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

Abstract

To provide a bisphenol composition including a specific amount of aromatic alcohol sulfonate, and a simple method of producing the same; and provide a method of producing a polycarbonate resin in which, by using the bisphenol composition including a specific amount of aromatic alcohol sulfonate, a melt polymerization reaction can be efficiently allowed to proceed, producing a polycarbonate resin with an excellent color tone.SOLUTION: The present invention provides: a bisphenol composition including an aromatic alcohol sulfonate of at least 0.1 mass ppb with respect to a bisphenol; a method of producing a bisphenol composition, including reacting a ketone or an aldehyde with an aromatic alcohol in the presence of sulfuric acid to produce the bisphenol composition; a method of producing a polycarbonate resin, including producing the polycarbonate resin using the bisphenol composition; and a polycarbonate resin including a specific amount of aromatic alcohol sulfonate.SELECTED DRAWING: None

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. Furthermore, it relates to a polycarbonate resin containing an aromatic alcohol sulfonate. Finally, it relates to a method for producing bisphenol from the reaction of an aromatic alcohol with a ketone or aldehyde. A bisphenol composition, which is one embodiment of the present invention, is useful as a resin raw material such as polycarbonate resin, epoxy resin, aromatic polyester resin, or as an additive such as a curing agent, color developer, fade inhibitor, or other disinfectant or antifungal agent. [Background technology]

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

[0003] Furthermore, several methods for producing bisphenol are known, including 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 Publication No. 2008-214248 [Patent Document 2] Japanese Patent Application Laid-Open No. 62-138443 [Patent Document 3] Japanese Patent Publication No. 2014-40376 [Patent Document 4] Japanese Patent Publication No. 2015-51935 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, when the present inventors produced 2,2-bis(4-hydroxy-3-methylphenyl)propane using the method described in Patent Document 1, and used the obtained 2,2-bis(4-hydroxy-3-methylphenyl)propane to produce a polycarbonate resin by a melt polymerization reaction, the melt polymerization reaction did not proceed as expected. Furthermore, it was found that increasing the amount of catalyst in the melt polymerization reaction was necessary to produce the polycarbonate resin. Moreover, the amount of catalyst needed to advance the melt polymerization reaction 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 target polycarbonate resin.

[0006] The first object of the present invention, made in view of the above circumstances, is to provide a bisphenol composition containing a specific amount of aromatic alcohol sulfonate and a simple method for producing the same. Furthermore, the present invention provides a method for producing a polycarbonate resin that can efficiently carry out a melt polymerization reaction and produce a polycarbonate resin by using the bisphenol composition containing a specific amount of aromatic alcohol sulfonate. Moreover, the present invention provides a polycarbonate resin containing aromatic alcohol sulfonate.

[0007] Furthermore, while a manufacturing method using hydrogen chloride gas as a catalyst (Patent Document 2) is known as a highly versatile method for producing bisphenol, hydrogen chloride gas is highly corrosive, and specialized equipment is required for industrial implementation. A manufacturing method using hydrochloric acid as a catalyst (Patent Document 1) handles less hydrogen chloride than a manufacturing method using hydrogen chloride gas as a catalyst, but concentrated hydrochloric acid is corrosive and difficult to handle. It also has the problem of requiring a reaction time. A manufacturing method using a mixture of hydrochloric acid and sulfuric acid as a catalyst (Patent Document 3) has the problem of corrosiveness because it uses hydrochloric acid. In a manufacturing method using sulfuric acid as a catalyst (Patent Document 4), side reactions such as sulfonation of phenol are likely to occur, and it is necessary to use a relatively large amount of various solvents to suppress them (Non-Patent Document 1). In addition, sulfuric acid must be used, and as a result, side reactions such as condensation (multiplication) of the raw materials, such as ketones and aldehydes, are known to occur, resulting in coloring components. Furthermore, as a result of the inventors' investigations, it was found that the bisphenol reaction solution solidifies, and a problem arises in that a reaction time is required.

[0008] A second objective of the present invention, taken in view of these circumstances, is to provide a simple, efficient, and industrially advantageous method for producing bisphenol that does not impair the hue when used as a resin raw material or color developer, produces few by-products, and is industrially advantageous. [Means for solving the problem]

[0009] The inventors of the present invention conducted diligent research to solve the first problem described above, and as a result, discovered that polycarbonate resin can be efficiently produced by using a bisphenol composition containing a specific amount of aromatic alcohol sulfonate, thus completing the present invention.

[0010] In other words, the gist of the present invention, which solves the first problem described above, is found in the following [1] to [9]. [1] A bisphenol composition containing 0.1 ppb by mass or more of an aromatic alcohol sulfonate relative to bisphenol. [2] The bisphenol composition according to [1], wherein the molar ratio of diphenyl carbonate to bisphenol is 1.1, and the mixture of bisphenol and diphenyl carbonate is heated in an aluminum block heater heated to 194°C for 90 minutes, and the phenol production rate in the reaction solution 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. X represents a metal atom. [ka] (In the formula, R 5 ~R 8 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. X represents a hydrogen atom or a metal atom. [4] The bisphenol composition according to [3], wherein X in general formula (1) and / or 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 aromatic alcohol sulfonate relative to bisphenol is 1.0% by mass or less. [6] The bisphenol composition according to any one of [1] to [5], wherein the bisphenol content in the composition is 95.0% by mass or more. [7] A method for producing a bisphenol composition, comprising reacting a ketone or aldehyde with an aromatic alcohol in the presence of sulfuric acid to produce the bisphenol composition described in any of [1] to [6]. A method for producing a polycarbonate resin, comprising reacting a bisphenol composition described in any of [1] to [6] [8]. [9] A polycarbonate resin containing 1 ppb by mass or more of aromatic alcohol sulfonates.

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

[0012] In other words, the gist of the present invention lies in the following

[10] to

[16] .

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

[11] The method for producing bisphenol according to

[10] , wherein the monoalkyl sulfate is produced from the reaction of sulfuric acid and a fatty acid alcohol.

[12] A 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 into a reaction solution containing an aromatic alcohol.

[13] A 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] A 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] A method for producing bisphenol according to

[14] , wherein the thiol is mixed with the ketone or aldehyde, and then the monoalkyl sulfate is mixed. Bisphenol is produced by the method for producing bisphenol described in any of

[16]

[10] to

[15] , and the obtained bisphenol is reacted to produce a polycarbonate resin. A method for manufacturing polycarbonate resin. [Effects of the Invention]

[0013] According to one aspect of the present invention, a bisphenol composition containing a specific amount of an aromatic alcohol sulfonate and a simple method for producing the same are provided. In other words, according to the present invention, it is possible to provide a bisphenol composition containing a specific amount of aromatic alcohol sulfonate that can efficiently carry out the melt polymerization reaction in the production of polycarbonate resin from bisphenol and 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 the disappearance of water bubbles on the oil-water interface during washing can be accelerated, and a bisphenol composition containing an appropriate amount of aromatic alcohol sulfonate can be prepared simply and productively, thus providing a method for producing the above-mentioned bisphenol composition. Furthermore, it is possible to provide a method for producing polycarbonate resin in which the melt polymerization reaction is efficient and the resulting polycarbonate resin has excellent color tone, as well as polycarbonate with excellent color tone.

[0014] According to another aspect of the present invention, by using monoalkyl sulfate as a catalyst, the acid strength of the catalyst can be controlled, suppressing the condensation (multimerization) and discoloration of the ketones and aldehydes in the raw materials, and enabling the simple, efficient, and high-yield production of bisphenol with reduced by-reaction product formation and product discoloration. Furthermore, it is possible to produce polymer materials such as polycarbonate with reduced discoloration using this bisphenol.

[0015] Thus, according to the present invention, a simple, efficient, and industrially advantageous method for producing various types of bisphenols can be provided. Furthermore, by using the bisphenol produced by the production method of the present invention as a raw material for polymer materials such as polycarbonate resins, epoxy resins, and aromatic polyester resins, these resins can be produced efficiently, and polymer materials such as polycarbonate resins with excellent physical properties can be produced while suppressing the deterioration of hue due to coloring. [Modes for carrying out the invention]

[0016] The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is just one example of how the present invention can be carried out, and the present invention is not limited to the following description as long as it does not exceed the gist of the invention. In this specification, when the expression "~" is used, it is intended to include the numerical values ​​or physical properties before and after it.

[0017] [Bisphenol composition] One embodiment of the present invention, a bisphenol composition, contains an aromatic alcohol sulfonate at a concentration of 0.1 ppb by mass or more relative to bisphenol. Such bisphenol compositions are suitable as raw materials for polymers such as polycarbonate resins, and offer the advantage of efficiently carrying out polymerization reactions to produce polymers.

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

[0019] The following describes each component of the bisphenol composition.

[0020] <Aromatic alcohol sulfonates> "Aromatic alcohol sulfonates" are salts of aromatic alcohol sulfonic acid, and examples include sodium salts, potassium salts, and lithium salts of aromatic alcohol sulfonic acid. "Aromatic alcohol sulfonic acid" is a compound in which one hydrogen atom of an aromatic hydrocarbon is replaced by a hydroxyl group (OH group), and another hydrogen atom of an aromatic ring is replaced by a sulfonic acid group (SO2OH group). Furthermore, aromatic alcohol sulfonic acid may have a substituted structure (i.e., a structure with substituents other than OH groups and SO2OH groups) or an unsubstituted structure.

[0021] Furthermore, the aromatic hydrocarbon that forms the main skeleton of the aromatic alcohol sulfonate may be monocyclic (benzene ring) or polycyclic (naphthalene ring, anthracene ring, etc.). The aromatic alcohol sulfonate is preferably hydroxybenzenesulfonic acid. Hydroxybenzenesulfonic acid may have substituents. Among these, 4-hydroxybenzenesulfonates and / or 2-hydroxybenzenesulfonates, which may have substituents, 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 explanation will cover general formulas (1) and (2).

[0022] Examples of 4-hydroxybenzenesulfonates include 4-hydroxybenzenesulfonates that may contain substituents, as shown in the following general formula (1).

