composition (Method 4) can be suitably used as a raw material for polycarbonate resins.

[0047] [Method of producing bisphenol composition] The method for producing the bisphenol composition is not particularly limited, but examples thereof include the following methods. (Method 1) A method of obtaining a bisphenol composition by mixing solid bisphenol with an aromatic alcohol sulfonate having a content of 0.1 mass ppb or more relative to the bisphenol. (Method 2) A method of obtaining a bisphenol composition by mixing molten bisphenol with an aromatic alcohol sulfonate having a content of 0.1 mass ppb or more relative to the bisphenol. (Method 3) A method in which an aromatic alcohol sulfonate is produced as a by-product during the production of bisphenol, and the by-product is purified as necessary to obtain a bisphenol composition. (Method 4) A method in which a bisphenol crystallization composition containing more than 100 ppm by mass and 1% by mass or less of an aromatic alcohol sulfonate salt relative to bisphenol is dissolved in a solvent to form a solution, and the solution is washed with water to obtain an organic phase from which the bisphenol composition is crystallized.

[0048] In the methods (Method 1) and (Method 2) of mixing an aromatic alcohol sulfonate with solid or molten bisphenol, the quality of the bisphenol composition is affected by the quality of the solid or molten bisphenol used, which tends to result in variations in the quality of the resulting bisphenol composition. In addition, the aromatic alcohol sulfonate must be prepared separately. For this reason, (Method 3) a method in which aromatic alcohol sulfonate is by-produced in a reaction system for producing bisphenol, thereby allowing the bisphenol composition to contain hydroxybenzenesulfonate, and (Method 4) a method in which a bisphenol composition is obtained by crystallizing a bisphenol crystallization composition are preferred.

[0049] The above (Method 3) and (Method 4) will be explained in detail below.

[0050] <Production Method (Method 3)> As a method for obtaining a bisphenol composition by producing an aromatic alcohol sulfonate together with bisphenol in a reaction system during the production of bisphenol, there is a method for producing bisphenol by condensing a ketone or aldehyde with an aromatic alcohol in the presence of sulfuric acid as an acid catalyst. According to this method, an aromatic alcohol sulfonate derived from the aromatic alcohol can be produced in the reaction system.

[0051] If the amount of aromatic alcohol sulfonate by-produced in the bisphenol reaction system is too large, it can be purified to adjust the amount of aromatic alcohol sulfonate contained in the bisphenol composition to fall within the specified range. For example, the obtained bisphenol product can be further washed with water, crystallized, suspended, and washed by sprinkling to remove a portion of the aromatic alcohol sulfonate contained in the bisphenol product, thereby controlling the amount of aromatic alcohol sulfonate contained in the bisphenol composition to fall within the specified range. Details will be described later.

[0052] As a method for producing bisphenol utilizing a reaction between a ketone or an aldehyde and an aromatic alcohol, a method for producing bisphenol according to one embodiment of the present invention can be adopted. This method is a method for producing bisphenol that includes a step of producing bisphenol from a reaction between an aromatic alcohol and a ketone or an aldehyde, in which a reaction liquid used in the reaction is separated into an organic phase and an aqueous phase, and the aqueous phase contains a monoalkyl sulfate. The bisphenol obtained by the production method according to this embodiment has extremely high purity and little coloration, and therefore can be used in the production of high-purity polycarbonate. For example, a high-purity polycarbonate can be obtained by polycondensing the bisphenol obtained by the production method of the present invention with diphenyl carbonate in the presence of a transesterification catalyst.

[0053] In the production of bisphenol, it is preferred to produce bisphenol by condensing an aromatic alcohol with a ketone or an aldehyde using sulfuric acid as a catalyst and further using an aliphatic alcohol.

[0054] The reaction for producing bisphenols proceeds, for example, according to the following reaction formula (4): By using, for example, sulfuric acid as a catalyst in this reaction, hydroxybenzenesulfonates represented by the following general formulas (1A) and / or (2A), which correspond to the aromatic alcohols used as raw materials, can be produced as by-products.

[0055] [ka] (In the formula, R 11 ~R 16 has the same meaning as in general formula (3). 12 and R 13 is preferably a proton, since if it is sterically bulky, the condensation reaction does not proceed easily.

[0056] [ka] (In the formula, R 11 ~R 14 has the same meaning as in general formula (3).

[0057] [ka] (In the formula, R 12 ~R 14 has the same meaning as in general formula (3).

[0058] (aromatic alcohol) The aromatic alcohol used as a raw material for bisphenol is usually a compound represented by the following general formula (5).

[0059] [ka] (In the formula, R 11 ~R 14 has the same meaning as in general formula (3). 12 and R 13 is preferably a proton, since if it is sterically bulky, the condensation reaction does not proceed easily.

[0060] Specific examples of the compound represented by the general formula (5) include phenol, methylphenol, dimethylphenol, ethylphenol, propylphenol, butylphenol, methoxyphenol, ethoxyphenol, propoxyphenol, butoxyphenol, aminophenol, benzylphenyl, and phenylphenol.

[0061] (ketone or aldehyde) The ketone or aldehyde is usually a compound represented by the following general formula (6):

[0062] [ka] (In the formula, R 15 ,R 16 has the same meaning as in general formula (3).

[0063] Specific examples of the compound represented by the general formula (6) include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanaldehyde, hexanealdehyde, heptanealdehyde, octanaldehyde, nonanealdehyde, decanealdehyde, undecanealdehyde, and dodecanealdehyde; ketones such as acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, and dodecanone; and benzaldehyde. aryl alkyl ketones such as phenyl methyl ketone, phenyl ethyl ketone, phenyl propyl ketone, cresyl methyl ketone, cresyl ethyl ketone, cresyl propyl ketone, xylyl methyl ketone, xylyl ethyl ketone, and xylyl propyl ketone; and cyclic alkane ketones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, and cyclododecanone.

[0064] In a condensation reaction of an aromatic alcohol with a ketone or an aldehyde, if the molar ratio of aromatic alcohol to ketone or aldehyde ((moles of aromatic alcohol / moles of ketone) or (moles of aromatic alcohol / moles of aldehyde)) is low, the ketone or aldehyde is likely to polymerize, and if it is high, the aromatic alcohol is lost unreacted. For these reasons, the molar ratio of aromatic alcohol to ketone or aldehyde is preferably 1.5 or more, more preferably 1.6 or more, and even more preferably 1.7 or more, and is also preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

[0065] In the condensation reaction of an aromatic alcohol with a ketone or an aldehyde, the ketone or aldehyde is usually supplied to a mixed solution of an aromatic alcohol and an acid catalyst. The ketone or aldehyde can be supplied all at once or in portions. However, since the reaction to produce bisphenol is an exothermic reaction, the ketone or aldehyde is preferably supplied in portions, such as by dropping it little by little.

[0066] (sulfuric acid) Sulfuric acid that can be used as a catalyst can be supplied to the reaction system by using an aqueous solution of sulfuric acid (raw material sulfuric acid) diluted with water, called concentrated sulfuric acid or dilute sulfuric acid. Concentrated or dilute sulfuric acid may be used as the raw material sulfuric acid. However, if the concentration of the raw material sulfuric acid is too high, it may promote the polymerization of ketones or aldehydes or cause sulfonation of the produced bisphenol. Furthermore, when an aliphatic alcohol or thiol is used in combination, it may promote the dehydration dimerization of the aliphatic alcohol or cause deterioration of the thiol. On the other hand, if the concentration of the raw material sulfuric acid used is too low, the reaction time becomes long and bisphenol cannot be produced efficiently. Therefore, the mass concentration of the raw material sulfuric acid used is preferably 50% by mass or more, more preferably 60% by mass or more. Furthermore, when the sulfuric acid concentration is high (i.e., the water concentration in the sulfuric acid is low) and the amount of solvent (described in detail below) premixed with acetone is small relative to the amount of water contained in the sulfuric acid, acetone may polymerize to mesityl oxide (dimerization product) or the like, promoting the dehydration dimerization of aliphatic alcohols and possibly causing oxidative decomposition of thiols. Therefore, the mass concentration of the raw material sulfuric acid used is preferably 95% by mass or less, more preferably 90% by mass or less. On the other hand, when the sulfuric acid concentration is high (i.e., the water concentration in the sulfuric acid is low) and the amount of solvent (described in detail below) premixed with acetone is large relative to the amount of water contained in the sulfuric acid, acetone suppresses the polymerization of mesityl oxide (dimerization product) or the like, suppresses the dehydration dimerization of aliphatic alcohols, and suppresses the oxidative decomposition of thiols. Therefore, the concentration of sulfuric acid used is preferably 90% by weight or more, more preferably 95% by weight or more.

[0067] If the molar ratio of sulfuric acid to ketone or aldehyde ((moles of sulfuric acid / moles of ketone) or (moles of sulfuric acid / moles of aldehyde)) is low, the sulfuric acid will be diluted with water by-produced during the condensation reaction, requiring a long reaction time. On the other hand, if the ratio is high, the ketone or aldehyde may be polymerized. For these reasons, the molar ratio of sulfuric acid to ketone or aldehyde is preferably 0.0001 or more, more preferably 0.01 or more, even more preferably 0.05 or more, particularly preferably 0.1 or more, and is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less, and particularly preferably 3 or less.

[0068] (Reaction solution) The reaction mixture used in the reaction of an aromatic alcohol with a ketone or an aldehyde is separated into an organic phase and an aqueous phase, and the aqueous phase contains a monoalkyl sulfate. The aromatic alcohol is contained in the organic phase, and the ketone or the aldehyde is separated into the organic phase. The inclusion of a monoalkyl sulfate controls the acid strength of the catalyst and suppresses condensation (polymerization) and coloration of the raw material ketone or aldehyde. This suppresses excessive production of aromatic alcohol sulfonic acid, and enables simple and efficient production of bisphenol with reduced product coloration. At the same time, the remaining aliphatic alcohol used to generate the monoalkyl sulfate dissolves the produced bisphenol, suppressing solidification of the reaction solution, improving the mixing state, and shortening the reaction time.

[0069] (monoalkyl sulfate) Examples of monoalkyl sulfates include monomethyl sulfate, monoethyl sulfate, monopropyl sulfate, monoisopropyl sulfate, monobutyl sulfate, monoisobutyl sulfate, mono-t-butyl sulfate, monopentyl sulfate, monoisopentyl sulfate, monohexyl sulfate, monoheptyl sulfate, monooctyl sulfate, monononyl sulfate, monodecyl sulfate, monoundecyl sulfate, monododecyl sulfate, mono(hydroxyethyl) sulfate, mono(2-hydroxyethoxyethyl) sulfate, mono(2-(2'-hydroxyethoxy)ethoxyethyl) sulfate, etc. Among these, monoalkyl sulfates having 8 or less carbon atoms are preferably used because the lipophilicity increases as the number of carbon atoms increases, making it difficult for the monoalkyl sulfate to move between the organic phase and the aqueous phase. The method for producing monoalkyl sulfate is not particularly limited, but a method of producing it by reacting sulfuric acid with an aliphatic alcohol can be mentioned, as it allows monoalkyl sulfate to be obtained simply and inexpensively.

[0070] The concentration of monoalkyl sulfate can be determined, for example, by taking a part of the aqueous phase obtained after mixing an aliphatic alcohol with sulfuric acid, 1 The concentration can be determined by HNMR analysis. Examples of the aqueous phase obtained after mixing an aliphatic alcohol and sulfuric acid include (1) an aqueous phase obtained by mixing an aliphatic alcohol and sulfuric acid, (2) an aqueous phase obtained by mixing an aliphatic alcohol, an aromatic alcohol, a solvent, a thiol, and sulfuric acid and allowing the mixture to stand, (3) an aqueous phase obtained by mixing an aliphatic alcohol and an aromatic alcohol, then supplying sulfuric acid, mixing, and allowing the mixture to stand, (4) an aqueous phase obtained by mixing an aliphatic alcohol, a solvent, and an aromatic alcohol, then supplying sulfuric acid, mixing, and allowing the mixture to stand, and (5) an aqueous phase obtained by allowing a bisphenol reaction solution to stand. The concentration of monoalkyl sulfate in the reaction solution is preferably 0.0001 wt% or more and 50 wt% or less. Examples of methods for preparing monoalkyl sulfate include a method of mixing sulfuric acid shown below with an aliphatic alcohol shown below, and a method of mixing a monoalkyl metal sulfate such as sodium monoalkyl sulfate with sulfuric acid. In the present invention, the monoalkyl sulfate present in the bisphenol production step may be a pre-prepared monoalkyl sulfate mixed with at least a portion of the reaction raw materials, or may be produced by causing sulfuric acid and an aliphatic alcohol to coexist in the reaction system for producing bisphenol, and the monoalkyl sulfate may be present in the reaction system.

[0071] Since mixing of an aliphatic alcohol with sulfuric acid generates heat, it is preferable to carry out the mixing at a temperature below the boiling point of the aliphatic alcohol. The reaction for producing bisphenol from an aromatic alcohol and a ketone or aldehyde is preferably carried out in a solvent. Therefore, the monoalkyl sulfate may be supplied after the aromatic alcohol, solvent, ketone or aldehyde, and optionally thiol are supplied to a reactor, or the monoalkyl sulfate may be supplied to a reactor before the ketone or aldehyde is supplied and mixed with the aromatic alcohol, and then the ketone or aldehyde is mixed therewith. However, since there is a risk of the ketone or aldehyde being polymerized, the method of supplying the monoalkyl sulfate to a reactor before the ketone or aldehyde is supplied to a reactor and then mixing the ketone or aldehyde therewith is preferred.

[0072] (fatty alcohol) Examples of aliphatic alcohols include alkyl alcohols having 1 to 12 carbon atoms, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol, i-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, ethylene glycol, diethylene glycol, and triethylene glycol. As the number of carbon atoms in the aliphatic alcohol increases, lipophilicity increases, making it difficult to mix with sulfuric acid and to obtain a monoalkyl sulfate. Therefore, alkyl alcohols having 8 or less carbon atoms are preferred, and methanol is particularly preferred.

[0073] If the molar ratio of aliphatic alcohol to sulfuric acid (moles of aliphatic alcohol / moles of sulfuric acid) is low, the amount of monoalkyl sulfate generated will be small and the reaction will take a long time, while if it is high, the sulfuric acid concentration will decrease. For these reasons, the molar ratio of aliphatic alcohol to sulfuric acid is preferably 0.0001 or more, more preferably 0.01 or more, even more preferably 0.05 or more, particularly preferably 0.1 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.

[0074] (thiol) In addition, in the reaction of condensing an aromatic alcohol with a ketone or an aldehyde, a thiol can be used as a co-catalyst. Examples of the thiol used as a co-catalyst include mercaptocarboxylic acids such as mercaptoacetic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and 4-mercaptobutyric acid, methyl mercaptan, ethyl mercaptan, propyl mercaptan, 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 pentadecyl mercaptan.

[0075] If the molar ratio of the thiol to the ketone or aldehyde ((moles of the thiol / moles of the ketone) or (moles of the thiol / moles of the aldehyde)) is low, the effect of improving the selectivity of bisphenol by using a thiol co-catalyst will not be obtained, and if it is high, the thiol may be mixed into the bisphenol, resulting in a deterioration in quality. For these reasons, the molar ratio of the thiol to the ketone and aldehyde is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less.

[0076] From the viewpoint of suppressing oxidative decomposition of the thiol, it is preferable to premix the thiol with a ketone or aldehyde before subjecting it to the reaction. The method of mixing the thiol with a ketone or aldehyde may be to mix the thiol with the ketone or aldehyde, or to mix the thiol with the ketone or aldehyde. Furthermore, the method of mixing the mixed solution of the thiol and the ketone or aldehyde with raw material sulfuric acid may be to mix the raw material sulfuric acid with the mixed solution, or to mix the mixed solution with the raw material sulfuric acid, but it is preferable to mix the mixed solution with the raw material sulfuric acid. Furthermore, it is more preferable to supply the raw material sulfuric acid and aromatic alcohol to a reaction vessel, and then supply the mixed solution to the reaction vessel and mix them.

[0077] (solvent) Aromatic hydrocarbons can be used as the solvent for the reaction to produce the bisphenol composition. Furthermore, the solvent used in the production of bisphenol can be recovered and purified by distillation or the like and reused. Examples of aromatic hydrocarbons that can be used include benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, and mesitylene. When reusing the solvent, a solvent with a low boiling point is preferred. Alternatively, a large amount of the aromatic alcohol may be used as a solvent instead of a solvent. In this case, the unreacted aromatic alcohol is lost, but this loss can be reduced by recovering and purifying it by distillation or the like and reusing it.

[0078] For example, if the amount of solvent used in the reaction to produce bisphenol is too small relative to the amount of sulfuric acid used to prepare monoalkyl sulfate, the produced bisphenol may decompose, potentially resulting in a decrease in the amount of bisphenol obtained. On the other hand, if the amount is too large relative to the amount of sulfuric acid, the rate of the condensation reaction between ketone or aldehyde and aromatic alcohol may decrease, potentially requiring more time to produce bisphenol. Therefore, the amount of solvent used is preferably 0.05 times or more, more preferably 0.1 times or more, and preferably 10 times or less, more preferably 5 times or less relative to the amount of sulfuric acid. In particular, when high-concentration sulfuric acid is used, the amount is preferably 1 time or more, more preferably 2 times or more, and preferably 10 times or less, more preferably 5 times or less relative to the amount of sulfuric acid. Alternatively, a large amount of aromatic alcohol may be used in place of the solvent, and since unreacted aromatic alcohol is a loss, it can be recovered and purified by distillation or the like and reused.

[0079] (Bisphenol production reaction) The reaction for producing bisphenol is a condensation reaction. If the reaction temperature for the reaction is too high, the oxidative decomposition of the co-catalyst by the catalyst tends to proceed, whereas if the reaction temperature is too low, the time required for the reaction increases. Therefore, the temperature is preferably 0°C or higher and 50°C or lower.

[0080] The reaction time for the production reaction is preferably within 30 hours, more preferably within 25 hours, and even more preferably within 20 hours, and is usually 15 hours or more, since too long a reaction time can lead to decomposition of the produced bisphenol. The reaction can be stopped by adding water in an amount equal to or greater than the amount of sulfuric acid used to reduce the sulfuric acid concentration.

[0081] (Bisphenol purification) The bisphenol obtained by the above-mentioned bisphenol production reaction can be purified by a conventional method. For example, purification can be performed by simple means such as crystallization or column chromatography. As an example, after the condensation reaction, the reaction solution is separated and the resulting organic phase is washed with water or saline, and further neutralized and washed with sodium bicarbonate water, if necessary. If necessary, the washed organic phase may be cooled and crystallized. When a large amount of aromatic alcohol is used, it is preferable to distill off excess aromatic alcohol by distillation before crystallization during purification and then perform crystallization.

[0082] <Production Method (Method 4)> (Method 4) is a method in which a bisphenol crystallization composition containing more than 100 ppm by mass and 1% by mass or less of an aromatic alcohol sulfonate salt relative to the bisphenol is dissolved in a solvent to form a solution, and the solution is washed with water to obtain an organic phase from which a bisphenol composition is crystallized. As described above, it is preferable that the bisphenol composition contains a small amount of components that inhibit the melt polymerization reaction. In order to produce such a bisphenol composition, the production method (Method 4) is suitable.

[0083] The present inventors have clarified that bisphenol is likely to contain components that inhibit melt polymerization reactions. They have also found that by using a bisphenol crystallization composition (hereinafter sometimes simply referred to as a "bisphenol crystallization composition") containing more than 100 ppm by mass and 1% by mass or less of an aromatic alcohol sulfonate salt relative to bisphenol, washing a solution containing the bisphenol crystallization composition with water, separating the oil from the water, and crystallizing the resulting organic phase, the components that inhibit melt polymerization reactions (melt polymerization reaction-inhibiting components) can be easily removed.

[0084] This is presumably because, by using a bisphenol crystallization composition containing more than 100 ppm by mass and not more than 1% by mass of an aromatic alcohol sulfonate salt relative to the bisphenol, the aromatic alcohol sulfonate contained in the bisphenol crystallization composition acts as a surfactant, facilitating separation into an aqueous phase and an organic phase during water washing, reducing the amount of melt polymerization reaction inhibitory components remaining in the organic phase in which the bisphenol composition is dissolved, and allowing the melt polymerization reaction inhibitory components to be easily and efficiently removed into the aqueous phase.

[0085] In this way, by using the production method (Method 4), a bisphenol composition, in particular a bisphenol composition with a low content of components inhibiting the melt polymerization reaction, can be obtained simply and efficiently. Furthermore, by using the bisphenol composition obtained in the production method (Method 4), a melt polymerization reaction can be stably carried out, and a polycarbonate resin can be stably produced by the melt polymerization reaction.

[0086] In the bisphenol crystallization composition, if the aromatic alcohol sulfonate is more than 1% by mass relative to the bisphenol, the aromatic alcohol sulfonate is likely to remain in excess in the bisphenol composition after crystallization, which may reduce the reactivity with the carbonate diester. The aromatic alcohol sulfonate relative to the bisphenol is usually 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less. Furthermore, if the amount of aromatic alcohol sulfonate relative to bisphenol is 100 ppm by mass or less, the surfactant effect is insufficient, the organic phase and the aqueous phase are difficult to separate during oil-water separation, and components contained in bisphenol that inhibit the reaction with the carbonate diester tend to remain in large amounts in the organic phase. Furthermore, it takes a long time to separate the organic phase and the aqueous phase, which is undesirable from an economic standpoint. The amount of aromatic alcohol sulfonate relative to bisphenol contained in the bisphenol crystallization composition is usually more than 100 ppm by mass, preferably 150 ppm by mass or more, more preferably 195 ppm by mass or more, and even more preferably 300 ppm by mass or more.

[0087] As an example of the production method (Method 4), a bisphenol composition can be produced from a crude bisphenol product by the following method. A bisphenol crystallization composition containing more than 100 ppm by mass and 1% by mass or less of an aromatic alcohol sulfonate salt relative to the bisphenol is mixed with an organic solvent (e.g., toluene, xylene, trimethylbenzene, etc.) and stirred at 60 to 95°C to obtain a solution (A) in which the bisphenol and the aromatic alcohol sulfonate salt are dissolved. 0.1 to 10 parts by mass of water (e.g., demineralized water, ion-exchanged water, etc.) is added per part by mass of the solution (A), and the mixture is stirred at 60 to 95°C for 0.1 to 1 hour. After stirring, the mixture is allowed to stand at 60 to 95°C to separate the oil and water. After the oil-water separation, the aqueous phase is removed to obtain an organic phase (A). Bisphenol is precipitated from the organic phase (A). The bisphenol composition is then obtained by solid-liquid separation and drying.

[0088] Examples of methods for precipitating bisphenol from the organic phase (A) include a method in which the temperature is lowered from 60 to 95° C. to 0 to 20° C. over 1 to 10 hours for crystallization. The crystallization time is about 1 to 10 hours.

[0089] The method for solid-liquid separation of the precipitated bisphenol composition is not particularly limited, and conventional methods such as filtration, centrifugation, and decantation can be used. The drying method may be drying under reduced pressure or drying under normal pressure. The drying temperature can be appropriately determined, but is preferably 50 to 120°C, since a high drying temperature may cause the bisphenol composition to fuse and make it impossible to remove it from the device.

[0090] A bisphenol crystallization composition containing more than 100 ppm by mass and 1% by mass or less of an aromatic alcohol sulfonate relative to the bisphenol is preferably obtained by reacting an aromatic alcohol with a ketone or aldehyde in the presence of a sulfuric acid catalyst, as in the above-described (Method 3). A bisphenol crystallization composition containing such a specific amount of aromatic alcohol sulfonate can be obtained, for example, by reacting at a molar ratio of sulfuric acid to aromatic alcohol (moles of sulfuric acid / moles of aromatic alcohol) of 0.1 to 10 (preferably 0.3 to 5, more preferably 0.5 to 3) at 0 to 80°C (preferably 5 to 70°C, more preferably 10 to 60°C) for 0.05 to 10 hours (preferably 0.1 to 5 hours).

[0091] In addition, a bisphenol crystallization composition containing an aromatic alcohol sulfonate in an amount of more than 100 ppm by mass and not more than 1% by mass relative to the bisphenol can be obtained by mixing a predetermined amount of an aromatic alcohol sulfonate with commercially available bisphenol or the like.