[0023] [ka]

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

[0025] Among these, when R 1 ~R 4 has a large number of carbon atoms, in the case of by-producing in the reaction system during the production of bisphenol described later, the lipophilicity of the hydroxybenzenesulfonate increases, the effect of the surfactant is reduced, the residual amount of the benzenesulfonate with respect to bisphenol increases, and the color tone of the polycarbonate tends to deteriorate. When R 1 ~R 4 has a small number of carbon atoms, it becomes possible to control the residual amount of the benzenesulfonate with respect to bisphenol to be small, and since the polymerization stability of the polycarbonate is improved, it is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

[0026] In general formula (1), R1 ~R 4 Specifically, an aryl group having a 4-hydroxyphenyl group (R 1 ~R 4 (where R is a hydrogen atom), 4-hydroxytolyl group (for example, R 1 R is a methyl group 2 ~R 4 (where is a hydrogen atom), 4-hydroxyxyl R group (for example, R 1 ,R 4 R is a methyl group 2 ,R 3 Examples include hydrogen atoms, but this is not limited to them.

[0027] In general formula (1), X is a metal atom. Examples of metal atoms include Group 1 elements of the periodic table, such as lithium, sodium, potassium, and cesium atoms. Of these, sodium or potassium atoms are preferred due to their low industrial cost, and sodium atoms are more preferred, but the formula is not limited to these.

[0028] Furthermore, examples of 2-hydroxybenzenesulfonates include 2-hydroxybenzenesulfonates that may have substituents, as shown in the following general formula (2).

[0029] [ka]

[0030] In general formula (2), R 5 ~R 8Examples of these include hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, and aryl groups, each independently. Alkyl groups, alkoxy groups, and aryl groups may be substituted or unsubstituted. For example, hydrogen atoms, halogen atoms such as fluoro groups, chloro groups, bromo groups, and iodine groups; linear or branched alkyl groups having 1 to 12 carbon atoms, such as methyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butyl groups, i-butyl groups, t-butyl groups, n-pentyl groups, i-pentyl groups, n-hexyl groups, n-heptyl groups, n-octyl groups, n-nonyl groups, n-decyl groups, n-undecyl groups, and n-dodecyl groups; and cyclic alkyl groups having 3 to 12 carbon atoms, such as cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, and cyclododecyl groups. Examples include 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 groups; alkyl groups having an aryl group as a substituent, such as benzyl groups; and aryl groups that may have an alkyl group as a substituent, such as phenyl, tolyl, and xylyl groups.

[0031] Of these, R 5 ~R 8 When the number of carbon atoms is high, the lipophilicity of hydroxybenzenesulfonate increases when it is produced as a by-product in the reaction system during the production of bisphenol, as described later. This reduces the effect of the surfactant, increases the amount of benzenesulfonate remaining in the bisphenol, and tends to worsen the color of the polycarbonate. 1 ~R 4 When the number of carbon atoms is small, it becomes possible to control the amount of benzenesulfonate remaining in bisphenol, which improves the polymerization stability of polycarbonate. Therefore, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferred.

[0032] In general formula (2), R5 ~R 8 Specifically, an aryl group having a 2-hydroxyphenyl group is a 2-hydroxyphenyl group (R 5 ~R 8 (where R is a hydrogen atom), 2-hydroxytolyl group (for example, R 7 is a methyl group, R 5 , R 6 , R 8 Examples include hydrogen atoms, but this is not limited to them.

[0033] In general formula (2), X is a metal atom. Examples of metal atoms include Group 1 elements of the periodic table, such as lithium, sodium, potassium, and cesium atoms. Of these, sodium or potassium atoms are preferred due to their low industrial cost, and sodium atoms are more preferred, but the formula is not limited to these.

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

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

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

[0037] For example, the bisphenol composition contains a predetermined amount of aromatic alcohol sulfonate, but it may also contain 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 is detected in untreated compositions at levels on the order of tens of ppb. Whether or not this sodium 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 is present, the reaction with diphenyl carbonate proceeds to produce bisphenol, while if a sulfonate is not present, bisphenol is not produced. In the present invention, if the phenol production rate in the reaction solution obtained after heating a mixture of bisphenol and diphenyl carbonate, in which the molar ratio of diphenyl carbonate to bisphenol is 1.1, is 0.3 area% or more, it can be determined that the sulfonate required for the present invention has been produced.

[0039] <Bisphenol> The bisphenol contained in a bisphenol composition is usually represented by the following general formula (3) It is a compound that can be found in other compounds.

[0040] [ka]

[0041] In the above general formula (3), R 11 ,R 12 ,R 13 ,R 14 They may be the same or they may be different. Also, there are two R in general formula (3). 11 ,R 12 ,R 13 ,R 14These may also be different from each other, but due to the convenience of synthesis and ease of availability, two Rs each are used. 11 ,R 12 ,R 13 ,R 14 It is preferable that they are the same. 11 ~R 14 For example, R in general formula (1) 1 ~R 4 and R in general formula (2) 5 ~R 8 Examples similar to those given as examples (R 1 Reach biR 7 R 11 To, R 2 and R 8 R 12 To, R 3 and R 6 R 13 To, R 4 R 14 These correspond to the respective items. The same applies to preferred items.

[0042] R 15 ,R 16Examples of these include hydrogen atoms, alkyl groups, alkoxy groups, and aryl groups, which can be substituted or unsubstituted. For example, hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butyl groups, i-butyl groups, t-butyl groups, n-pentyl groups, i-pentyl groups, n-hexyl groups, n-heptyl groups, n-octyl groups, 2-ethylhexyl groups, n-nonyl groups, n-decyl groups, n-undecyl groups, n-dodecyl groups, and other linear or branched alkyl groups having 1 to 20 carbon atoms, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cyclododecyl groups, and other cyclic alkyl groups having 3 to 20 carbon atoms, methoxy groups, ethoxy groups, Examples 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 that 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 The two groups may be bonded or bridged to each other, such as R 15 ,R 16 Examples of such linking groups include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclododecylidene, fluorenylidene, xanthonylidene, and thioxanthonylidene.

[0044] The bisphenols included in the bisphenol composition are 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, 2,2-bis(4-hydroxyphenyl)pentane, and 2,2-bis(4-hydroxy-3 Examples include, but are not limited to, 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, 2,2-bis(4-hydroxy-3-methylphenyl)propane is a suitable bisphenol.

[0045] For the aromatic alcohol sulfonate contained in the bisphenol composition to fully exhibit its effect as a polymerization catalyst during the production of polymers such as polycarbonate resins, the content of the aromatic alcohol sulfonate relative to the bisphenol should be 0.1 ppb by mass or more, 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. On the other hand, if the content of aromatic alcohol sulfonates relative to bisphenol is high, the color tone of polycarbonates using the bisphenol composition deteriorates. Therefore, the content is usually 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.

[0046] Furthermore, the bisphenol composition mainly consists of bisphenol and typically contains 95.0% by mass or more of bisphenol. The bisphenol content 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. Furthermore, it is preferable that the bisphenol composition contains a low amount of components other than bisphenol and aromatic alcohol sulfonates. In particular, when used as a raw material for polycarbonate resin, it is preferable that the bisphenol composition contains a low amount of components that inhibit polymerization with diester carbonate. In the method for producing the bisphenol composition described later (Method 4), components that inhibit polymerization with diester carbonate can be efficiently removed, and a bisphenol composition with an extremely low content of components that inhibit polymerization with diester carbonate can be obtained. Therefore, the bisphenol composition obtained by Method 4 of the method for producing the bisphenol composition can be suitably used as a raw material for polycarbonate resin.

[0047] [Method for producing bisphenol composition] There are no particular restrictions on the method for producing the bisphenol composition, but examples include the following methods. (Method 1) A method for obtaining a bisphenol composition by mixing solid bisphenol with an aromatic alcohol sulfonate whose content relative to the bisphenol is 0.1 ppb by mass or more. (Method 2) A method for obtaining a bisphenol composition by mixing molten bisphenol with an aromatic alcohol sulfonate whose content relative to the bisphenol is 0.1 ppb by mass or more. (Method 3) A method for producing a bisphenol composition by generating an aromatic alcohol sulfonate as a by-product during the production of bisphenol, and purifying it as necessary. (Method 4) A method to obtain a bisphenol composition by crystallizing an organic phase obtained from an organic phase after washing the solution with water, by dissolving a bisphenol crystallization composition containing an aromatic alcohol sulfonate salt in more than 100 ppm by mass and less than 1% by mass relative to bisphenol in a solvent.

[0048] (Method 1), (Method 2) Solid or molten bisphenol mixed with aromatic alcohol sulfonate In methods involving the mixing of bisphenol salts, the quality of the bisphenol composition is affected by the quality of the solid or molten bisphenol used, leading to variability in the quality of the resulting bisphenol composition. Furthermore, aromatic alcohol sulfonates must be prepared separately. Therefore, (Method 3) a method in which aromatic alcohol sulfonates are produced as a by-product in the reaction system for producing bisphenol to include hydroxybenzene sulfonates in the bisphenol composition, and (Method 4) a method in which a bisphenol composition is obtained by crystallization of a bisphenol crystallization composition are preferred.

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

[0050] <(Method 3) manufacturing method> One method for producing a bisphenol composition by generating aromatic alcohol sulfonates as a by-product along with bisphenol in the reaction system during the production of bisphenol is to produce bisphenol by condensing a ketone or aldehyde with an aromatic alcohol in the presence of sulfuric acid, which acts as an acid catalyst. This method allows for the generation of aromatic alcohol sulfonates derived from aromatic alcohols within the reaction system.

[0051] If too much aromatic alcohol sulfonate is produced as a by-product in the bisphenol reaction system, it can be purified to adjust the composition to contain aromatic alcohol sulfonate within the specified range for the bisphenol composition. For example, the obtained bisphenol product can be further washed with water, crystallized, suspended, and sprinkled to remove some of the aromatic alcohol sulfonate contained in the bisphenol product, thereby controlling the content to be within the specified range for the bisphenol composition. Further details will be described later.

[0052] As a method for producing bisphenol using the reaction of a ketone or aldehyde with an aromatic alcohol, one embodiment of the present invention can be employed, which is a method for producing bisphenol having a step of producing bisphenol from the reaction of an aromatic alcohol with a ketone or aldehyde, wherein the reaction solution used in the reaction is separated into an organic phase and an aqueous phase, and the aqueous phase contains monoalkyl sulfate. The bisphenol obtained by the manufacturing method according to this embodiment is of very high purity and has little discoloration, so it can be used in a method for producing high-purity polycarbonate. For example, high-purity polycarbonate can be obtained by polycondensing the bisphenol obtained by the manufacturing method of the present invention with diphenyl carbonate in the presence of a transesterification catalyst.