[0092] <Uses of bisphenol compositions> The bisphenol composition can be used as a constituent, curing agent, additive, or precursor thereof for various thermoplastic resins such as polyether resins, polyester resins, polyarylate resins, polycarbonate resins, polyurethane resins, and acrylic resins, and various thermosetting resins such as epoxy resins, unsaturated polyester resins, phenolic resins, polybenzoxazine resins, and cyanate resins, which are used in a variety of applications including optical materials, recording materials, insulating materials, transparent materials, electronic materials, adhesive materials, and heat-resistant materials. It is also useful as an additive for color developers and anti-fading agents for thermal recording materials, as well as for disinfectants, antibacterial and antifungal agents.

[0093] Among these, it is preferably used as a raw material (monomer) for thermoplastic resins and thermosetting resins because it can impart good mechanical properties, and more preferably as a raw material for polycarbonate resins and epoxy resins. It is also preferably used as a color developer, and more preferably in combination with a leuco dye or a discoloration temperature regulator.

[0094] [Polycarbonate resin and its manufacturing method] Next, a polycarbonate resin made from a bisphenol composition and a method for producing the same will be described. A polycarbonate resin according to one embodiment of the present invention is a polycarbonate resin containing 1 ppb by mass or more of an aromatic alcohol sulfonate in the resin. From the viewpoint of ensuring excellent color tone, the content of aromatic alcohol sulfonate in the resin is preferably 1 ppb by mass or more, more preferably 5 ppb by mass or more, even more preferably 8 ppb by mass or more, and particularly preferably 10 ppb by mass or more, and is 1.0% by mass or less, preferably 100 ppm by mass or less, more preferably 80 ppm by mass or less, and even more preferably 50 ppm by mass or less. Furthermore, an index for evaluating color tone is yellowness (also referred to as "YI value" or "yellowness index value"), which can be measured in accordance with ASTM D1925. In evaluating the color tone of a polycarbonate resin, the YI is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

[0095] Polycarbonate resins made from a bisphenol composition as a raw material can be produced by reacting the aforementioned bisphenol composition or bisphenol obtained by the aforementioned bisphenol production method, and can be produced by, for example, a method of subjecting the bisphenol composition to a transesterification reaction with a carbonate diester such as diphenyl carbonate in the presence of an alkali metal compound and / or an alkaline earth metal compound. The transesterification reaction can be carried out by appropriately selecting a known method, but an example using a bisphenol composition and diphenyl carbonate as raw materials will be described below.

[0096] In the method for producing a polycarbonate resin, it is preferable to use an excess amount of diphenyl carbonate relative to the bisphenol in the bisphenol composition. A larger amount of diphenyl carbonate relative to the bisphenol is preferable, since the produced polycarbonate resin has fewer terminal hydroxyl groups and the polymer has excellent thermal stability. A smaller amount is preferable, since the transesterification reaction rate is faster and it is easier to produce a polycarbonate resin with the desired molecular weight. For these reasons, the amount of diphenyl carbonate used relative to 1 mole of bisphenol is usually 1.001 moles or more, preferably 1.002 moles or more. It is also usually 1.3 moles or less, preferably 1.2 moles or less.

[0097] As a method for supplying the raw materials, the bisphenol composition and diphenyl carbonate can be supplied in solid form, but it is preferable to melt one or both of them and supply them in a liquid state.

[0098] When producing a polycarbonate resin by the transesterification reaction of diphenyl carbonate and bisphenol, a transesterification catalyst is usually used. In the above-mentioned method for producing a polycarbonate resin, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound as the transesterification catalyst. These may be used alone or in any combination and ratio of two or more. In practice, it is desirable to use an alkali metal compound.

[0099] The catalytic amount of the transesterification catalyst used per mole 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, and is usually 100 μmol or less, preferably 50 μmol or less, more preferably 20 μmol or less.

[0100] When the amount of transesterification catalyst used is within the above range, it is easy to obtain the polymerization activity required to produce a polycarbonate resin having a desired molecular weight, and it is easy to obtain a polycarbonate resin that has excellent polymer color, does not undergo excessive polymer branching, and has excellent fluidity during molding.

[0101] To produce a polycarbonate resin by the above method, it is preferable to continuously feed both of the raw materials into a raw material mixing tank, and then continuously feed the resulting mixture and the transesterification catalyst into a polymerization tank. In the production of polycarbonate resins by the transesterification method, the two raw materials are usually supplied to a raw material mixing tank, stirred uniformly, and then supplied to a polymerization tank to which a transesterification catalyst is added, thereby producing a polymer.

[0102] In particular, the bisphenol produced by the bisphenol production method according to one embodiment of the present invention described above has extremely high purity and is little colored, and therefore can be used in the production of high-purity polycarbonate. For example, a high-purity polycarbonate can be obtained by polycondensing the bisphenol obtained by the production method of the present invention with diphenyl carbonate in the presence of a transesterification catalyst. [Example]

[0103] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention.

[0104] [Experiment I] [Raw materials and reagents] The reagents used were 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as "bisphenol C"), toluene, sodium hydroxide, potassium hydroxide, raw material sulfuric acid, dodecanethiol, methanol, acetone, and cesium carbonate manufactured by Wako Pure Chemical Industries, Ltd. The concentration of cresol sulfonic acid contained in bisphenol C was below the detection limit (less than 1 ppb), as described below. Here, if no special treatment is performed on the object to be measured, the detection limit is usually 1 ppb, but the detection limit can be reduced to 0.1 ppb by performing treatment such as concentration. Sodium phenolsulfonate was a reagent manufactured by Tokyo Chemical Industry Co., Ltd. The cresol sulfonic acid (hereinafter sometimes referred to as "4-hydroxy-3-methylbenzenesulfonic acid" or "2-hydroxy-3-methylbenzenesulfonic acid") solution used was a reagent manufactured by Kishida Chemical Co., Ltd. Diphenyl carbonate used was a product manufactured by Mitsubishi Chemical Corporation.

[0105] [analysis] (Time it takes for bubbles to disappear at the oil-water interface) The time it took for blisters on the oil-water interface to disappear was determined by visually counting the blisters on the interface and determining the time it took for the number of blisters to reach 10 or less. The time it took for blisters to disappear on the oil-water interface was evaluated as follows: less than 10 minutes: "S", 10 to 30 minutes: "A", 30 to 1 hour: "B", and 1 hour or more: "C".

[0106] (Qualitative and quantitative analysis of sodium 4-hydroxy-3-methylbenzenesulfonate and sodium 2-hydroxy-3-methylbenzenesulfonate) Qualitative analysis of sodium 4-hydroxy-3-methylbenzenesulfonate and sodium 2-hydroxy-3-methylbenzenesulfonate is as follows: 1 This was determined by H-NMR and Na analysis using an ICP mass spectrometer. 1 H-NMR (proton nuclear magnetic resonance ( 1 H NMR measurements were carried out using a JNM-ECS400 model manufactured by JEOL Ltd. The sodium atom concentration was measured by the following procedure. Nitric acid was added to bisphenol, and the mixture was decomposed under pressure and sealed using a microwave decomposition device. The resulting decomposition solution was diluted with pure water, and the sodium atom concentration in the bisphenol was measured using ELEMENT2 manufactured by Thermo Fisher Scientific.

[0107] Quantitative analysis of sodium 4-hydroxy-3-methylbenzenesulfonate and sodium 2-hydroxy-3-methylbenzenesulfonate was carried out using a high performance liquid chromatograph mass spectrometer under the following conditions and procedures, and a calibration curve prepared using standard substances was used. High-performance liquid chromatograph: Agilent 1200, Capcellpak C18 MG3 3μm 75mm x 4.6mm ID Method: Low-pressure gradient method ·Analysis temperature: 40℃ ·Eluent composition: Solution A: 1mmol / L ammonium formate aqueous solution, acetic acid; Solution B: acetonitrile At analysis time 0 minutes, the volume ratio of solution A to solution B was 99.5:0.5 (the same applies below). During the analysis time from 0 to 15 minutes, the eluent composition was gradually changed to A:B = 5:95. For analysis times of 15 to 25 minutes, the ratio of A solution to B solution was maintained at 5:95. The analysis was carried out at a flow rate of 1 ml / min. ·Mass spectrometer: Agilent LC / MS 6130 Method: ESI (using AJS probe)

[0108] (Phenol production rate) The yield of phenol produced by the reaction of bisphenol C with diphenyl carbonate was determined by high performance liquid chromatography (hereinafter referred to as LC) under the following procedures and conditions. Equipment: Shimadzu CTO-10 column thermostat Shimadzu Corporation detector SPD-M10AVP Shimadzu Corporation pump LC-10AD GL Science Inertsil ODS-II 5μm 150mm x 4.6mm ID Method: Isocratic method ·Analysis temperature: 40℃ Eluent composition: Water:Acetonitrile = 10:90 (volume ratio) At analysis time 0 minutes, the pump flow rate is 0.5 ml / min. During the analysis time from 0 to 15 minutes, the pump flow rate was gradually increased to 2 ml / min. The analysis was performed for 15 to 30 minutes with the pump flow rate maintained at 2 ml / min. The detection wavelength was 210 nm. The greater the amount of components present in bisphenol C that inhibit the reaction with diphenyl carbonate, the lower the rate of phenol production, and vice versa. The phenol production rate (initial polymerization activity) was calculated using the following formula. Phenol production rate (initial polymerization activity) = LC area of ​​phenol ÷ (LC area of ​​phenol + LC area of ​​diphenyl carbonate + LC area of ​​bisphenol C) × 100 (%) The LC area refers to the area of ​​a peak detected by high-performance chromatography.

[0109] (Composition of bisphenol C production reaction solution) The composition of the bisphenol C production reaction solution was analyzed by high performance liquid chromatography according to the following procedure and conditions. Equipment: Shimadzu LC-2010A, Imtakt ScherzoSM-C18 3μm 150mm x 4.6mm ID Low-pressure gradient method ·Analysis temperature: 40℃ ·Eluent composition: Solution A: Ammonium acetate: acetic acid: dechlorinated water = 3.000 g: 1 ml: 1 liter solution Solution B: Ammonium acetate: acetic acid: acetonitrile = 1.500 g: 1 ml: 900 ml solution At 0 minutes of analysis time, the ratio of solution A to solution B was 60:40 (volume ratio, same below). During the analysis time from 0 to 25 minutes, the eluent composition was gradually changed to A:B = 90:10. For analysis time of 25 to 30 minutes, the ratio of A solution to B solution is maintained at 90:10. The analysis was carried out at a flow rate of 0.8 ml / min.

[0110] (Reaction yield of bisphenol (based on acetone)) The reaction yield (mol %) of bisphenol C based on acetone was calculated by calculating the concentration of bisphenol C in the reaction solution from the peak detected at a wavelength of 280 nm by high-performance liquid chromatography, calculating the molar amount of bisphenol C in the bisphenol C production reaction solution from that concentration, and then calculating the molar amount of bisphenol C divided by the molar amount of the starting acetone × 100%.

[0111] (viscosity average molecular weight) The viscosity average molecular weight (Mv) was 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 viscometer, and calculating the viscosity average molecular weight (Mv) using the following formula. ηsp / C=[η](1+0.28ηsp) [η]=1.23×10 -4 Mv 0.83

[0112] (Terminal hydroxyl group concentration of polycarbonate resin) The terminal hydroxyl group concentration (OH concentration) of the polycarbonate resin was measured by colorimetry in accordance with the titanium tetrachloride / acetic acid method (see Makromol. Chem. 88, 215 (1965)).

[0113] (Pellet YI) Pellet YI (transparency of polycarbonate resin) was evaluated by measuring the YI value (yellowness index) of polycarbonate resin pellets in reflected light in accordance with ASTM D1925. A Konica Minolta CM-5 spectrophotometer was used, with measurement conditions of a 30 mm measurement diameter and SCE selected. A CM-A212 Petri dish calibration glass was fitted into the measurement section, and a CM-A124 zero calibration box was placed over it to perform zero calibration. White calibration was then performed using the built-in white calibration plate. Measurements were then performed using the CM-A210 white calibration plate, confirming L* of 99.40 ± 0.05, a* of 0.03 ± 0.01, b* of -0.43 ± 0.01, and YI of -0.58 ± 0.01. Pellets were measured by filling a cylindrical glass container with an inner diameter of 30 mm and a height of 50 mm to a depth of approximately 40 mm. The procedure of removing the pellet from the glass container and then measuring again was repeated twice, and the average value of the three measured values ​​was used.

[0114] [Reference example 1] A 1-L eggplant-shaped flask equipped with a magnetic rotor was charged with 242 g of cresol sulfonic acid solution (composition: 63% by mass of orthocresol sulfonic acid, 1.5% by mass of cresol, 3% by mass of sulfuric acid, 32.5% by mass of water), 38.4 g of sodium hydroxide, and 32 g of demineralized water, and the eggplant-shaped flask was placed in an ice bath and stirred. After confirming that the sodium hydroxide in the eggplant-shaped flask had completely dissolved, a 55.6% by mass sodium cresol sulfonate solution was prepared.

[0115] [Reference example 2] A portion of the sodium cresol sulfonate solution obtained in Reference Example 1 was placed in a 500 mL eggplant-shaped flask and evaporated to dryness under reduced pressure using an evaporator equipped with an oil bath. A portion of the resulting white solid was suspended and washed in 100 g of acetone, and then suspended and washed in 100 g of toluene to obtain 1.5 g of sodium cresol sulfonate. This sodium cresol sulfonate was used to prepare a 2.3 mass % aqueous solution of sodium cresol sulfonate.

[0116] [Reference example 3] Using sodium phenolsulfonate, a 2.3 mass % aqueous solution of sodium phenolsulfonate was prepared.

[0117] [Reference example 4] A 1-L separable flask equipped with a condenser, jacket, and anchor-type stirring blade was charged with 100 g of xylenol and 10 g of toluene. Then, 100 g of 98% sulfuric acid was slowly added and the mixture was stirred at 50°C for 1 hour. The resulting reaction solution was a slurry, which was then filtered under reduced pressure. The resulting cake was placed in a 500 mL eggplant-shaped flask, and toluene and 25% aqueous sodium hydroxide solution were added while monitoring the pH meter until neutralization occurred. The resulting slurry was filtered under reduced pressure, and the resulting cake was washed by suspension in toluene, then washed with water, and dried under reduced pressure on a rotary evaporator to obtain 10 g of a white solid. NMR analysis of the resulting white solid revealed that it was xylenol sulfonic acid (hereinafter sometimes referred to as 4-hydroxy-2,6-dimethylbenzenesulfonic acid). ICP mass spectrometry revealed that the sodium concentration in the white solid was 10% by mass, confirming that the white solid was sodium 4-hydroxy-2,6-dimethylbenzenesulfonate. Using this sodium xylenol sulfonate, a 2.3 mass % aqueous solution of sodium xylenol sulfonate was prepared.

[0118] [Example 1] 4.7 g of commercially available bisphenol C (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 μL of the sodium cresol sulfonate solution prepared in Reference Example 2 were mixed to prepare a bisphenol C composition containing 100 ppm by mass of sodium cresol sulfonate relative to bisphenol C. 4.7 g of the bisphenol C composition and 4.5 g of diphenyl carbonate were placed in a Teflon (registered trademark) test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the resulting reaction solution was taken out and the phenol production rate by reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, revealing that 0.5 area % of phenol was produced.

[0119] [Example 2] 4.7 g of commercially available bisphenol C and 20 μL of the sodium xylenol sulfonate solution prepared in Reference Example 4 were mixed to prepare a bisphenol C composition containing 100 ppm by mass of sodium xylenol sulfonate relative to bisphenol C. 4.7 g of the bisphenol C composition and 4.5 g of diphenyl carbonate were placed in a Teflon test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the resulting reaction solution was taken out and the phenol production rate by reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, revealing that 0.4 area % of phenol was produced.

[0120] [Example 3] 4.7 g of commercially available bisphenol C and 20 μL of the sodium phenolsulfonate solution prepared in Reference Example 3 were mixed to prepare a bisphenol C composition containing 100 ppm by mass of sodium phenolsulfonate relative to bisphenol C. 4.7 g of the bisphenol C composition and 4.5 g of diphenyl carbonate were placed in a Teflon test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the resulting reaction solution was taken out and the phenol production rate by reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, revealing that 0.6 area % of phenol was produced.

[0121] [Example 4] Using 4.7 g of commercially available bisphenol C and the sodium cresol sulfonate solution prepared in Reference Example 2, the concentration of the bisphenol C composition was 230 mass ppb 20 μL of the aqueous solution obtained by preparing the sodium cresol sulfonate solution was added to the solution, and a bisphenol C composition containing 1 ppb of sodium cresol sulfonate by mass relative to bisphenol C was prepared. 4.7 g of the bisphenol C composition and 4.5 g of diphenyl carbonate were placed in a Teflon test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the resulting reaction solution was taken out and the phenol production rate by reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, revealing that 0.3 area % of phenol was produced.

[0122] [Comparative Example 1] As the bisphenol C composition, commercially available bisphenol C was used as is. 4.7 g of the bisphenol C composition, 4.5 g of diphenyl carbonate, and 20 μL of a 33.7 μg / g aqueous potassium hydroxide solution were placed in a Teflon (registered trademark) test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the resulting reaction solution was taken and the phenol production rate by reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, revealing that 0.1 area % of phenol was produced. To accurately determine the content of aromatic alcohol sulfonates in bisphenol, 10 g of the bisphenol C composition, 1.5 mL of orthoxylene, and 1.0 mL of acetonitrile were placed in a 10 mL glass container designed for centrifugation and heated to completely dissolve the mixture to form a homogeneous solution. The resulting solution was allowed to cool to room temperature to obtain a solid. A glass filter and a receiver were then placed in the tube, and 1 g of liquid was extracted from the solid using a centrifuge (2000 rpm for 10 minutes). After concentrating the bisphenol C composition as described above, the aromatic alcohol sulfonates were analyzed. However, the concentration was below the detection limit of 0.1 ppb by mass, and no aromatic alcohol sulfonates were detected.

[0123] Comparative Example 2 Commercially available bisphenol C 4.7g Cresol sulfonic acid was diluted and added to prepare a bisphenol C composition containing 5 ppm by mass of cresol sulfonic acid relative to bisphenol C. 4.7 g of the bisphenol C composition and 4.5 g of diphenyl carbonate were placed in a Teflon test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the resulting reaction solution was taken and the rate of phenol production by the reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, but no phenol was found to be produced.

[0124] Comparative Example 3 Commercially available bisphenol C 4.7g Cresol sulfonic acid Addition of bisphenol C Cresol sulfonic acid A bisphenol C composition containing 100 ppm by mass was prepared. 4.7 g of the bisphenol C composition and 4.5 g of diphenyl carbonate were placed in a Teflon test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the resulting reaction solution was taken and the rate of phenol production by the reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, but no phenol was found to be produced.

[0125] The phenol production rates by reaction with diphenyl carbonate for Examples 1 to 4 and Comparative Examples 1 to 3 are summarized in Table 1. A comparison of Example 1 with Comparative Example 1 shows that the bisphenol C composition containing sodium cresol sulfonate has a high initial polymerization activity (phenol production rate). Furthermore, a comparison of Examples 1 and 4 with Comparative Examples 2 and 3 shows that the initial polymerization activity is high when the cresol sulfonic acid contained in the bisphenol C composition is a salt of sodium cresol sulfonate.

[0126] [Table 1]

[0127] [Example 5] (Production of bisphenol crystallization composition) A 1-L separable flask equipped with a condenser, a jacket, and an anchor-type stirring blade was charged with 100 g of commercially available bisphenol C and 0.18 g of the sodium cresol sulfonate solution prepared in Reference Example 1, to prepare a bisphenol C composition containing 0.1 mass % of sodium orthocresol sulfonate.

[0128] (Production of bisphenol composition) 163 g of toluene was placed in the separable flask and heated to 80° C. to form a homogeneous solution. 40 g of demineralized water was added to the homogeneous solution, and the mixture was mixed for 10 minutes while maintaining the temperature at 80° C., and then allowed to stand to separate the oil and water. The time it took for the bubbles on the oil-water interface to disappear was 1 minute 34 seconds.Then, the aqueous phase was removed from the separable flask to obtain an organic phase. The obtained organic phase was cooled from 80°C to 10°C to crystallize bisphenol C, and the solid-liquid separation was carried out using a centrifugal separator to obtain wet bisphenol C. The wet bisphenol C was placed in a 1 L eggplant-shaped flask and dried under reduced pressure using a rotary evaporator equipped with a water bath at 80°C, to obtain 95 g of a bisphenol C composition that was washed with water and dried. A portion of the bisphenol C composition was taken out and the amounts of sodium 4-hydroxy-3-methylbenzenesulfonate and sodium 2-hydroxy-3-methylbenzenesulfonate were confirmed using a high-performance liquid chromatograph mass spectrometer. The composition was found to contain 35 ppm by mass of sodium 4-hydroxy-3-methylbenzenesulfonate and 2 ppm by mass of sodium 2-hydroxy-3-methylbenzenesulfonate.

[0129] (Measurement of phenol production rate) 4.7 g of the water-washed and dried bisphenol C composition, 4.5 g of diphenyl carbonate, and 20 μL of a 33.7 ppm by mass aqueous potassium hydroxide solution were placed in a Teflon (registered trademark) test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the resulting reaction solution was taken and the phenol production rate by reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, revealing that 1.2 area % of phenol was produced.

[0130] [Example 6] The same procedure as in Example 5 was carried out, except that commercially available bisphenol C from a different production lot was used instead of the commercially available bisphenol C used in Example 5. As a result, a portion of the resulting reaction solution was taken out and the phenol production rate by reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, and it was found that phenol was produced in an amount of 1.2 area %.

[0131] [Example 7] The same procedure as in Example 5 was carried out, except that commercially available bisphenol C of a different production lot was used instead of the bisphenol C used in Examples 5 and 6. As a result, a portion of the resulting reaction solution was taken out and the phenol production rate by reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, and it was found that phenol was produced in an amount of 1.2 area %.

[0132] Comparative Example 4 A 1-L separable flask equipped with a condenser, jacket, and anchor-type stirring blade was charged with 100 g of commercially available bisphenol C and 163 g of toluene, and the mixture was heated to 80°C to form a homogeneous solution. 40 g of demineralized water was added to the homogeneous solution, and the mixture was mixed for 10 minutes while maintaining the temperature at 80°C, after which the mixture was allowed to stand to separate the oil and water. The water bubbles at the oil-water interface did not disappear even after 5 hours. The aqueous phase was removed from the separable flask, and the resulting organic phase, with some water bubbles remaining, was cooled from 80°C to 10°C to crystallize bisphenol C. The resulting organic phase was then subjected to solid-liquid separation in a centrifuge to obtain wet bisphenol C. The wet bisphenol C was charged into a 1-L eggplant-shaped flask and dried under reduced pressure using a rotary evaporator equipped with an 80°C water bath, yielding 96 g of bisphenol C that was washed and dried with water.

[0133] 4.7 g of the bisphenol C, 4.5 g of diphenyl carbonate, and 20 μL of a 33.7 ppm by mass aqueous potassium hydroxide solution were placed in a Teflon (registered trademark) test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the resulting reaction solution was taken out and the phenol production rate by reaction with diphenyl carbonate was confirmed by high performance liquid chromatography, revealing that 0.2 area % of phenol was produced. To accurately determine the content of aromatic alcohol sulfonates in bisphenol, 10 g of the bisphenol C composition, 1.5 mL of orthoxylene, and 1.0 mL of acetonitrile were placed in a 10 mL glass container designed for centrifugation and heated to completely dissolve the mixture to form a homogeneous solution. The resulting solution was allowed to cool to room temperature to obtain a solid. A glass filter and a receiver were then placed in the tube, and 1 g of liquid was extracted from the solid using a centrifuge (2000 rpm for 10 minutes). After concentrating the bisphenol C composition as described above, the aromatic alcohol sulfonates were analyzed. However, the concentration was below the detection limit of 0.1 ppb by mass, and no aromatic alcohol sulfonates were detected.

[0134] For Examples 5 to 7 and Comparative Example 4, the amount of sodium cresol sulfonate (total amount of 4-hydroxy-3-methylbenzenesulfonic acid and sodium 2-hydroxy-3-methylbenzenesulfonate) contained in the bisphenol crystallization composition (bisphenol C before washing (water washing and crystallization)), the time it takes for bubbles to disappear at the oil-water interface, the amount of sodium cresol sulfonate (total amount of sodium 4-hydroxy-3-methylbenzenesulfonate and sodium 2-hydroxy-3-methylbenzenesulfonate) contained in the bisphenol composition (bisphenol C after washing (water washing, crystallization, and drying)), and the production rate of phenol by reaction with diphenyl carbonate are summarized in Table 2.