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

[0054] The reaction for the formation of bisphenol is carried out, for example, according to the reaction formula (4) shown below. In this reaction, by using sulfuric acid as a catalyst, for example, a hydroxybenzene sulfonate, represented by the following general formulas (1A) and / or (2A), corresponding to the aromatic alcohol starting material, can be produced as a by-product.

[0055] [ka] (In the formula, R 11 ~R 16 This is equivalent to the one in general formula (3). Also, R 12 and R 13 Since a condensation reaction is less likely to proceed if the material is sterically bulky, a proton is preferable.

[0056] [ka] (In the formula, R 11 ~R 14 This is equivalent to the one in general formula (3).

[0057] [ka] (In the formula, R 12 ~R 14 This is equivalent to the one in general formula (3).

[0058] (Aromatic alcohol) The aromatic alcohols used as raw materials for bisphenol are typically compounds represented by the following general formula (5).

[0059] [ka] (In the formula, R 11 ~R 14 This is equivalent to the one in general formula (3). Also, R 12 and R 13 Since a condensation reaction is less likely to proceed if the material is sterically bulky, a proton is preferable.

[0060] Examples of compounds represented by the above general formula (5) include phenol, methylphenol, dimethylphenol, ethylphenol, propylphenyl, butylphenol, methoxyphenol, ethoxyphenol, propoxyphenol, butoxyphenol, aminophenol, benzylphenyl, and phenylphenol.

[0061] (Ketones or aldehydes) Ketones or aldehydes are typically compounds represented by the following general formula (6).

[0062] [ka] (In the formula, R 15 ,R 16 This is equivalent to the one in general formula (3).

[0063] Specifically, compounds represented by the above general formula (6) include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanaldehyde, hexaldehyde, heptanealdehyde, octanealdehyde, nonanaldehyde, decanealdehyde, undecanealdehyde, and dodecanealdehyde; ketones such as acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, and dodecanone; and benzaldehyde. Examples include aryl alkyl ketones such as phenylmethyl ketone, phenylethyl ketone, phenylpropyl ketone, cresyl methyl ketone, cresyl ethyl ketone, cresyl propyl ketone, xylyl methyl ketone, xylyl ethyl ketone, and xylyl propyl ketone, as well as cyclic alkan ketones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, and cyclododecanone.

[0064] In a reaction involving the condensation of an aromatic alcohol with a ketone or aldehyde, a low molar ratio of aromatic alcohol to ketone or aldehyde ((moles of aromatic alcohol / moles of ketone) or (moles of aromatic alcohol / moles of aldehyde)) can lead to excessive ketone or aldehyde formation, while a high molar ratio can result in the loss of unreacted aromatic alcohol. Therefore, the molar ratio of aromatic alcohol to ketone or aldehyde is preferably 1.5 or higher, more preferably 1.6 or higher, even more preferably 1.7 or higher, and also preferably 15 or lower, more preferably 10 or lower, and even more preferably 8 or lower.

[0065] In reactions involving the condensation of aromatic alcohols with ketones or aldehydes, the ketone or aldehyde is typically supplied to a mixed solution of the aromatic alcohol and an acid catalyst. While the ketone or aldehyde can be supplied all at once or in stages, it is preferable to supply it in stages, such as by adding it dropwise, because the reaction that produces bisphenol is an exothermic reaction.

[0066] (sulfuric acid) Sulfuric acid that can be used as a catalyst can be supplied into the reaction system by using an aqueous solution of sulfuric acid (raw material sulfuric acid) which is sulfuric acid diluted with water, known as concentrated sulfuric acid or dilute sulfuric acid. Either 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 expansion of ketones or aldehydes, or cause sulfonation of the resulting bisphenol. Furthermore, when used in combination with aliphatic alcohols or thiols (described later), it may promote the dehydration and dimerization of aliphatic alcohols, or cause degradation of thiols. On the other hand, if the concentration of the raw material sulfuric acid used is too low, the reaction time will be prolonged, making it impossible to efficiently produce bisphenol. Therefore, the mass concentration of the raw material sulfuric acid used is preferably 50% by mass or higher, more preferably 60% by mass or higher. Furthermore, if the sulfuric acid concentration is high (i.e., the water concentration in the sulfuric acid is low) and the amount of solvent pre-mixed with acetone (details described later) is small relative to the amount of water contained in the sulfuric acid, there is a risk that acetone will increase in volume to form mesityl oxide (dimerization product), promoting the dehydration dimerization of aliphatic alcohols and 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, if the sulfuric acid concentration is high (i.e., the water concentration in the sulfuric acid is low) and the amount of solvent pre-mixed with acetone (details described later) is large relative to the amount of water contained in the sulfuric acid, acetone can suppress the increase in volume to form mesityl oxide (dimerization product), suppress the dehydration dimerization of aliphatic alcohols, and suppress the oxidative decomposition of thiols. Therefore, the concentration of the 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 too low, the sulfuric acid will be diluted by the water produced as a by-product during the condensation reaction, resulting in a longer reaction time. On the other hand, if it is too high, the ketone or aldehyde may be excessively expanded. For these reasons, the molar ratio of sulfuric acid to ketone or aldehyde is preferably 0.0001 or higher, more preferably 0.01 or higher, even more preferably 0.05 or higher, particularly preferably 0.1 or higher, and also preferably 10 or lower, more preferably 8 or lower, even more preferably 5 or lower, and particularly preferably 3 or lower.

[0068] (Reaction solution) The reaction solution used for the reaction between aromatic alcohols and ketones or aldehydes is separated into an organic phase and an aqueous phase, the aqueous phase containing monoalkyl sulfate. The aromatic alcohol is contained in the organic phase, and the ketone or aldehyde is separated into the organic phase. By including monoalkyl sulfate, the acidity of the catalyst can be controlled, suppressing the condensation (excessive addition) and discoloration of the ketone or aldehyde raw materials. Therefore, excessive production of aromatic alcohol sulfonic acid is suppressed, and bisphenol with reduced product discoloration can be produced simply and efficiently. Furthermore, the residual aliphatic alcohol used to generate the monoalkyl sulfate simultaneously 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, monot-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, and mono(2-(2'-hydroxyethoxy)ethoxyethyl) sulfate. Among these, monoalkyl sulfates with 8 or fewer carbon atoms are preferred because increasing the number of carbon atoms increases lipophilicity, making it difficult for monoalkyl sulfates to move between the organic and aqueous phases. ru. While there are no particular limitations on the method for producing monoalkyl sulfates, one method that allows for the simple and inexpensive acquisition of monoalkyl sulfates is the reaction between sulfuric acid and an aliphatic alcohol.

[0070] The concentration of monoalkyl sulfate can be determined, for example, by taking a portion of the aqueous phase obtained after mixing an aliphatic alcohol and sulfuric acid, and then... 1 This can be determined by analysis using 1H NMR. Examples of aqueous phases 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 it to stand; (3) an aqueous phase obtained by mixing an aliphatic alcohol and an aromatic alcohol, then supplying sulfuric acid, mixing, and allowing it 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 it to stand; and (5) an aqueous phase obtained by allowing the bisphenol reaction solution to stand. The concentration of monoalkyl sulfate in the reaction solution is preferably 0.0001% by weight or more and 50% by weight or less. Methods for preparing monoalkyl sulfate include mixing sulfuric acid and an aliphatic alcohol as shown below, and mixing a monoalkyl metal sulfate salt such as monoalkyl sodium sulfate with sulfuric acid. In this invention, the monoalkyl sulfate present in the bisphenol production process may be prepared in advance and mixed with at least a portion of the reaction raw materials, or it may be produced by coexisting sulfuric acid and an aliphatic alcohol in the reaction system for bisphenol production and then present in the reaction system.

[0071] Since mixing an aliphatic alcohol with sulfuric acid generates heat, it is preferable to perform the mixing below the boiling point of the aliphatic alcohol. The reaction to produce bisphenol from an aromatic alcohol and a ketone or aldehyde is preferably carried out in a solvent. Therefore, the monoalkyl sulfate can be supplied to the reactor after supplying the aromatic alcohol, solvent, ketone or aldehyde, and optionally a thiol, or it can be supplied to the reactor before supplying and mixing the ketone or aldehyde, and the monoalkyl sulfate can be mixed with the aromatic alcohol, etc., and then the ketone or aldehyde can be mixed. However, there is a risk of excessive ketone or aldehyde formation, so it is preferable to supply the monoalkyl sulfate to the reactor before supplying the ketone or aldehyde, and then mix the ketone or aldehyde with it.

[0072] (Aliphatic alcohols) Examples of aliphatic alcohols include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol, i-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, ethylene glycol, diethylene glycol, triethylene glycol, and other alkyl alcohols having 1 to 12 carbon atoms. As the number of carbon atoms increases, the lipophilicity of the aliphatic alcohol increases, making it difficult to mix with sulfuric acid and thus difficult to obtain monoalkyl sulfate. Therefore, alkyl alcohols with 8 or fewer 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 produced will be small and the reaction will take a long time, and 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 higher, more preferably 0.01 or higher, even more preferably 0.05 or higher, particularly preferably 0.1 or higher, and also preferably 10 or lower, more preferably 5 or lower, and even more preferably 3 or lower.

[0074] (Thiol) Furthermore, in reactions involving the condensation of aromatic alcohols with ketones or aldehydes, thiols can be used as co-catalysts. Examples of thiols that can be used as co-catalysts include mercaptocarboxylic acids such as mercaptoacetic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and 4-mercaptobutyric acid, as well as 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 too low, the effect of improving the selectivity of bisphenol by using a thiol co-catalyst cannot be obtained, and if it is too high, the thiol may be mixed into the bisphenol and the quality may deteriorate. For these reasons, the molar ratio of the thiol to the ketone and aldehyde is preferably 0.001 or higher, more preferably 0.005 or higher, even more preferably 0.01 or higher, and also preferably 1 or lower, more preferably 0.5 or lower, and even more preferably 0.1 or lower.