[0135] Example 5 shows that sodium cresol sulfonate acts as a surfactant, since the bisphenol C composition obtained by adding sodium cresol sulfonate to obtain a composition for bisphenol crystallization and then washing (water washing and crystallization) had a short time for water bubbles to disappear at the oil-water interface. Furthermore, since the yield of phenol produced by the reaction with diphenyl carbonate in Example 5 was higher than in Example 1, it can be inferred that, in addition to the catalytic effect of promoting the reaction with diphenyl carbonate, washing after obtaining a composition for bisphenol crystallization by adding sodium cresol sulfonate efficiently removes components contained in the bisphenol C composition that inhibit the reaction with diphenyl carbonate. Furthermore, Examples 5 to 7 show that even when bisphenol C from different production lots is used as a raw material, by adding cresol sulfonic acid to obtain a crude bisphenol product and then washing, it is possible to similarly remove components contained in bisphenol C that inhibit the reaction with diphenyl carbonate, and bisphenol C compositions of stable quality can be stably produced. Furthermore, the results of the phenol production rate by reaction with diphenyl carbonate in Examples 5 to 7 show that the obtained bisphenol C compositions can be stably reacted with diphenyl carbonate.

[0136] Comparative Example 4 is an example in which bisphenol C was produced in the same manner as in Examples 5 to 7, except that commercially available bisphenol C was used as is, rather than adding sodium cresol sulfonate to commercially available bisphenol C to form a bisphenol crystallization composition. Comparative Example 4 shows that the bisphenol C obtained by washing (water washing and crystallization) commercially available bisphenol C also had a low production rate of phenol by reaction with diphenyl carbonate, and that the washing did not sufficiently remove components that inhibit the reaction.

[0137] [Table 2]

[0138] [Example 8] (Production of bisphenol crystallization composition) A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 35.0 g (1.1 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 77.7 g (0.7 mol) of 88 wt. % sulfuric acid. Then, 72.6 g of toluene, 255.0 g (2.4 mol) of orthocresol, and 7.3 g (0.04 mol) of dodecanethiol were added to the separable flask, and the temperature inside the separable flask was raised to 50°C. 57.0 g (1.0 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction solution was orange. This reaction solution was allowed to react for 15 hours at 50°C. After the reaction was completed, 135.0 g of toluene and 175.5 g of dechlorinated water were added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand and it was confirmed that the substances that had precipitated during the reaction had dissolved in the organic and aqueous phases, and then the lower aqueous phase was removed. A saturated sodium bicarbonate solution was then added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase had reached 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was taken out and the amount of bisphenol C produced was confirmed by high performance liquid chromatography, and the reaction yield was found to be 85 mol % based on acetone. This organic phase was cooled from 80°C to 30°C, and when the temperature reached 30°C, 1 g of seed crystals of bisphenol C was added to confirm precipitation. Thereafter, the organic phase was cooled to 10°C, and after the temperature reached 10°C, it was filtered under reduced pressure using a glass filter to obtain 239.9 g of a composition for crystallization of bisphenol C as a wet cake.

[0139] A portion of the bisphenol C crystallization composition was taken out and the amounts of sodium 4-hydroxy-3-methylbenzenesulfonate and sodium 2-hydroxy-3-methylbenzenesulfonate were confirmed using a high-performance liquid chromatograph mass spectrometer. The composition was found to contain 35 ppm by mass of sodium 4-hydroxy-3-methylbenzenesulfonate and 160 ppm by mass of sodium 2-hydroxy-3-methylbenzenesulfonate.

[0140] (Production of bisphenol composition) The entire amount of the bisphenol C crystallization composition and 449 g of toluene were placed in a fully jacketed, 1-liter separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80°C. After confirming that the solution had become homogeneous, the organic phase was thoroughly washed with 600 g of demineralized water in two portions. The time it took for the bubbles on the oil-water interface to disappear was about 5 minutes. The resulting organic phase was cooled from 80°C to 10°C. It was then filtered using a centrifuge (at 3,000 rpm for 10 minutes) to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, low boiling points were distilled off under reduced pressure at an oil bath temperature of 100°C to obtain 180.9 g of a bisphenol C composition.

[0141] 10 g of the bisphenol C composition, 1.5 mL of orthoxylene, and 1.5 mL of acetonitrile were placed in a 10 mL glass container designed for centrifugation and heated to completely dissolve the mixture to form a homogeneous solution. The solution was allowed to cool to room temperature, yielding a solid. A glass filter and a receiver were then placed in the glass container to form a centrifuge tube, and 1 g of liquid was extracted from the solid using a centrifuge (2000 rpm for 10 minutes). A portion of the resulting liquid was removed and the amounts of 4-hydroxy-3-methylbenzenesulfonic acid and sodium 2-hydroxy-3-methylbenzenesulfonate were determined using a high-performance liquid chromatograph mass spectrometer. The liquid contained 5 ppb by mass of sodium 4-hydroxy-3-methylbenzenesulfonate and 3 ppb by mass of sodium 2-hydroxy-3-methylbenzenesulfonate.

[0142] (Measurement of phenol production rate) 4.7 g of the obtained bisphenol C composition, 4.5 g of diphenyl carbonate, and 20 μL of a 33.7 ppm by mass aqueous potassium hydroxide solution were placed in a Teflon (registered trademark) test tube and heated for 90 minutes in an aluminum block heater heated to 194° C. A portion of the obtained reaction solution was taken and the initial polymerization activity was confirmed by high performance liquid chromatography, which showed that phenol was produced in an amount of 1.6 area %.

[0143] (Manufacturing of polycarbonate resin) A 150 mL glass reactor equipped with a stirrer and a distillation tube was charged with 100.00 g (0.39 mol) of the bisphenol C composition, 86.49 g (0.4 mol) of diphenyl carbonate, and 479 μL of a 400 ppm by mass aqueous cesium carbonate solution. The glass reactor was depressurized to approximately 100 Pa, and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated three times to replace the interior of the reactor with nitrogen. The reactor was then immersed in a 200°C oil bath to dissolve the contents. The stirrer was rotated at 100 rpm, and the pressure in the reactor was reduced from 101.3 kPa absolute to 13.3 kPa over 40 minutes while distilling off phenol, a by-product of the oligomerization reaction of bisphenol C and diphenyl carbonate in the reactor. The pressure in the reactor was then maintained at 13.3 kPa, and a transesterification reaction was carried out for 80 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa absolute pressure to 399 Pa over 40 minutes, and the distilled phenol was removed from the system. The temperature outside the reactor was then raised to 280°C, and the absolute pressure inside the reactor was reduced to 30 Pa, and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the reactor's agitator reached a predetermined stirring power. The reactor was then restored to an absolute pressure of 101.3 kPa with nitrogen, and the gauge pressure was then increased to 0.2 MPa. Polycarbonate was extracted from the bottom of the reactor in the form of strands, yielding a strand-like polycarbonate resin. The strands were then pelletized using a rotary cutter to yield pellet-like polycarbonate resin. The polycarbonate had a viscosity average molecular weight (Mv) of 24,800, a terminal hydroxyl group concentration (OH concentration) of 769 ppm by mass, and a pellet YI of 7.62. When the Na concentration of a portion of the polycarbonate was measured using an ICP mass spectrometer, 0.1 ppm by mass was detected. (Aromatic alcohol sulfonate content in polycarbonate resin) 0.2 g of the resulting polycarbonate and 1 mL of methylene chloride were placed in a 50 mL Erlenmeyer flask equipped with a stirrer and dissolved. Then, 4 mL of methanol was slowly added dropwise while thoroughly stirring. After the addition was complete, the Erlenmeyer flask was placed in a water bath and extracted for 30 minutes. The entire solution was transferred to a 15 mL centrifuge tube and centrifuged at 5,000 rpm for 15 minutes. After centrifugation, 3 mL of the supernatant was transferred to a 50 mL eggplant-shaped flask. The 50 mL eggplant-shaped flask was placed in a rotary evaporator equipped with a water bath, and the water bath was set to 45°C to evaporate to dryness. 0.5 mL of methanol was added to the resulting dry product, which was then sealed and ultrasonically extracted for 5 minutes. A portion of the resulting solution was analyzed by high-performance liquid chromatography mass spectrometry, detecting 3 ppb by mass of 2-hydroxy-3-methylbenzenesulfonic acid. Since the amount of Na contained in the polycarbonate is greater than the amount of 2-hydroxy-3-methylbenzenesulfonic acid contained in the polycarbonate, the 2-hydroxy-3-methylbenzenesulfonic acid contained in the polycarbonate is sodium 2-hydroxy-3-methylbenzenesulfonate, and its concentration is 3 ppb by mass (3 ppb by mass ÷ molecular weight of 2-hydroxy-3-methylbenzenesulfonic acid 188.2 g / mol × sodium 2-hydroxy-3-methylbenzenesulfonate 210.2 g / mol).

[0144] [Experiment 2] [Raw materials and reagents] Ortho-cresol used was a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. or a product manufactured by Nippon Steel Chemical Co., Ltd. Acetone and methanol used were special grade reagents manufactured by Wako Pure Chemical Industries, Ltd. or products manufactured by Taishin Chemical Co., Ltd. Dodecanethiol used was a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. or a product manufactured by Kao Corporation. Toluene used was a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. or a product manufactured by Cosmo Oil Co., Ltd.

[0145] The sulfuric acid used was a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. or a product manufactured by Kaname Pharmaceutical Co., Ltd. Acetonitrile, acetic acid, ammonium acetate, ethyl acetate, ortho-xylene, para-xylene, xylene, mesitylene, chlorobenzene, isopropyl alcohol, 1-octanol, ethylene glycol, 2,6-xylenol, phenol, dodecanal, cyclohexanone, cycloheptanone, methyl ethyl ketone, methyl isobutyl ketone, 3.3.5-trimethylcyclohexanone, sodium hydroxide, sodium bicarbonate, acetophenone, deuterated chloroform, heptane, cesium carbonate, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane were all reagent grades manufactured by Wako Pure Chemical Industries, Ltd.

[0146] 3-Mercaptopropionic acid, fluorenone, 2-ethylhexanal, 2-phenylphenol, 2-cyclohexylphenol, 2-cyclohexylphenol, and 2-benzylphenol were reagents manufactured by Tokyo Chemical Industry Co., Ltd. 2,2-bis(4-hydroxyphenyl)propane and diphenyl carbonate were products manufactured by Mitsubishi Chemical Corporation. The 1,1-bis(4-hydroxyphenyl)dodecane used was a product manufactured by Shinryo Corporation.

[0147] [analysis] Analysis of monomethyl sulfate and mono(2-hydroxyethyl) sulfate was performed using proton nuclear magnetic resonance ( 1 This was measured using proton nuclear magnetic resonance ( 1 H NMR measurements were carried out using a JNM=ECS400 model manufactured by JEOL Ltd. The bisphenols produced were analyzed by high performance liquid chromatography mass spectrometry (LCMS) under the following conditions.

[0148] Separation equipment: Agilent Technologies Agilent 1200, ImtaktScherzo SM-C18 3 μm, 150 mm x 4.6 mm ID. Low-pressure gradient method. Analysis temperature: 40°C. 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: 1000 mL solution. At analysis time 0 min, the eluent composition was 60:40 (volume ratio; same below). From analysis time 0 to 25 min, the eluent composition was gradually changed to 90:10 (volume ratio of Solution A:B). From analysis time 25 to 30 min, the eluent composition was maintained at 90:10 (volume ratio of Solution A:B). Analysis was performed at a flow rate of 1.0 mL / min. The detection wavelength was 280 nm.

[0149] (Mass spectrometer): Agilent LC / MS 6130 manufactured by Agilent Technologies. The ion source used was an ESI (postive / negative) AJS probe. The composition of the bisphenol reaction solution was analyzed by high performance liquid chromatography according to the following procedure and conditions.