[0076] From the viewpoint of suppressing the oxidative decomposition of thiols, it is preferable to pre-mix thiols with ketones or aldehydes before using them in the reaction. The method of mixing thiols with ketones or aldehydes is to mix the ketones or aldehydes with the thiols, or to mix the ketones or aldehydes with the thiols. Furthermore, the method of mixing the mixture of thiols with ketones or aldehydes and the raw material sulfuric acid is to mix the raw material sulfuric acid with the mixture, or to mix the mixture with the raw material sulfuric acid, but it is preferable to mix the mixture with the raw material sulfuric acid. Moreover, it is even more preferable to supply the raw material sulfuric acid and aromatic alcohol to the reaction vessel first, and then supply the mixture to the reaction vessel and mix it.

[0077] (solvent) Aromatic hydrocarbons can be used as solvents in the reaction for producing bisphenol compositions. Furthermore, the solvent used in the production of bisphenol can be recovered and purified by distillation or other means 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, instead of using a solvent, a large amount of the aromatic alcohol raw material can be used as a substitute. In this case, unreacted aromatic alcohol will be lost, but this loss can be reduced by recovering and purifying it through distillation or other means and reusing it.

[0078] If the amount of solvent supplied to the reaction to produce bisphenol is too small, for example, compared to the amount of sulfuric acid used to prepare the monoalkyl sulfate, the produced bisphenol may decompose, potentially reducing the amount of bisphenol obtained. On the other hand, if the amount of solvent is too large relative to the amount of sulfuric acid, the condensation reaction rate between the ketone or aldehyde and the aromatic alcohol may decrease, potentially increasing the time required to produce bisphenol. Therefore, the amount of solvent used is preferably 0.05 times or more, more preferably 0.1 times or more, preferably 10 times or less, and more preferably 5 times or less, relative to the amount of sulfuric acid. In particular, when using highly concentrated sulfuric acid, the amount of solvent is preferably 1 time or more, more preferably 2 times or more, preferably 10 times or less, and more preferably 5 times or less, relative to the amount of sulfuric acid. Alternatively, a large amount of aromatic alcohol can be used as a solvent instead of a solvent. Unreacted aromatic alcohol is a loss, so it can be recovered and purified by distillation or other means and reused.

[0079] (Bisphenol formation reaction) The reaction for the formation of bisphenol is a condensation reaction. If the reaction temperature is too high, the oxidative decomposition of the co-catalyst by the catalyst proceeds easily, and if it is too low, the reaction time becomes long. Therefore, the preferred temperature is between 0°C and 50°C.

[0080] The reaction time for the product formation reaction is preferably within 30 hours, more preferably within 25 hours, and even more preferably within 20 hours, and usually 15 hours or more, because if it is too long, the produced bisphenol may decompose. It is also possible to stop the reaction by adding an amount of water equal to or greater than the amount of sulfuric acid used to lower the sulfuric acid concentration.

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

[0082] <(Method 4) manufacturing method> Method 4 involves dissolving a bisphenol crystallization composition containing more than 100 ppm by mass and 1% by mass or less of an aromatic alcohol sulfonate relative to bisphenol in a solvent to form a solution, and then obtaining a bisphenol composition by crystallization from the organic phase obtained after washing the solution with water. As described above, it is preferable that the bisphenol composition contains a low amount of components that inhibit the melt polymerization reaction. The manufacturing method (Method 4) is suitable for producing such a bisphenol composition.

[0083] The inventors have revealed that components that inhibit the melt polymerization reaction are readily present in bisphenol. They have found that by using a bisphenol crystallization composition (hereinafter sometimes simply referred to as "bisphenol crystallization composition") containing an aromatic alcohol sulfonate in an amount of more than 100 ppm by mass and 1% by mass or less relative to bisphenol, and then washing the solution obtained by dissolving the bisphenol crystallization composition with water, separating the oil and water, and crystallizing the resulting organic phase, components that inhibit the melt polymerization reaction (melt polymerization reaction inhibitors) can be easily removed.

[0084] This is presumed to be because, by using a bisphenol crystallization composition containing an aromatic alcohol sulfonate in a concentration of more than 100 ppm by mass and less than or equal to 1% by mass relative to bisphenol, the aromatic alcohol sulfonate contained in the bisphenol crystallization composition acts as a surfactant, making it easier to separate into the aqueous phase and the organic phase during washing with water. This reduces the residue of components that inhibit the melt polymerization reaction in the organic phase where the bisphenol composition dissolves, and allows for easy and efficient removal of these components into the aqueous phase.

[0085] Thus, by using the manufacturing method of (Method 4), a bisphenol composition, in particular a bisphenol composition with a low content of molten polymerization reaction inhibitors, can be obtained simply and efficiently. Furthermore, the bisphenol composition obtained by the manufacturing method (Method 4) can be used to stably carry out a melt polymerization reaction, thereby stably producing polycarbonate resin by melt polymerization.

[0086] In bisphenol crystallization compositions, if the aromatic alcohol sulfonate content is greater than 1% by mass relative to bisphenol, an excess of aromatic alcohol sulfonate tends to remain in the bisphenol composition after crystallization, which may reduce the reactivity with diester carbonate. The aromatic alcohol sulfonate content relative to 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 aqueous phase are difficult to separate in oil-water separation, and a large amount of components that inhibit the reaction with diester carbonate contained in bisphenol tend to remain in the organic phase. In addition, it takes a long time to separate the organic phase and 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 manufacturing 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 relative to bisphenol is mixed with an organic solvent (e.g., toluene, xylene, trimethylbenzene, etc.) and stirred at 60-95°C to obtain a solution (A) in which bisphenol and aromatic alcohol sulfonate are dissolved. 0.1-10 parts by mass of water (e.g., demineralized water, ion-exchanged water, etc.) is added to 1 part by mass of solution (A), and the mixture is stirred at 60-95°C for 0.1-1 hour. After stirring, the mixture is allowed to stand at 60-95°C to separate the oil and water. After oil and water separation, the aqueous phase is removed to obtain an organic phase (A). Bisphenol is precipitated from the organic phase (A). Subsequently, a bisphenol composition is obtained by solid-liquid separation and drying.

[0088] One method for precipitating bisphenol from the above organic phase (A) is to crystallize by gradually lowering the temperature from 60-95°C to 0-20°C over 1-10 hours. The crystallization time is approximately 1-10 hours.

[0089] The method for separating the precipitated bisphenol composition into solid and liquid is not particularly limited, and conventional methods such as filtration, centrifugation, and decantation can be used. Furthermore, the drying method may be either reduced-pressure drying or drying at atmospheric pressure. The drying temperature can be determined as appropriate, but from the viewpoint that if the drying temperature is too high, the bisphenol composition will fuse together and become impossible to remove from the apparatus, it is preferably 50 to 120°C.

[0090] Furthermore, a bisphenol crystallization composition containing more than 100 ppm by mass and 1% by mass or less of aromatic alcohol sulfonate relative to bisphenol is preferably obtained by reacting an aromatic alcohol with a ketone or aldehyde in the presence of a sulfuric acid catalyst, similar to the method described above (Method 3). Such a bisphenol crystallization composition containing a specific amount of aromatic alcohol sulfonate can be obtained, for example, by setting the molar ratio of sulfuric acid to aromatic alcohol (moles of sulfuric acid / moles of aromatic alcohol) to 0.1 to 10 (preferably 0.3 to 5, more preferably 0.5 to 3) and reacting 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] Furthermore, a bisphenol crystallization composition containing more than 100 ppm by mass and 1% by mass or less of aromatic alcohol sulfonate relative to bisphenol can be obtained by mixing a predetermined amount of aromatic alcohol sulfonate with commercially available bisphenol or the like.

[0092] <Uses of bisphenol compositions> Bisphenol compositions can be used as components, curing agents, additives, or precursors for various thermoplastic resins such as polyether resins, polyester resins, polyarylate resins, polycarbonate resins, polyurethane resins, and acrylic resins, as well as 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. They are also useful as additives such as color developers, anti-fading agents, disinfectants, and antifungal agents for thermal recording materials.

[0093] Of these, it is preferable to use them as raw materials (monomers) for thermoplastic resins and thermosetting resins because they can impart good mechanical properties, and more preferably as raw materials for polycarbonate resins and epoxy resins. It is also preferable to use them as color developers, and more preferably in combination with leuco dyes and color change temperature adjusters.

[0094] [Polycarbonate resin and method for producing the same] Next, we will explain a polycarbonate resin using a bisphenol composition as a raw material and a method for producing the same. One embodiment of the present invention is a polycarbonate resin that contains an aromatic alcohol sulfonate salt at a concentration of 1 ppb by mass or more. From the viewpoint of ensuring excellent color tone, the content of aromatic alcohol sulfonates 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, particularly preferably 10 ppb by mass or more, and also preferably 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, there is a measure of yellowness (also called "YI value" or "Yellowness Index value") used to evaluate the color tone, which can be measured according to ASTM D1925. In evaluating the color tone of polycarbonate resin, a YI value of 50 or less is preferable, a value of 30 or less is more preferable, and a value of 20 or less is even more preferable.

[0095] Polycarbonate resins using bisphenol compositions as raw materials can be produced by reacting the aforementioned bisphenol compositions or bisphenols obtained by the aforementioned methods for producing bisphenols. These can be produced by, for example, a transesterification reaction between the bisphenol composition and a diester carbonate such as diphenyl carbonate in the presence of an alkali metal compound and / or an alkaline earth metal compound. The above transesterification reaction can be carried out by appropriately selecting known methods, but an example using a bisphenol composition and diphenyl carbonate as raw materials is described below.

[0096] In a method for producing polycarbonate resin, it is preferable to use diphenyl carbonate in excess of bisphenol in the bisphenol composition. The amount of diphenyl carbonate used relative to bisphenol is preferably high in terms of having fewer terminal hydroxyl groups in the produced polycarbonate resin and having excellent thermal stability of the polymer, and preferably low in terms of having a fast transesterification reaction rate and facilitating the production of polycarbonate resin with a desired molecular weight. For these reasons, the amount of diphenyl carbonate used per mole of bisphenol is usually 1.001 moles or more, preferably 1.002 moles or more. Also, it is usually 1.3 moles or less, preferably 1.2 moles or less.

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

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

[0099] The amount of transesterification catalyst used per mole of bisphenol or diphenyl carbonate is typically 0.05 μmol or more, preferably 0.08 μmol or more, more preferably 0.10 μmol or more, and also typically 100 μmol or less, preferably 50 μmol or less, more preferably 20 μmol or less.

[0100] By using a transesterification catalyst within the above range, it is easy to obtain the polymerization activity necessary to produce a polycarbonate resin with a desired molecular weight, and it is also easy to obtain a polycarbonate resin with excellent polymer hue, no excessive polymer branching, and excellent fluidity during molding.

[0101] To produce polycarbonate resin by the above method, it is preferable to continuously supply both of the above raw materials to a raw material mixing tank, and to continuously supply the resulting mixture and the transesterification catalyst to a polymerization tank. In the production of polycarbonate resin by the transesterification method, the two raw materials are typically supplied to a raw material mixing tank, uniformly stirred, 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, which is one embodiment of the present invention described above, is of very high purity and has little discoloration, so it can be used in the production of high-purity polycarbonate. For example, 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. [Examples]

[0103] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

[0104] [Experiment I] [Raw materials and reagents] 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 were reagents 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 later. While the detection limit is usually 1 ppb without any special treatment of the sample, it can be reduced to 0.1 ppb by performing treatments such as concentration. Sodium phenolsulfonate reagent from Tokyo Chemical Industry Co., Ltd. was used. The cresol sulfonic acid solution (hereinafter sometimes referred to as "4-hydroxy-3-methylbenzenesulfonic acid" or "2-hydroxy-3-methylbenzenesulfonic acid") was prepared using a reagent manufactured by Kishida Chemical Co., Ltd. The diphenyl carbonate used was a product manufactured by Mitsubishi Chemical Corporation.

[0105] [analysis] (Time of bubble disappearance at the oil-water interface) The time it takes for bubbles to disappear from the oil-water interface is determined by visually counting the bubbles on the interface until the number of bubbles is 10 or less. The time taken was defined as the time taken for the water bubbles to disappear from the oil-water interface. The evaluation method for the time taken for the water bubbles to disappear from the oil-water interface was as follows: less than 10 minutes was "S", 10 minutes or more but less than 30 minutes was "A", 30 minutes or more but less than 1 hour was "B", and 1 hour or more was "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 was performed. 1 H-NMR and ICP mass spectrometer The analysis was performed by Na analysis using a measuring device. 1 H-NMR (Proton Nuclear Magnetic Resonance) 11HNMR measurements were performed using a JEOL Ltd. JNM-ECS400 NMR spectrometer. The sodium atom concentration was measured using the following procedure: Bisphenol was mixed with nitric acid and subjected to pressurized, sealed decomposition using a microwave decomposition apparatus. The resulting decomposition solution was diluted with pure water, and the sodium atom concentration in the bisphenol was measured using a Thermo Fisher Scientific ELEMENT2.

[0107] Furthermore, quantitative analysis of sodium 4-hydroxy-3-methylbenzenesulfonate and sodium 2-hydroxy-3-methylbenzenesulfonate was performed using a high-performance liquid chromatograph mass spectrometer under the following procedure and conditions, and a calibration curve prepared using standard substances was used. • High-performance liquid chromatography system: Agilent 1200, Capcellpak C18 MG3 3μm 75mm×4.6mm ID Method: Low-pressure gradient method ·Analysis temperature: 40℃ ·Eluent composition: Solution A: 1 mM / L ammonium formate aqueous solution containing acetic acid; Solution B: Acetonitrile At an analysis time of 0 minutes, the ratio of solution A to solution B is 99.5:0.5 (volume ratio; the same applies below). During the analysis time of 0-15 minutes, gradually change the eluent composition from Solution A:Solution B = 5:95. Maintain a ratio of Solution A:Solution B of 5:95 for the 15-25 minute analysis time. Analysis was performed at a flow rate of 1 milliliter / minute. ·Mass spectrometer: Agilent LC / MS 6130 • Method: ESI (using AJS probe)

[0108] (Phenol production rate) The rate of phenol production by the reaction of bisphenol C with diphenyl carbonate was determined by high-performance liquid chromatography (hereinafter referred to as LC) under the following procedure and conditions. • Equipment: Shimadzu Corporation CTO-10 column thermostat Shimadzu Corporation's SPD-M10AVP detector Shimadzu Corporation pump LC-10AD Inertsil ODS-II 5μm 150mm×4.6mm ID, manufactured by GL Sciences Co., Ltd. Method: Isoccult method ·Analysis temperature: 40℃ • Eluent composition: Water:Acetonitrile = 10:90 (volume ratio) • At 0 minutes of analysis time, the pump flow rate is 0.5 ml / min. During the analysis time of 0-15 minutes, gradually increase the pump flow rate to 2 ml / min. The analysis was performed while maintaining a pump flow rate of 2 ml / min for 15-30 minutes. The detection wavelength was set to 210 nm. The more of the component that inhibits the reaction of bisphenol C with diphenyl carbonate, the lower the phenol production rate; and the less of the component that inhibits the reaction, the higher the phenol production rate. . 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 (%) Note that LC area refers to the area of ​​the peak detected by high-speed chromatography.

[0109] (Composition of the bisphenol C production reaction solution) The compositional analysis of the bisphenol C production reaction solution was performed by high-performance liquid chromatography under the following procedure and conditions. • Equipment: Shimadzu LC-2010A, Imtakt ScherzoSM-C18 3μm 150mm×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 of B liquid: ammonium acetate: acetic acid: acetonitrile = 1.500 g: 1 milliliter: 900 milliliters · At an analysis time of 0 minutes, mobile phase A: mobile phase B = 60:40 (volume ratio, the same below). From an analysis time of 0 to 25 minutes, gradually change the composition of the eluent to mobile phase A: mobile phase B = 90:10, From an analysis time of 25 to 30 minutes, maintain mobile phase A: mobile phase B = 90:10, Perform the analysis at a flow rate of 0.8 milliliters per minute.

[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 contained in the reaction solution from the peak detected at a wavelength of 280 nm by high performance liquid chromatography, calculating the molar amount of the bisphenol C contained in the bisphenol C production reaction solution from that concentration, and calculating it by the molar amount of the bisphenol C ÷ molar amount of raw material acetone × 100%.

[0111] (Viscosity average molecular weight) The viscosity average molecular weight (Mv) was calculated 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 tube, and calculating the viscosity average molecular weight (Mv) by 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 performing colorimetric determination in accordance with the titanium tetrachloride / acetic acid method (see Makromol.Chem. 88, 215 (1965)).

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

[0114] [Reference example 1] 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% of water), 38.4 g of sodium hydroxide, and 32 g of desalted water were placed in a 1 L pear-shaped flask equipped with a magnetic rotor, and the flask was stirred in an ice bath. After confirming that the sodium hydroxide in the pear-shaped flask was 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 round-bottom flask and dried under reduced pressure using an evaporator equipped with an oil bath. A portion of the resulting white solid was washed with 100 g of acetone, followed by washing with 100 g of toluene to obtain 1.5 g of sodium cresol sulfonate. Using this sodium cresol sulfonate, a 2.3% by mass aqueous solution of sodium cresol sulfonate was prepared.

[0116] [Reference example 3] A 2.3% by mass aqueous solution of sodium phenolsulfonate was prepared using sodium phenolsulfonate.

[0117] [Reference example 4] In a 1 L separable flask equipped with a condenser, jacket, and anchor-shaped stirring blade, 100 g of xylenol and 10 g of toluene were added, followed by the slow addition of 100 g of 98% sulfuric acid. The mixture was stirred at 50°C for 1 hour. The resulting reaction solution was a slurry, which was filtered under reduced pressure. The resulting cake was placed in a 500 mL round-bottom flask, and toluene and 25% sodium hydroxide aqueous solution were added while monitoring the pH until neutralization was achieved. The resulting slurry was filtered under reduced pressure, the resulting cake was suspended and washed with ruene, rinsed with water, and dried under reduced pressure using a rotary evaporator to obtain 10 g of a white solid. NMR of the obtained white solid revealed it to be xylenol sulfonic acid (hereinafter sometimes referred to as 4-hydroxy-2,6-dimethylbenzenesulfonic acid). ICP mass spectrometry showed that the Na concentration in the white solid was 10% by mass, indicating that the white solid was sodium 4-hydroxy-2,6-dimethylbenzenesulfonate. Using the sodium xylenol sulfonate, a 2.3% by 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 added to prepare a bisphenol C composition containing 100 ppm by mass of sodium cresol sulfonate relative to bisphenol C. 4.7 g of bisphenol C composition and 4.5 g of diphenyl carbonate were added to a Teflon® test tube and heated for 90 minutes on an aluminum block heater heated to 194°C. A portion of the resulting reaction solution was taken out and the rate of phenol production by reaction with diphenyl carbonate was confirmed by high-performance liquid chromatography, and it was found that 0.5 area percent of phenol was produced.

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

[0120] [Example 3] 4.7 g of commercially available bisphenol C and 20 μL of sodium phenolsulfonate solution prepared in Reference Example 3 were added to prepare a bisphenol C composition containing 100 ppm by mass of sodium phenolsulfonate relative to bisphenol C. 4.7 g of bisphenol C composition and 4.5 g of diphenyl carbonate were added to a Teflon test tube and heated for 90 minutes on an aluminum block heater heated to 194°C. A portion of the resulting reaction solution was taken out and the rate of phenol production by reaction with diphenyl carbonate was confirmed by high-performance liquid chromatography, and it was found that 0.6 area percent 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, a sodium cresol sulfonate solution with a concentration of 230 ppm by mass relative to the bisphenol C composition was prepared. 20 μL of this aqueous solution was added to the bisphenol C composition to prepare a bisphenol C composition containing 1 ppb by mass of sodium cresol sulfonate relative to the bisphenol C. 4.7 g of bisphenol C composition and 4.5 g of diphenyl carbonate were added to a Teflon test tube and heated for 90 minutes on an aluminum block heater heated to 194°C. A portion of the resulting reaction solution was taken out and the rate of phenol production by reaction with diphenyl carbonate was confirmed by high-performance liquid chromatography, and it was found that 0.3 area percent 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 bisphenol C composition, 4.5 g of diphenyl carbonate, and 20 μL of a 33.7 μg / g potassium hydroxide aqueous solution were added to a Teflon® test tube and heated for 90 minutes on an aluminum block heater heated to 194°C. A portion of the resulting reaction solution was taken out and the rate of phenol production by reaction with diphenyl carbonate was confirmed by high-performance liquid chromatography, and 0.1 area percent 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 specifically for centrifugation, heated to completely dissolve, and a homogeneous solution was obtained. The resulting solution was allowed to cool to room temperature to obtain a solid. Subsequently, a glass filter and receiver were installed to form a centrifuge 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 levels were below the detection limit of 0.1 mass ppb, and aromatic alcohol sulfonates could not be detected.