[0150] (Separator): Shimadzu LC-2010A, ImtaktScherzo SM-C18 3 μm 150 mm x 4.6 mm ID. Low-pressure gradient method. Analysis temperature: 40°C. 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 min, the solution A:B = 60:40 (volume ratio, same below). From analysis time 0 to 25 min, the eluent composition was gradually changed to solution A:B = 90:10, and from analysis time 25 to 30 min, the solution A:B = 90:10 was maintained. Analysis was performed at a flow rate of 0.8 mL / min. The detection wavelength was 280 nm.

[0151] The reaction yield (mol %) based on acetone was calculated by calculating the molar amount of bisphenol contained in the reaction solution from the analytical value of bisphenol obtained by high performance liquid chromatography, and then calculating the molar amount of bisphenol divided by the molar amount of the starting acetone × 100%. The reaction yield (area %) of the isopenyl cresol dimer (also referred to as "production rate") was calculated by dividing the area of ​​the isopenyl cresol dimer obtained by high-performance liquid chromatography by the area of ​​2,2-bis(4-hydroxy-3-methylphenyl)propane × 100 (area %). The production rates (area %) of substances other than the isopenyl cresol dimer can also be calculated in a similar manner. The yield (mol %) based on acetone according to the present invention was calculated by dividing the molar amount of the obtained bisphenol by the molar amount of the starting acetone × 100%.

[0152] [Reference example 5] 0.2 g of methanol was placed in a 50 ml eggplant-shaped flask, 0.5 g of 92 wt % sulfuric acid was slowly added thereto, and the mixture was shaken for 1 minute. This liquid was placed in a 5 mm diameter NMR sample tube, and a deuterated chloroform tube (2 mm diameter sealed tube) for locking was inserted into the sample. 1 HNMR was measured. 1 In the HNMR spectrum, a signal was observed at δ 4.0 ppm. When 9.7 mg of the reagent sodium monomethyl sulfate was added to the NMR sample tube, the peak at δ 4.0 ppm increased, confirming that the peak was the signal of the proton of monomethyl sulfate. From these results, it was confirmed that monomethyl sulfate is produced when sulfuric acid and methanol are mixed.

[0153] [Reference example 6] 0.2 g of ethylene glycol was placed in a 50 ml eggplant-shaped flask, and 0.5 g of 92 wt % sulfuric acid was slowly added thereto and shaken for 1 minute. This liquid was placed in a 5 mm diameter NMR sample tube, and a deuterated chloroform tube (2 mm diameter sealed tube) for locking was inserted into the sample. 1 HNMR was measured. 1 In the H NMR spectrum, broad signals believed to be 2-hydroxyethyl sulfate were detected at δ 3.98-3.99 ppm and 4.19-4.21 ppm, confirming that mixing sulfuric acid and ethylene glycol produces mono(2-hydroxyethyl) sulfate.

[0154] [Example 9] In a fully jacketed, 1-liter separable flask equipped with a thermometer, a stirrer, and a 100-mL dropping funnel, 35.0 g (1.1 mol) of methanol was placed under a nitrogen atmosphere, and then 77.7 g (0.7 mol) of 88 wt. % sulfuric acid was slowly added. A portion of the resulting solution was taken and placed in a 5 mm diameter NMR sample tube, and a deuterated chloroform tube (2 mm diameter sealed tube) for locking was inserted into the sample. 1 HNMR was measured. 1 A signal was observed at δ 4.0 ppm in the HNMR spectrum, confirming the generation of monomethyl sulfate. Furthermore, the amount of monomethyl sulfate generated was calculated from the integral of the δ 4.0 ppm peak assigned to monomethyl sulfate and the peak assigned to methanol, and was found to be 30 wt%. Subsequently, 72.6 g of toluene, 255.0 g (2.4 mol) of orthocresol, and 7.3 g (0.04 mol) of dodecanethiol were placed in a separable flask and the temperature inside the separable flask was raised to 50°C. 57.0 g (1.0 mol) of acetone was placed in the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction solution was orange. This reaction solution was reacted for 15 hours at 50°C. After the reaction was complete, 135.0 g of toluene and 175.5 g of dechlorinated water were added and the temperature was raised to 80°C. After the temperature reached 80°C, the mixture was left to stand, and it was confirmed that the material that had precipitated during the reaction had dissolved in the organic and aqueous phases, after which the lower aqueous phase was removed. The organic phase thus obtained was then neutralized by adding a saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase had reached 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the organic phase thus obtained and stirred for 10 minutes. After stirring, the mixture was left to stand, and the aqueous phase was removed. A portion of the organic phase thus obtained was removed, and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography. The reaction yield based on acetone was found to be 85 mol %. Furthermore, a peak observed at a retention time of 15.7 minutes in the high-performance liquid chromatograph was measured in the negative mode of high-performance liquid chromatography mass spectrometry, and a mass number of 295 (M +-1) was observed, and the peak at a retention time of 15.7 minutes was identified as a dimer of isopropenyl cresol. The production rate of the dimer of isopropenyl cresol was 0.7% by area. This organic phase was cooled to 80-30°C, and when the temperature reached 30°C, 1 g of seed crystals of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as bisphenol C) was added to confirm precipitation. The mixture was then cooled to 10°C, and after reaching 10°C, it was filtered under reduced pressure using a glass filter to obtain 239.9 g of crude bisphenol C as a wet cake.

[0155] The entire amount of crude bisphenol C and 449 g of toluene were placed in a fully jacketed, 1-liter separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80°C. After confirming that the solution had become homogeneous, the mixture was cooled to 10°C. This was followed by filtration under reduced pressure using a glass filter to obtain wet refined bisphenol C. Using an evaporator equipped with an oil bath, low boiling points were distilled off under reduced pressure at an oil bath temperature of 100°C, yielding 180.9 g (0.7 mol, 72 mol% yield based on acetone) of bisphenol C.

[0156] [Example 10] In a fully jacketed 1.5-liter separable flask equipped with a thermometer, a stirrer, and a dropping funnel, 0.1 g (3.1 mmol) of methanol was placed under a nitrogen atmosphere, and then 250 g (0.7 mol) of 80% by weight sulfuric acid was slowly added. A portion of the resulting solution was taken out and 1HNMR spectrum showed that 10 wtppm of monomethyl sulfate was generated. Subsequently, 320 g of toluene and 230.0 g (2.1 mol) of orthocresol were placed in a separable flask and the temperature inside the separable flask was raised to 30°C. 51.0 g (0.9 mol) of acetone and 5.3 g (0.03 mol) of dodecanethiol were placed in the dropping funnel and slowly added dropwise to the separable flask over 60 minutes so as to maintain the internal temperature at 30°C. After the dropwise addition of the acetone and dodecanethiol mixture was completed, the reaction solution was orange. The resulting reaction solution was mixed at 30°C for 1 hour, then heated to 45°C and reacted. After reaching 45°C (reaction completion), 175.5 g of demineralized water and 135 g of 28% aqueous sodium hydroxide solution were added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand and the substances that had precipitated during the reaction were confirmed to have dissolved in the organic and aqueous phases, after which the lower aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase had reached 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography. The reaction yield based on acetone was 69 mol %. The production rate of isopropenyl cresol dimer was 0.24 area %.

[0157] [Example 11] In a fully jacketed 1.5-liter separable flask equipped with a thermometer, a stirrer, and a dropping funnel, 12 g (3.1 mmol) of methanol was placed under a nitrogen atmosphere, and then 250 g (0.7 mol) of 80% by weight sulfuric acid was slowly added. A portion of the resulting solution was taken out and 1HNMR spectrum showed that 0.1 wt% of monomethyl sulfate was generated. Subsequently, 320 g of toluene and 230.0 g (2.1 mol) of orthocresol were placed in a separable flask and the temperature inside the separable flask was raised to 30°C. 51.0 g (0.9 mol) of acetone and 5.3 g (0.03 mol) of dodecanethiol were placed in the dropping funnel and slowly added dropwise to the separable flask over 60 minutes so that the internal temperature remained at 30°C. After the dropwise addition of the acetone and dodecanethiol mixture was completed, the reaction solution was orange. The resulting reaction solution was mixed at 30°C for 1 hour, then heated to 45°C and allowed to react. After reaching 45°C (reaction completion), 175.5 g of demineralized water and 135 g of 28% aqueous sodium hydroxide solution were added and the temperature was raised to 80°C. After the temperature reached 80°C, the mixture was allowed to stand and it was confirmed that the material that had precipitated during the reaction had dissolved in the organic and aqueous phases, after which the lower aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase had reached 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was determined by high-performance liquid chromatography. The reaction yield based on acetone was 63 mol %. The production rate of isopropenyl cresol dimer was 0.13 area %.

[0158] Comparative Example 5 A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-milliliter dropping funnel was charged with 58.5 g (0.6 mol) of 92 wt. % sulfuric acid, 54.3 g of toluene, 191.5 g (1.8 mol) of orthocresol, and 5.5 g (0.03 mol) of dodecanethiol under a nitrogen atmosphere, and the temperature inside the separable flask was raised to 50°C. 42.5 g (0.7 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, a reddish-brown reaction solution was obtained. After reacting this reaction solution for 30 minutes at 50°C, the reaction solution completely solidified and became unmixable. Subsequently, 100 g of dechlorinated water and 200 g of ethyl acetate were added, and the mixture was mixed for 5 minutes to dissolve the precipitate. The resulting solution was allowed to stand, and the aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was determined by high-performance liquid chromatography, which was found to be 40 mol %. The production rate of isopropenyl cresol dimer was 6.2 area %.

[0159] [Reference example 7] A fully jacketed 1.5-liter separable flask equipped with a thermometer, stirrer, and dropping funnel was charged with 12 g (3.1 mmol) of methanol, 320 g of toluene, 230.0 g (2.1 mol) of orthocresol, 51.0 g (0.9 mol) of acetone, and 5.3 g (0.03 mol) of dodecanethiol under a nitrogen atmosphere and heated to 30°C. 250 g (0.7 mol) of 70% sulfuric acid was added to the dropping funnel and slowly added dropwise to the separable flask so that the internal temperature remained at 30°C. After the addition of the sulfuric acid was complete, the reaction solution was reddish-brown in color. The reaction solution was mixed at 30°C for 1 hour and then heated to 45°C for reaction. After the reaction was complete, 175.5 g of dechlorinated water and 125 g of 28% aqueous sodium hydroxide solution were added and the temperature was raised to 80°C. After the temperature reached 80°C, the mixture was allowed to stand and it was confirmed that the material that had precipitated during the reaction had dissolved in the organic and aqueous phases, after which the lower aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase had reached 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was determined by high-performance liquid chromatography. The reaction yield based on acetone was 53 mol %. The production rate of isopropenyl cresol dimer was 0.3 area %.

[0160] [Reference example 8] A fully jacketed 1.5-liter separable flask equipped with a thermometer, a stirrer, and a dropping funnel was charged with 85 g of methanol, 168 g (1.6 mol) of ortho-cresol, and 30 g (0.5 mol) of acetone under a nitrogen atmosphere and heated to 10°C. 100 g of 98% sulfuric acid was charged into the dropping funnel and slowly added dropwise to the separable flask so as to maintain the internal temperature at 10°C. After the dropwise addition of the sulfuric acid was completed, the reaction solution was a reddish-brown homogeneous solution. This reaction solution was mixed at 10°C for 1 hour, then 200 g of toluene was added, and the temperature was raised to 30°C, resulting in two-phase separation. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography. Bisphenol C was found to be a trace amount (1 mol%), with several other by-products being produced.

[0161] Table 3 shows the type of catalyst, color tone of the reaction solution, properties of the reaction solution, reaction yield of bisphenol C, etc. for Examples 9 to 11, Comparative Example 5, and Reference Examples 7 and 8.

[0162] [Table 3]

[0163] Table 3 shows that when monomethyl sulfate is used as a catalyst, coloration of the reaction solution and the production of the by-product isopropenyl cresol dimer are suppressed, and bisphenol C with excellent color tone can be obtained in good yield without solidifying the reaction solution.