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

[0124] [Comparative Example 3] A bisphenol C composition containing 100 ppm by mass of cresol acid relative to bisphenol C was prepared by adding 4.7 g of commercially available bisphenol C and a commercially available cresol acid solution. 4.7 g of bisphenol C composition and 4.5 g of diphenyl carbonate were added to a Teflon test tube and heated for 90 minutes on an aluminum block heater heated to 194°C. A portion of the resulting reaction solution was taken out and the rate of phenol production by reaction with diphenyl carbonate was checked by high-performance liquid chromatography, but no phenol was produced.

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

[0126] [Table 1]

[0127] [Example 5] (Manufacturing of compositions for bisphenol crystallization) A bisphenol C composition containing 0.1% by mass of orthocresolsulfonate sodium was prepared by adding 100 g of commercially available bisphenol C and 0.18 g of the sodium cresol sulfonate solution prepared in Reference Example 1 to a 1 L separable flask equipped with a condenser, jacket, and anchor-shaped stirring blade.

[0128] (Manufacturing of bisphenol compositions) 163g of toluene was placed in the above-mentioned separable flask and heated to 80°C to form a homogeneous solution. 40g of demineralized water was added to the homogeneous solution and mixed for 10 minutes while maintaining the temperature at 80°C, then allowed to stand to separate the oil and water. The time it took for the water bubbles to disappear from the oil-water interface was 1 minute and 34 seconds. After that, the separable flask Then the aqueous phase was removed to obtain the organic phase. The obtained organic phase was cooled from 80°C to 10°C to crystallize bisphenol C, and then solid-liquid separation was performed using a centrifuge 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 an 80°C water bath to obtain 95 g of the washed and dried bisphenol C composition. When a portion of the above bisphenol C composition was taken out and the amounts of sodium 4-hydroxy-3-methylbenzenesulfonate and sodium 2-hydroxy-3-methylbenzenesulfonate were determined using a high-performance liquid chromatography-mass spectrometer, it 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 washed and dried bisphenol C composition, 4.5 g of diphenyl carbonate, and 20 μL of a 33.7 ppm by mass potassium hydroxide aqueous solution were added to a Teflon® test tube and heated for 90 minutes on 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, and 1.2 area percent of phenol was produced.

[0130] [Example 6] The procedure was carried out in the same manner as in Example 5, except that a commercially available bisphenol C from a different manufacturing lot was used compared to the commercially available bisphenol C used in Example 5. As a result, when 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, 1.2 area percent of phenol was produced.

[0131] [Example 7] The procedure was carried out in the same manner as in Example 5, except that commercially available bisphenol C from a different manufacturing lot was used compared to the bisphenol C used in Examples 5 and 6. As a result, when 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, 1.2 area percent of phenol was produced.

[0132] [Comparative Example 4] 100 g of commercially available bisphenol C and 163 g of toluene were placed in a 1 L separable flask equipped with a condenser, jacket, and anchor-shaped stirring blade, and the temperature was raised to 80°C to obtain a homogeneous solution. 40 g of demineralized water was added to the homogeneous solution, and after mixing at 80°C for 10 minutes, the mixture was allowed to stand to separate the oil and water. The water bubbles on 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, which still had some water bubbles remaining, was cooled from 80°C to 10°C to crystallize bisphenol C, and solid-liquid separation was performed using a centrifuge to obtain wet bisphenol C. The wet bisphenol C was placed in a 1 L pear-shaped flask and dried under reduced pressure using a rotary evaporator equipped with an 80°C water bath to obtain 96 g of washed and dried bisphenol C.

[0133] In a Teflon® test tube, add 4.7g of the bisphenol C and diphenyl carbonate. 4.5 g and 20 μL of a 33.7 ppm by mass potassium hydroxide aqueous solution were added, and the mixture was heated for 90 minutes on an aluminum block heater heated to 194°C. A portion of the resulting reaction solution was taken out, and the rate of phenol production by reaction with diphenyl carbonate was confirmed by high-performance liquid chromatography, revealing that 0.2 area percent 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 are placed in a 10 mL glass container specifically for centrifugation, heated, and completely dissolved to obtain a homogeneous solution. The obtained solution was allowed to cool to room temperature to obtain a solid. Then, a glass filter and receiver were set up to form a centrifuge 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, aromatic alcohol sulfonates were analyzed. However, aromatic alcohol sulfonates could not be detected as the detection limit was less than 0.1 mass ppb.

[0134] Table 2 summarizes 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 of bubble disappearance on 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 rate of phenol production by reaction with diphenyl carbonate for Examples 5 to 7 and Comparative Example 4.

[0135] From Example 5, it can be seen that the bisphenol C composition obtained by adding sodium cresol sulfonate to obtain a bisphenol crystallization composition and then washing (washing with water and crystallization) shows that the time it takes for water bubbles to disappear at the oil-water interface is short, indicating that sodium cresol sulfonate acts as a surfactant. Furthermore, since the rate of phenol production by reaction with diphenyl carbonate in Example 5 is higher than in Example 1, it can be inferred that, in addition to the catalytic effect that promotes the reaction with diphenyl carbonate, components that inhibit the reaction with diphenyl carbonate contained in the bisphenol C composition are efficiently removed by washing after adding sodium cresol sulfonate to obtain the bisphenol crystallization composition. Furthermore, as shown in Examples 5-7, even when using bisphenol C from different manufacturing lots as raw materials, it is possible to similarly remove components that inhibit the reaction with diphenyl carbonate contained in bisphenol C by adding cresol sulfonic acid to obtain a crude bisphenol product and then washing it, thereby enabling the stable production of a bisphenol C composition with stable quality. In addition, the results of the phenol production rate by reaction with diphenyl carbonate in Examples 5-7 show that the obtained bisphenol C composition can stably undergo the reaction with diphenyl carbonate.

[0136] Comparative Example 4 is an example of producing bisphenol C in the same manner as in Examples 5 to 7, except that commercially available bisphenol C was used as is, without adding sodium cresol sulfonate to commercially available bisphenol C to create a bisphenol crystallization composition. From Comparative Example 4, it can be seen that the bisphenol C obtained by washing (washing with water and crystallization) commercially available bisphenol C also has a low rate of phenol production through reaction with diphenyl carbonate, indicating that components that inhibit the reaction cannot be sufficiently removed by this washing.

[0137] [Table 2]

[0138] [Example 8] (Manufacturing of compositions for bisphenol crystallization) In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 35.0 g (1.1 mol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 77.7 g (0.7 mol) of 88% sulfuric acid. Then, 72.6 g of toluene, 255.0 g (2.4 mol) of ortho-cresol, and 7.3 g (0.04 mol) of dodecanethiol were added to the separateable flask in a reactor, and the temperature inside the flask was raised to 50°C. 57.0 g (1.0 mol) of acetone was added to the dropping funnel and slowly supplied to the separateable flask dropwise over 30 minutes. After the addition of acetone was complete, the reaction solution was orange in color. This reaction solution was allowed to react at 50°C for 15 hours. 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 reaching 80°C, the mixture was allowed to stand to confirm that the precipitated material had dissolved in the organic and aqueous phases, and then the aqueous phase was withdrawn. Subsequently, saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the aqueous phase was 9 or higher. After withdrawing the 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 withdrawn. A portion of the obtained organic phase was isolated, and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography. The reaction yield, based on acetone, was 85 mol%. This organic phase was cooled from 80°C to 30°C, and precipitation was confirmed by adding 1 g of bisphenol C seed crystals when it reached 30°C. Subsequently, it was 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 the bisphenol C crystallization composition 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 determined using a high-performance liquid chromatograph-mass spectrometer. The results showed that it contained 35 ppm by mass of sodium 4-hydroxy-3-methylbenzenesulfonate and 160 ppm by mass of sodium 2-hydroxy-3-methylbenzenesulfonate.

[0140] (Manufacturing of bisphenol compositions) 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 formed, the organic phase was thoroughly washed in two separate washes with 600g of desalted water. The time it took for the water bubbles to disappear from the oil-water interface was approximately 5 minutes. The obtained organic phase was cooled from 80°C to 10°C. Then, it was filtered using a centrifuge (3000 rpm for 10 minutes) to obtain wet, purified bisphenol C. Using an evaporator equipped with an oil bath, the light-boiling components were removed under reduced pressure at an oil bath temperature of 100°C to obtain 180.9 g of 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 specifically for centrifugation, and heated to completely dissolve and obtain a homogeneous solution. The solution was allowed to cool to room temperature to obtain a solid. Then, a glass filter and a receiver were placed in the glass container to make 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 obtained liquid was taken out, and the amounts of 4-hydroxy-3-methylbenzenesulfonic acid and sodium 2-hydroxy-3-methylbenzenesulfonate were checked using a high-performance liquid chromatograph-mass spectrometer. It was found to contain 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 potassium hydroxide aqueous solution were added to a Teflon® test tube and heated for 90 minutes on an aluminum block heater heated to 194°C. A portion of the resulting reaction solution was taken out and the initial polymerization activity was confirmed by high-performance liquid chromatography, which showed that 1.6 area percent of phenol had been formed.