[0164] [Example 12] 566 kg of 88% sulfuric acid was supplied to a 1 cubic meter, fully jacketed, glass-lined reactor equipped with a thermometer, a stirrer, and a dropping tank. 255 kg of methanol was supplied to the dropping tank, and the methanol was slowly added dropwise to the reactor to obtain a monomethyl sulfate solution. 530 kg of toluene, 1,861 kg (17.2 kmol) of ortho-cresol, and 53 kg of dodecyl mercaptan were supplied to a 8 cubic meter, fully jacketed, glass-lined reactor equipped with a thermometer, a stirrer, and a dropping tank. 413 kg (7.1 kmol) of acetone was then supplied to the dropping tank. The monomethyl sulfate solution was then slowly pumped into the 8 cubic meter, glass-lined reactor, and acetone was slowly added so that the internal temperature of the reactor did not exceed 30°C. After the acetone was added, the internal temperature of the reactor was raised to 50°C and the mixture was mixed for 15 hours to complete the reaction. Subsequently, 985 kg of toluene, 1278 kg of water, and 1160 kg of 28 wt% sodium hydroxide solution were slowly added to the reactor so that the internal temperature of the reactor was below 50°C. The reactor was then heated to 80°C, allowed to stand, and the lower aqueous phase was removed. 599 kg of 1.5 wt% sodium bicarbonate solution was added to the resulting organic phase, mixed, and allowed to stand, and the lower aqueous phase was removed. The resulting organic phase was slowly cooled to 10°C, yielding a slurry from which bisphenol C precipitated. The filtrate was separated from this slurry using a centrifuge, yielding 1627 kg of wet cake. This wet cake was fed to a fully jacketed, 6.8 cubic meter stainless steel crystallization tank, followed by the addition of 2442 kg of toluene. The crystallization tank was heated to 80°C, 551 kg of pure water was added and mixed, and the mixture was allowed to stand, and the lower aqueous phase was removed. Furthermore, 552 kg of pure water was added to the crystallization tank, mixed, and allowed to stand, and the lower aqueous phase was removed. To the resulting organic phase, 27 kg of a 0.001 wt % sodium chloride solution was added and cooled to 10°C, resulting in the precipitation of bisphenol C, yielding a slurry. This slurry was separated by centrifugation and washed with 780 kg of toluene, yielding 1,537 kg of wet cake. The resulting wet cake was fed to a 6.5 cubic meter dryer and thoroughly dried, yielding 1,440 kg of bisphenol (5.6 kmol, 79 mol% yield based on acetone). The amounts of acetone used and the reaction yields of bisphenol C for Examples 9 and 12 are summarized in Table 4.As a result, it was found that bisphenol could be produced in the same manner even when the amount of acetone was increased.

[0165] [Table 4]

[0166] [Example 13] A fully jacketed 200 mL separable flask equipped with a thermometer, stirrer, and 100 mL dropping funnel was charged with 6.9 g (0.2 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 15.4 g (0.1 mol) of 92 wt% sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 14.4 g of toluene, 50.6 g (0.5 mol) of orthocresol, and 1.4 g (0.01 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 11.2 g (0.20 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction was allowed to proceed for 5 hours at 40°C. After the reaction was complete, 50.0 g of toluene and 50.0 g of dechlorinated water were added, and the temperature was raised to 80°C. After the temperature reached 80°C, the mixture was allowed to stand and it was confirmed that the material that had precipitated during the reaction had dissolved in the organic and aqueous phases, after which the lower aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase had reached 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography, revealing a reaction yield of 89 mol% based on acetone.

[0167] [Example 14] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-milliliter dropping funnel was charged with 21.2 g (0.7 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 46.5 g (0.4 mol) of 92 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 122.4 g of ortho-xylene, 137.7 g (1.3 mol) of ortho-cresol, and 4.4 g (0.02 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 34.3 g (0.6 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction was allowed to proceed for 2 hours at 40°C. After the reaction was complete, 100.0 g of ortho-xylene and 100.0 g of dechlorinated water were added, and the temperature was raised to 80°C. After the temperature reached 80°C, the mixture was allowed to stand and it was confirmed that the material that had precipitated during the reaction had dissolved in the organic and aqueous phases, after which the lower aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase had reached 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography, revealing a reaction yield of 88 mol% based on acetone.

[0168] [Example 15] The same procedure as in Example 14 was repeated, except that 137.4 g of paraxylene was added to the separable flask instead of 122.4 g of orthoxylene, and after completion of the reaction, 100 g of paraxylene was added instead of 100 g of orthoxylene. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography, and the reaction yield based on acetone was found to be 91 mol %.

[0169] [Example 16] The same procedure as in Example 114 was repeated, except that 122.4 g of xylene was added to the separable flask instead of 122.4 g of orthoxylene, and after completion of the reaction, 100 g of xylene was added instead of 100 g of orthoxylene. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography, revealing that the reaction yield based on acetone was 88 mol %.

[0170] [Example 17] The same procedure as in Example 14 was repeated, except that 122.2 g of mesitylene was added to the separable flask instead of 122.4 g of orthoxylene, and after completion of the reaction, 100 g of mesitylene was added instead of 100 g of orthoxylene. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography, revealing that the reaction yield based on acetone was 85 mol %.

[0171] [Example 18] The same procedure as in Example 14 was repeated, except that 65.0 g of chlorobenzene was added to the separable flask instead of 122.4 g of orthoxylene, and after completion of the reaction, 100 g of chlorobenzene was added instead of 100 g of orthoxylene. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography, revealing that the reaction yield based on acetone was 60 mol %.

[0172] The types of solvents and reaction yields for Examples 13 to 18 are summarized in Table 5. As a result, it became clear that bisphenol C could be obtained in good yield even when the type of solvent was changed.

[0173] [Table 5]

[0174] [Example 19] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 26.1 g (0.4 mol) of isopropyl alcohol under a nitrogen atmosphere, followed by the slow addition of 58.3 g (0.5 mol) of 90 wt. % sulfuric acid. Subsequently, 54.5 g of toluene, 191.5 g (1.8 mol) of ortho-cresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 42.5 g (0.7 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction was allowed to proceed for 2 hours at 40°C. After the reaction was complete, 100.0 g of toluene and 100.0 g of dechlorinated water were added, and the temperature was raised to 80°C. After the temperature reached 80°C, the mixture was allowed to stand and it was confirmed that the material that had precipitated during the reaction had dissolved in the organic and aqueous phases, after which the lower aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase had reached 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography, revealing a reaction yield of 84 mol% based on acetone.

[0175] [Example 20] The same procedure as in Example 19 was repeated, except that 26.2 g (0.2 mol) of 1-octanol was supplied instead of 26.1 g of isopropyl alcohol. A portion of the resulting organic phase was taken out, and the amount of bisphenol C produced was confirmed by high performance liquid chromatography. The reaction yield was 82 mol% based on acetone.

[0176] [Example 21] The same procedure as in Example 19 was repeated, except that 18.4 g (0.3 mol) of ethylene glycol was supplied instead of 26.1 g of isopropyl alcohol. A portion of the resulting organic phase was taken out, and the amount of bisphenol C produced was confirmed by high performance liquid chromatography. The reaction yield based on acetone was found to be 75 mol%.

[0177] The types of aliphatic alcohol and reaction yields for Examples 13 and 19 to 21 are summarized in Table 6. As a result, it became clear that bisphenol C can be obtained in good yield even when the type of aliphatic alcohol is changed.

[0178] [Table 6]

[0179] [Example 22] The same procedure as in Example 19 was repeated, except that 2.9 g (0.01 mol) of 3-mercaptopropionic acid was supplied instead of 5.5 g of dodecanethiol, and 26.3 g (0.8 mol) of methanol was supplied instead of 26.1 g of isopropyl alcohol. A portion of the obtained organic phase was taken out, and the amount of bisphenol C produced was confirmed by high performance liquid chromatography, revealing that the reaction yield based on acetone was 98 mol%.

[0180] [Example 23] The same procedure as in Example 19 was repeated, except that 2.9 g (0.01 mol) of 3-mercaptopropionic acid was supplied instead of 5.5 g of dodecanethiol, and 18.4 g (0.3 mol) of ethylene glycol was supplied instead of 26.1 g of isopropyl alcohol. A portion of the obtained organic phase was removed, and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography, revealing that the reaction yield based on acetone was 89 mol%.

[0181] The types of aliphatic alcohols, types of thiols, and reaction yields for Examples 13 and 21 to 23 are summarized in Table 7. As a result, it became clear that bisphenol C could be obtained in good yield even when the types of aliphatic alcohols and thiols were changed.

[0182] [Table 7]

[0183] [Example 24] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-milliliter dropping funnel was charged with 1.7 g (0.1 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 33.0 g (0.3 mol) of 92 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 18 g of toluene, 63.0 g (0.7 mol) of phenol, and 1.7 g (0.05 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 16.0 g (0.3 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction was allowed to proceed for 2 hours at 40°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the resulting organic phase was removed and analyzed by high-performance liquid chromatography, which revealed that 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) had been produced. The amount was 73.2 area %.

[0184] [Example 25] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 8.7 g (0.3 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 19.4 g (0.2 mol) of 90 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 18.1 g of toluene, 63.8 g (0.7 mol) of phenol, and 1.8 g (0.01 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 44.9 g (0.2 mol) of dodecanal was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the dropwise addition of dodecanal, the reaction was allowed to proceed for 2 hours at 40°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and the pH of the lower aqueous phase was confirmed to be 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the resulting organic phase was removed and analyzed by high-performance liquid chromatography, revealing the formation of 1,1-bis(4-hydroxyphenyl)dodecane. The resulting organic phase was transferred to a 1-liter eggplant-shaped flask, and toluene, ethyl acetate, and phenol were distilled off using an evaporator. Heptane and isopropyl alcohol were added to the remaining liquid to induce crystallization. The resulting slurry was subjected to solid-liquid separation using a vacuum filter equipped with a glass filter, yielding a white solid. This white solid was transferred to a 500-mL eggplant-shaped flask and dried using an evaporator, yielding 30.5 g (0.1 mol, yield 35 mol%) of 1,1-bis(4-hydroxyphenyl)dodecane.

[0185] [Example 26] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 8.7 g (0.3 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 19.4 g (0.2 mol) of 90 wt% sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 18.2 g of toluene, 63.8 g (0.6 mol) of orthocresol, and 1.8 g (0.01 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 44.9 g (0.2 mol) of dodecanal was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the dodecanal addition was complete, the reaction was allowed to proceed for 2 hours at 40°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the obtained organic phase was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter, which showed a mass number of 381 (M + -1) was observed, indicating that 1,1-bis(4-hydroxy-3-methylphenyl)dodecane was produced. The production of 1,1-bis(4-hydroxy-3-methylphenyl)dodecane was confirmed using high-performance liquid chromatography, and was found to be 60.7 area %.

[0186] [Example 27] A fully jacketed, 1-liter separable flask equipped with a thermometer, a stirrer, and a 100-mL tank was charged with 26 g (0.8 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 58.5 g (0.5 mol) of 90 wt% sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 60 g of toluene, 197.0 g (1.8 mol) of ortho-cresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 50°C. 136 g (0.8 mol) of fluorenone was then added and slowly added dropwise to the separable flask over 30 minutes. The reaction was then allowed to proceed for 2 hours at 50°C. After completion of the reaction, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. The resulting organic phase was neutralized with saturated sodium bicarbonate solution, and the pH of the lower aqueous phase was confirmed to be 9 or higher. After removing the lower aqueous phase, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was taken and analyzed by high performance liquid chromatography, which revealed that 9,9-bis(4-hydroxy-3-methylphenyl)fluorene had been produced. The production rate was 85.6% by area.

[0187] [Example 28] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-milliliter dropping funnel was charged with 26.2 g (mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 58.5 g (0.6 mol) of 92 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 58.5 g of toluene, 192 g (1.8 mol) of orthocresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 50°C. 71.8 g (0.7 mol) of cyclohexanone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the addition of cyclohexanone, the reaction was allowed to proceed for 5 hours at 50°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the organic phase obtained was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the organic phase obtained and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the organic phase obtained was taken out and measured using a high-performance liquid chromatograph mass meter, which showed a mass number of 295 (M + -1) was observed, indicating that 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane was produced. The production rate of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane was confirmed using high-performance liquid chromatography, and was found to be 70.8 area %.

[0188] [Example 29] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 26.2 g (0.8 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 58.5 g (0.6 mol) of 92 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 58.5 g of toluene, 191 g (1.8 mol) of ortho-cresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 50°C. 42.5 g (0.4 mol) of cycloheptanone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the addition of cycloheptanone, the mixture was allowed to react for 5 hours at 50°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the obtained organic phase was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter in negative mode, and mass number 309 (M + -1) was observed, indicating that 1,1-bis(4-hydroxy-3-methylphenyl)cycloheptane was produced. The production rate of 1,1-bis(4-hydroxy-3-methylphenyl)cycloheptane was confirmed using high-performance liquid chromatography, and was found to be 25.9 area %.

[0189] [Example 30] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 26.2 g (0.8 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 58.5 g (0.6 mol) of 92 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 58.5 g of toluene, 191.5 g (1.8 mol) of orthocresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 50°C. 52.7 g (0.7 mol) of methyl ethyl ketone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the dropwise addition of methyl ethyl ketone, the mixture was allowed to react for 5 hours at 50°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the obtained organic phase was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter, which showed a mass number of 269 (M + -1) was observed, indicating that 2,2-bis(4-hydroxy-3-methylphenyl)butane was produced. The production rate of 2,2-bis(4-hydroxy-3-methylphenyl)butane was confirmed using high-performance liquid chromatography, and was found to be 47.6 area %.

[0190] [Example 31] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 26.2 g (0.8 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 58.5 g (0.6 mol) of 92 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 58.5 g of toluene, 191.5 g (1.8 mol) of orthocresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 50°C. 73.2 g (0.7 mol) of methyl isobutyl ketone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the dropwise addition of methyl isobutyl ketone, the mixture was allowed to react for 5 hours at 50°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the obtained organic phase was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter in negative mode, and a mass number of 297 (M + -1) was observed, indicating that 2,2-bis(4-hydroxy-3-methylphenyl)-4-methylpentane was produced. The production rate of 2,2-bis(4-hydroxy-3-methylphenyl)-4-methylpentane was confirmed using high-performance liquid chromatography, and was found to be 65.7% by area.

[0191] [Example 32] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 26.2 g (0.8 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 58.5 g (0.6 mol) of 92 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 18 g of toluene, 72 g (0.6 mol) of 2,6-xylenol, and 1.8 g (0.01 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 14.6 g (0.3 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction was allowed to proceed for 2 hours at 40°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. The resulting organic phase was then neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the resulting organic phase was removed and analyzed by high-performance liquid chromatography, confirming that 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane had been produced. The production rate of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane was 41.9 area %.

[0192] [Example 33] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 5.0 g (0.2 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 100 g (0.9 mol) of 92 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 54.3 g of toluene, 152 g (1.6 mol) of phenol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 50°C. 81 g (0.6 mol) of 3,3,5-trimethylcyclohexanone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the dropwise addition of 3,3,5-trimethylcyclohexanone, the reaction was allowed to proceed for 2 hours at 50°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the obtained organic phase was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter in negative mode, and mass number 309 (M + -1) was observed, indicating that 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was produced. The production rate of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was confirmed using high-performance liquid chromatography, and was found to be 62.5 area %.

[0193] [Example 34] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 4 g (0.1 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 84 g (0.7 mol) of 85 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 54 g of toluene, 151 g (1.4 mol) of orthocresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 70 g (0.6 mol) of acetophenone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the dropwise addition of acetophenone, the mixture was allowed to react for 2 hours at 40°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the obtained organic phase was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter in negative mode, and mass number 317 (M + -1) was observed, indicating that 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane was produced. The production rate of 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane was confirmed using high-performance liquid chromatography, and was found to be 48.2 area %.

[0194] [Example 35] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 18 g (0.6 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 25.8 g (0.2 mol) of 85 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Then, 24 g of toluene, 75 g (0.4 mol) of 2-phenylphenol, and 2.4 g (0.01 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 10.5 g (0.2 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction was allowed to proceed for 2 hours at 40°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the obtained organic phase was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter in negative mode, and a mass number of 379 (M + -1) was observed, indicating that 2,2-bis(4-hydroxy-3-phenylphenyl)propane was produced. The production rate of 2,2-bis(4-hydroxy-3-phenylphenyl)propane was confirmed using high-performance liquid chromatography, and was found to be 9.0 area %.

[0195] [Example 36] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 9 g (0.3 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 22 g (0.2 mol) of 85 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Then, 24 g of toluene, 50 g (0.3 mol) of 2-cyclohexylphenol, and 2.4 g (0.01 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 9 g (0.2 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction was allowed to proceed for 2 hours at 40°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. The resulting organic phase was neutralized with saturated sodium bicarbonate solution, and the pH of the lower aqueous phase was confirmed to be 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the resulting organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand and the aqueous phase was removed. A portion of the resulting organic phase was taken out and measured using a high-performance liquid chromatograph mass meter in negative mode, revealing a mass number of 391 (M + -1) was observed, indicating that 2,2-bis(4-hydroxy-3-cyclohexylphenyl)propane was produced. The production rate of 2,2-bis(4-hydroxy-3-cyclohexylphenyl)propane was confirmed using high-performance liquid chromatography, and was found to be 22.9 area %.

[0196] [Example 37] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 1.1 g (0.03 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 25.8 g (0.2 mol) of 85 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 7.5 g of toluene, 50 g (0.3 mol) of 2-benzylphenol, and 2.7 g (0.01 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 40°C. 7.7 g (0.1 mol) of acetone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the acetone addition was complete, the reaction was allowed to proceed for 2 hours at 40°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the organic phase obtained was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the organic phase obtained and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the organic phase obtained was taken out and measured using a high-performance liquid chromatograph mass meter, which showed a mass number of 407 (M + -1) was observed, indicating that 2,2-bis(4-hydroxy-3-benzylphenyl)propane was produced. The production rate of 2,2-bis(4-hydroxy-3-benzylphenyl)propane was confirmed using high-performance liquid chromatography, and was found to be 60.0 area %.

[0197] [Example 38] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 41.6 g (1.3 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 100 g (0.8 mol) of 80 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 54.3 g of toluene, 130 g (1.4 mol) of phenol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 30°C. 73 g (0.5 mol) of 2-ethylhexanal was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the addition of 2-ethylhexanal, the reaction was allowed to proceed for 2 hours at 30°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the obtained organic phase was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter in negative mode, and a mass number of 297 (M + -1) was observed, indicating that 1,1-bis(4-hydroxyphenyl)-2-ethylhexane was produced. The production rate of 1,1-bis(4-hydroxyphenyl)-2-ethylhexane was confirmed using high-performance liquid chromatography, and was found to be 52.4 area %.

[0198] [Example 39] A fully jacketed, 1-liter separable flask equipped with a thermometer, stirrer, and 100-mL dropping funnel was charged with 41.6 g (1.3 mol) of methanol under a nitrogen atmosphere, followed by the slow addition of 100 g (0.8 mol) of 80 wt. % sulfuric acid to generate a solution containing monomethyl sulfate. Subsequently, 54.3 g of toluene, 150 g (1.4 mol) of orthocresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature inside the separable flask was raised to 30°C. 73 g (0.5 mol) of 2-ethylhexanal was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the addition of 2-ethylhexanal, the reaction was allowed to proceed for 2 hours at 30°C. After the reaction was complete, 100.0 g of ethyl acetate and 100.0 g of dechlorinated water were added and mixed. The mixture was then allowed to stand, and the lower aqueous phase was removed. Thereafter, the obtained organic phase was neutralized by adding saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 9 or higher. After the lower aqueous phase was removed, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, the mixture was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter in negative mode, and a mass number of 325 (M + -1) was observed, indicating that 1,1-bis(4-hydroxy-3-methylphenyl)-2-ethylhexane was produced. When the production rate of 1,1-bis(4-hydroxy-3-methylphenyl)-2-ethylhexane was confirmed using high performance liquid chromatography, it was found to be 67.4 area %. The aromatic alcohols, ketones or aldehydes and the synthesized bisphenols for Examples 23 to 39 are summarized in Table 8. As a result, it was revealed that various bisphenols can be synthesized by using monoalkyl sulfate as a catalyst.

[0199] [Table 8a]

[0200] [Table 8b]

[0201] [Example 40] A -10°C refrigerant was flowed into the jacket of a fully jacketed, 1-liter separable flask equipped with a thermometer, a stirrer, and a 100-mL dropping funnel. Under a nitrogen atmosphere, 240 g of toluene, 9 g of methanol, and 172.5 g (1.60 mol) of ortho-cresol were added and the internal temperature was cooled to -5°C. Then, 67.5 g of 98 wt% sulfuric acid was added. A mixture of 4.1 g of dodecanethiol and 45.8 g (0.79 mol) of acetone was placed in the dropping funnel. When the internal temperature of the separable flask reached -5°C, the mixture was slowly added dropwise over 1 hour. After the addition, the mixture was stirred at 10°C for 1 hour, then heated to 45°C and stirred at 45°C for 1 hour. To the resulting reaction solution, 128 g of a 28 wt% aqueous sodium hydroxide solution was added. While heating to 80°C, a 28 wt% aqueous sodium hydroxide solution was added to adjust the pH to between 5 and 8. After the internal temperature reached 80°C, the aqueous phase was removed and washed with saturated sodium bicarbonate water and then with water. A portion of the resulting organic phase was removed and the amount of bisphenol C produced was confirmed by high performance liquid chromatography, and the reaction yield based on acetone was found to be 80 mol%.

[0202] [Example 41] A 150 mL glass reactor equipped with a stirrer and a distillation tube was charged with 100 g (0.39 mol) of bisphenol C obtained in Example 9, 86.5 g (0.4 mol) of diphenyl carbonate, and 479 μL of a 400 ppm by mass aqueous cesium carbonate solution. The pressure in the glass reactor was reduced to approximately 100 Pa, and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated three times to replace the atmosphere in the reactor with nitrogen. The reactor was then immersed in a 200°C oil bath to dissolve the contents. The stirrer was rotated at 100 rpm, and the pressure in the reactor was reduced from 101.3 kPa absolute to 13.3 kPa over 40 minutes while distilling off phenol, a by-product of the oligomerization reaction of bisphenol C and diphenyl carbonate in the reactor. The pressure in the reactor was then maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa absolute pressure to 399 Pa over 40 minutes, and the distilled phenol was removed from the system. The temperature outside the reactor was then raised to 280°C, and the absolute pressure inside the reactor was reduced to 30 Pa, and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the reactor's agitator reached a predetermined stirring power. The reactor was then restored to an absolute pressure of 101.3 kPa with nitrogen, and the gauge pressure was then increased to 0.2 MPa. Polycarbonate was extracted from the bottom of the reactor in the form of strands, yielding a strand-like polycarbonate resin. The strands were then pelletized using a rotary cutter to yield pellet-like polycarbonate resin.

[0203] The viscosity average molecular weight (Mv) of the polycarbonate was 25,000. The pellet YI was 7.6. [Industrial Applicability]

[0204] The present invention provides a bisphenol composition suitable as a raw material for producing polycarbonate resins, and a method for producing the same. Furthermore, the bisphenol composition of the present invention contains an aromatic alcohol sulfonate, which allows efficient melt polymerization reaction with a carbonate diester, thereby producing polycarbonate resins with excellent color tone.

Claims

1. A bisphenol composition, wherein the content of a bisphenol represented by general formula (3) in the bisphenol composition is 95.0 mass% or more, and the bisphenol composition contains an aromatic alcohol sulfonate represented by general formula (1) and / or general formula (2) in an amount of 1 ppb by mass or more and 1.0 mass% or less, based on the bisphenol. 【Chemistry 1】 (In the formula, R 11 to R 14 each independently represent any one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an aryl group. R 15 and R 16 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. Two groups within R 15 and R 16 may be bonded to or bridged with each other.) 【Chemistry 2】 (In the formula, R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group; and X represents a metal atom.) 【Transformation 3】 (In the formula, R 5 to R 8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group; and X represents a metal atom.) 2. The bisphenol composition according to claim 1, wherein R 1 to R 8 in the general formula (1) and / or the general formula (2) each independently represent a hydrogen atom or a methyl group.

3. 3. The bisphenol composition according to claim 1, wherein a phenol production rate in a reaction liquid obtained by heating a mixture of bisphenol and diphenyl carbonate, in which the molar ratio of diphenyl carbonate to bisphenol is 1.1, in an aluminum block heater heated to 194°C for 90 minutes is 0.3 area % or more.

4. 4. The bisphenol composition according to claim 1, wherein X in the general formula (1) and / or the general formula (2) is a sodium atom or a potassium atom.

5. A method for producing a polycarbonate resin, comprising reacting the bisphenol composition according to any one of claims 1 to 4 to produce a polycarbonate resin.

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