[0143] (Manufacturing of polycarbonate resin) 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 cesium carbonate aqueous solution were placed in a 150 mL glass reaction vessel equipped with a stirrer and a distillation tube. The glass reaction vessel was reduced to approximately 100 Pa, and then the pressure was restored to atmospheric pressure with nitrogen, a process that was repeated three times to replace the inside of the reaction vessel with nitrogen. After that, the reaction vessel was immersed in an oil bath at 200°C to dissolve the contents. The stirrer was set to rotate at 100 revolutions per minute, and the pressure inside the reaction vessel was reduced from 101.3 kPa to 13.3 kPa absolute pressure over 40 minutes while distilling off the phenol produced as a by-product of the oligomerization reaction between bisphenol C and diphenyl carbonate. Subsequently, the pressure inside the reaction vessel was maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off the phenol. Subsequently, the external temperature of the reaction vessel was raised to 250°C, and the internal pressure of the reaction vessel was reduced from 13.3 kPa to 399 Pa in absolute pressure over 40 minutes to remove the distilled phenol from the system. Then, the external temperature of the reaction vessel was raised to 280°C, and the absolute pressure of the reaction vessel was reduced to 30 Pa to carry out the polycondensation reaction. The polycondensation reaction was terminated when the stirrer in the reaction vessel reached a predetermined stirring power. Next, the reaction vessel was repressurized to 101.3 kPa in absolute pressure using nitrogen, and then increased to 0.2 MPa in gauge pressure. Polycarbonate was extracted from the bottom of the reaction vessel in strand form to obtain strand-shaped polycarbonate resin. Subsequently, the strands were pelletized using a rotary cutter to obtain pellet-shaped polycarbonate resin. The viscosity-average molecular weight (Mv) of the polycarbonate was 24,800, and the terminal hydroxyl group concentration (OH concentration) was 769 ppm by mass. The pellet YI was 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. (Content of aromatic alcohol sulfonates in polycarbonate resin) In a 50 mL Erlenmeyer flask equipped with a stirring bar, 0.2 g of the obtained polycarbonate and 1 mL of methylene chloride were placed and dissolved. Then, while stirring thoroughly, 4 mL of methanol was added. The solution was slowly added dropwise, and after the addition was complete, the Erlenmeyer flask was placed in a water bath and extracted for 30 minutes. The entire volume of the obtained solution was collected in a 15 mL centrifuge tube and centrifuged at 5000 rpm for 15 minutes. After centrifugation, 3 mL of the supernatant was collected in a 50 mL round-bottom flask. The 50 mL round-bottom 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 dry material obtained by evaporation to dryness, and after sealing the flask, it was extracted with ultrasound for 5 minutes. A portion of the obtained solution was analyzed with a high-performance liquid chromatograph, and 3 ppb by mass of 2-hydroxy-3-methylbenzenesulfonic acid was detected. Since the amount of sodium 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] Orthocresol used was either a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. or a product manufactured by Nippon Steel Chemical Corporation. Acetone and methanol used were either special-grade reagents manufactured by Wako Pure Chemical Industries, Ltd. or products manufactured by Daishin Chemical Co., Ltd. Dodecanethiol was obtained using either a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. or a product manufactured by Kao Corporation. Toluene used was either a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. or a product manufactured by Cosmo Oil Co., Ltd.

[0145] For the sulfuric acid used, we used either 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, orthoxylene, paraxylene, 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 prepared using special grade reagents 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. 1,1-bis(4-hydroxyphenyl)dodecane was a product manufactured by Shinryo Co., Ltd.

[0147] [analysis] Analysis of monomethyl sulfate and mono(2-hydroxyethyl) sulfate is performed using proton nuclear magnetic resonance ( 1 The measurement was performed using proton nuclear magnetic resonance (HNMR). 1 1HNMR measurements were performed using a JEOL Ltd. JNM=ECS400 spectroscopy machine. The generated bisphenol was analyzed using high-performance liquid chromatography-mass spectrometry (LCMS). The measurement was performed by [method / condition]. High-performance liquid chromatography-mass spectrometry (LCMS) was performed using the following procedure and conditions.

[0148] (Separation equipment): Agilent 1200, manufactured by Agilent Technologies, Inc., with ImtaktScherzo SM-C18 3μm 150mm x 4.6mm ID. Low-pressure gradient method. Analysis temperature 40℃. Eluent composition: Solution A: Ammonium acetate:acetic acid:dechlorinated water = 3,000g:1ml:1L solution. Solution B: Ammonium acetate:acetic acid:acetonitrile = 1,500g:1ml:1,000ml solution. At 0 minutes of analysis, Solution A:Solution B = 60:40 (volume ratio, the same applies below). From 0 to 25 minutes of analysis, the eluent composition was gradually changed to Solution A:Solution B = 90:10, and from 25 to 30 minutes of analysis, it was maintained at Solution A:Solution B = 90:10, and the 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, Inc. The ion source uses an ESI (Positive / Negative) AJS probe. The compositional analysis of the bisphenol reaction solution was performed by high-performance liquid chromatography under the following procedure and conditions.

[0150] (Separation apparatus): Shimadzu LC-2010A, ImtaktScherzoSM-C18 3μm 150mm×4.6mm ID. Low-pressure gradient method. Analysis temperature 40℃. Eluent composition: Solution A: Ammonium acetate:acetic acid:dechlorinated water = 3,000g:1ml:1L solution. Solution B: Ammonium acetate:acetic acid:acetonitrile = 1,500g:1ml:900ml solution. At 0 minutes of analysis, Solution A:Solution B = 60:40 (volume ratio, same below). From 0 to 25 minutes of analysis, the eluent composition was gradually changed to Solution A:Solution B = 90:10, and from 25 to 30 minutes of analysis, it was maintained at Solution A:Solution B = 90:10, and the 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 determining the molar amount of bisphenol contained in the reaction solution from the analytical value of bisphenol obtained by high-performance liquid chromatography, and then dividing the molar amount of bisphenol by the molar amount of raw material acetone and multiplying by 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 and multiplying by 100 (area %). The production rate (area %) of substances other than the isopenyl cresol dimer can be calculated using the same method. The acetone-based yield (mol%) according to the present invention was calculated as follows: molar amount of bisphenol obtained ÷ molar amount of raw material acetone × 100%

[0152] [Reference example 5] 0.2g of methanol was placed in a 50ml round-bottom flask, and 0.5g of 92% by weight sulfuric acid was slowly added and shaken for 1 minute. This solution was placed in a 5mmφ NMR sample tube, and a deuterated chloroform tube (2mmφ sealed tube) for locking was inserted into the sample. 1 HNMR was measured. 1 A signal was observed at δ4.0 ppm on the 1H NMR spectrum. When 9.7 mg of the reagent sodium monomethyl sulfate was added to the NMR sample tube, the peak at δ4.0 ppm increased, confirming that this peak was the proton signal of monomethyl sulfate. From this result, 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 round-bottom flask, and 0.5 g of 92 wt% sulfuric acid was slowly added and shaken for 1 minute. This solution 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. 1On the HNMR spectrum, broad signals considered to be sulfuric acid (2-hydroxyethyl) were detected at δ 3.98 - 3.99 ppm and 4.19 - 4.21 ppm. From these results, it was confirmed that mono(2-hydroxyethyl) sulfate was formed by mixing sulfuric acid and ethylene glycol.

[0154] [Example 9] 35.0 g (1.1 mol) of methanol was placed in a 1-liter separable flask with a full jacket equipped with a thermometer, a stirrer, and a 100-milliliter dropping funnel 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 out, placed in a 5 mmφ NMR sample tube, and a deuterated chloroform tube for locking (2 mmφ sealed tube) was inserted into the sample 1 to measure HNMR. 1A signal at δ4.0 ppm was observed on the 1H NMR spectrum, confirming the generation of monomethyl sulfate. Furthermore, the amount of monomethyl sulfate generated was calculated from the integral of the peaks attributed to δ4.0 ppm (monomethyl sulfate) and methanol, resulting in an amount of 30% by weight. 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 addition of acetone was complete, the reaction solution was orange in color. This reaction solution was allowed to react 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 reaching 80°C, the mixture was allowed to stand to allow the precipitated material to dissolve in both the organic and aqueous phases. The lower aqueous phase was then 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 out, and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography (HPL). The reaction yield, based on acetone, was 85 mol%. Furthermore, a peak observed at a retention time of 15.7 minutes in the HPL was measured using HPL mass spectrometry in Negative mode, and the mass number was 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 isopropenyl cresol dimer was 0.7 area%. This organic phase was cooled from 80 to 30°C, and when it reached 30°C, 1 g of seed crystal 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as bisphenol C) was added and precipitation was confirmed. After that, it was 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 1-liter fully jacketed separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80°C. After confirming that a homogeneous solution had been formed, it was cooled to 10°C. Subsequently, wet-purified bisphenol C was obtained by vacuum filtration using a glass filter. Using an evaporator equipped with an oil bath, the light-boiling components were removed by distillation under reduced pressure at an oil bath temperature of 100°C to obtain 180.9 g of bisphenol C (0.7 mol, yield 72 mol% based on acetone).

[0156] [Example 10] In a fully jacketed 1.5-liter separable flask equipped with a thermometer, stirrer, and dropping funnel, 0.1 g (3.1 mmol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 250 g (0.7 mol) of 80% sulfuric acid. A portion of the resulting solution was taken out, 1¹HNMR spectroscopy revealed that 10 wt ppm 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 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 to maintain the internal temperature at 30°C. After the addition of the acetone and dodecanethiol mixture was complete, the reaction solution was orange in color. The resulting reaction solution was mixed at 30°C for 1 hour, and then the temperature was raised to 45°C to allow the reaction to proceed. After reaching 45°C (completion of the reaction), 175.5 g of desalinated water and 135 g of 28% sodium hydroxide aqueous solution were added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand to allow the precipitated material to dissolve in both the organic and aqueous phases. The lower aqueous phase was then 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 out, and the amount of bisphenol C produced was determined by high-performance liquid chromatography. The reaction yield, based on acetone, was 69 mol%. The production rate of isopropenyl cresol dimers was 0.24 area%.

[0157] [Example 11] In a fully jacketed 1.5-liter separable flask equipped with a thermometer, stirrer, and dropping funnel, 12 g (3.1 mmol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 250 g (0.7 mol) of 80% sulfuric acid. A portion of the resulting solution was taken out, 1¹HNMR spectroscopy revealed 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 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 to maintain the internal temperature at 30°C. After the addition of the acetone and dodecanethiol mixture was complete, the reaction solution was orange in color. The resulting reaction solution was mixed at 30°C for 1 hour, and then the temperature was raised to 45°C to allow the reaction to proceed. After reaching 45°C (completion of the reaction), 175.5 g of desalinated water and 135 g of 28% sodium hydroxide aqueous solution were added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand to allow the precipitated material to dissolve in both the organic and aqueous phases. The lower aqueous phase was then 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 the mixture was 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 determined by high-performance liquid chromatography. The reaction yield, based on acetone, was 63 mol%. The production rate of isopropenyl cresol dimers was 0.13 area%.

[0158] [Comparative Example 5] A fully-jacketed 1-liter separable flask equipped with a thermometer, a stirrer, and a 100-milliliter dropping funnel was charged under a nitrogen atmosphere with 58.5 g (0.6 mol) of 92 wt% sulfuric acid, 54.3 g of toluene, 191.5 g (1.8 mol) of ortho-cresol, and 5.5 g (0.03 mol) of dodecanethiol, and the temperature inside the separable flask was set to 50 °C. 42.5 g (0.7 mol) of acetone was placed in the dropping funnel and slowly dropped into the separable flask over 30 minutes for supply. After the dropping of acetone was completed, the reaction solution was reddish-brown. When this reaction solution was reacted at 50 °C for 30 minutes, the reaction solution completely solidified and became impossible to mix. Then, 100 g of dechlorinated water and 200 g of ethyl acetate were added, and the mixture was stirred for 5 minutes to dissolve the precipitate. The resulting solution was allowed to stand, and the aqueous phase was removed. Then, a saturated sodium hydrogen carbonate solution was added to the obtained organic phase for neutralization, and it was confirmed that the pH of the lower aqueous phase became 9 or higher. After extracting the lower aqueous phase, dechlorinated water was added to the obtained organic phase and stirred for 10 minutes. After stirring, it was allowed to stand and the aqueous phase was extracted. When a part of the obtained organic phase was taken out and the amount of bisphenol C produced was confirmed by high performance liquid chromatography, it was 40 mol%. Also, the production rate of the dimer of isopropenyl cresol was 6.2 area%.

[0159] [Reference Example 7] In a fully jacketed 1.5-liter separable flask equipped with a thermometer, stirrer, and dropping funnel, 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 were placed under a nitrogen atmosphere and heated to 30°C. 250 g (0.7 mol) of 70% sulfuric acid was placed in the dropping funnel and slowly added dropwise to the separable flask while maintaining the internal temperature at 30°C. After the addition of sulfuric acid was complete, the reaction solution was reddish-brown in color. This reaction solution was mixed at 30°C for 1 hour, and then the temperature was raised to 45°C to allow the reaction to proceed. After the reaction was complete, 175.5 g of dechlorinated water and 125 g of 28% sodium hydroxide aqueous solution were added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand to allow the precipitated material to dissolve in both the organic and aqueous phases. The lower aqueous phase was then 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 out, 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 dimers was 0.3 area%.

[0160] [Reference example 8] In a full-jacketed 1.5-liter separable flask equipped with a thermometer, a stirrer, and a dropping funnel, 85 g of methanol, 168 g (1.6 mol) of ortho-cresol, and 30 g (0.5 mol) of acetone were placed in the separable flask under a nitrogen atmosphere and cooled to 10°C. 100 g of 98% sulfuric acid was placed in the dropping funnel and slowly dropped into the separable flask while maintaining the internal temperature at 10°C. After the dropping of the sulfuric acid was completed, the reaction solution was a uniform reddish-brown solution. This reaction solution was mixed at 10°C for 1 hour as it was, then 200 g of toluene was added, the temperature was raised to 30°C, and two-phase separation was carried out. A part of the obtained organic phase was taken out, and the amount of bisphenol C produced by high-performance liquid chromatography was confirmed. It was found that bisphenol C was present in trace amounts (1 mol%), and a plurality of other by-products were produced.

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

[0162]

Table 3

[0163] From Table 3, it was found that when methyl hydrogen sulfate was used as a catalyst, the coloring of the reaction solution and the formation of a dimer of isopropenyl cresol as a by-product were suppressed, and bisphenol C with excellent color tone could 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 glass-lined, fully jacketed reaction vessel equipped with a thermometer, stirrer, and dropper. 255 kg of methanol was supplied to the dropper and slowly added to the reaction vessel to obtain a monomethyl sulfate solution. 530 kg of toluene, 1861 kg (17.2 kilomol) of ortho-cresol, and 53 kg of dodecyl mercaptan were supplied to an 8 cubic meter glass-lined, fully jacketed reaction vessel equipped with a thermometer, stirrer, and dropper. 413 kg (7.1 kilomol) of acetone was supplied to the dropper. Subsequently, the monomethyl sulfate solution was slowly transferred to the 8 cubic meter glass-lined reaction vessel, and then acetone was slowly added to ensure that the internal temperature of the reaction vessel did not exceed 30°C. After the acetone was added, the internal temperature of the reaction vessel was raised to 50°C and the mixture was stirred 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 supplied to the reaction vessel so that the internal temperature remained below 50°C. The temperature was then raised to 80°C, and after standing, the lower aqueous phase was removed. 599 kg of 1.5 wt% sodium bicarbonate solution was added to the obtained organic phase and mixed, and after standing, the lower aqueous phase was removed. The obtained organic phase was slowly cooled to 10°C, yielding a slurry liquid with precipitated bisphenol C. The filtrate of this slurry liquid was separated using a centrifuge to obtain 1627 kg of wet cake. This wet cake was supplied to a fully jacketed 6.8 cubic meter stainless steel crystallization tank, and then 2442 kg of toluene was supplied. The crystallization tank was heated to 80°C, 551 kg of pure water was added and mixed, and after standing, the lower aqueous phase was removed. Furthermore, 552 kg of pure water was added to the crystallization tank and mixed, and after standing, the lower aqueous phase was removed. 27 kg of a 0.001 wt% sodium chloride solution was added to the obtained organic phase and cooled to 10°C, causing bisphenol C to precipitate and yield a slurry. The slurry was separated into filtrate using a centrifuge, washed with 780 kg of toluene, and 1537 kg of wet cake was obtained. The obtained wet cake was fed into a 6.5 cubic meter dryer and thoroughly dried to obtain bisphenol C. 1440 kg (5.6 kilomol, yield 79 mol% based on acetone) was obtained. Table 4 summarizes the amount of acetone used and the reaction yield of bisphenol C for Examples 9 and 12. The results showed that bisphenol could be produced similarly even when the amount of acetone was increased.

[0165] [Table 4]

[0166] [Example 13] In a fully jacketed 200 ml separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 6.9 g (0.2 mol) of methanol was added 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 of monomethyl sulfate. Subsequently, 14.4 g of toluene, 50.6 g (0.5 mol) of ortho-cresol, and 1.4 g (0.01 mol) of dodecanethiol were added, and the temperature in 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 addition of acetone was complete, the reaction was allowed to proceed at 40°C for 5 hours. 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 reaching 80°C, the mixture was allowed to stand to allow the precipitated material to dissolve in both the organic and aqueous phases. The lower aqueous phase was then removed. The resulting organic phase was neutralized with a 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 out, and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography. The reaction yield, based on acetone, was 89 mol%.

[0167] [Example 14] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 21.2 g (0.7 mol) of methanol was added 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 of monomethyl sulfate. Subsequently, 122.4 g of orthoxylene, 137.7 g (1.3 mol) of orthocresol, and 4.4 g (0.02 mol) of dodecanethiol were added, and the temperature in 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 addition of acetone was complete, the reaction was allowed to proceed at 40°C for 2 hours. After the reaction was complete, 100.0 g of orthoxylene and 100.0 g of dechlorinated water were added, and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand to allow the precipitated material to dissolve in both the organic and aqueous phases. The lower aqueous phase was then removed. The resulting organic phase was neutralized with saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 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 out, and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography. The reaction yield, based on acetone, was 88 mol%.

[0168] [Example 15] The procedure was carried out in the same manner as in Example 14, except that 137.4 g of paraxylene was added to the separable flask instead of 122.4 g of orthoxylene, and after the reaction was complete, 100 g of paraxylene was added instead of 100 g of orthoxylene. 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 91 mol%.

[0169] [Example 16] The procedure of Example 114 was repeated, except that 122.4 g of xylene was used instead of 122.4 g of orthoxylene in the separable flask, and 100 g of xylene was added instead of 100 g of orthoxylene after the reaction was completed. A part of the obtained organic phase was taken out, and the amount of bisphenol C produced by high performance liquid chromatography was confirmed. As a result, the reaction yield based on acetone was 88 mol%.

[0170] [Example 17] The procedure of Example 14 was repeated, except that 122.2 g of mesitylene was used instead of 122.4 g of orthoxylene in the separable flask, and 100 g of mesitylene was added instead of 100 g of orthoxylene after the reaction was completed. A part of the obtained organic phase was taken out, and the amount of bisphenol C produced by high performance liquid chromatography was confirmed. As a result, the reaction yield based on acetone was 85 mol%.

[0171] [Example 18] The procedure of Example 14 was repeated, except that 65.0 g of chlorobenzene was used instead of 122.4 g of orthoxylene in the separable flask, and 100 g of chlorobenzene was added instead of 100 g of orthoxylene after the reaction was completed. A part of the obtained organic phase was taken out, and the amount of bisphenol C produced by high performance liquid chromatography was confirmed. As a result, the reaction yield based on acetone was 60 mol%.

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

[0173]

Table 5

[0174] [Example 19] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 26.1 g (0.4 mol) of isopropyl alcohol was added under a nitrogen atmosphere, followed by the slow addition of 58.3 g (0.5 mol) of 90% 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 addition of acetone was complete, the reaction was allowed to proceed at 40°C for 2 hours. 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 reaching 80°C, the mixture was allowed to stand to allow the precipitated material to dissolve in both the organic and aqueous phases. The lower aqueous phase was then removed. The resulting organic phase was neutralized with a 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 out, and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography. The reaction yield, based on acetone, was 84 mol%.

[0175] [Example 20] The procedure was carried out in the same manner as in Example 19, 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, based on acetone, was 82 mol%.

[0176] [Example 21] The procedure was carried out in the same manner as in Example 19, 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 75 mol%.

[0177] Table 6 summarizes the types of aliphatic alcohols and reaction yields for Examples 13 and 19-21. The results clearly show that bisphenol C can be obtained in good yield even when the type of aliphatic alcohol is changed.

[0178] [Table 6]

[0179] [Example 22] Instead of 5.5g of dodecanethiol, use 2.9g of 3-mercaptopropionic acid (0.01 The procedure was carried out in the same manner as in Example 19, except that 26.3 g (0.8 mol) of methanol 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, and the reaction yield based on acetone was 98 mol%.

[0180] [Example 23] The procedure was carried out in the same manner as in Example 19, 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 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 89 mol%.

[0181] Table 7 summarizes the types of aliphatic alcohols and thiols used, along with the reaction yields, for Examples 13 and 21-23. The results clearly show that bisphenol C can be obtained in good yield even when the types of aliphatic alcohols and thiols are changed.

[0182] [Table 7]

[0183] [Example 24] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 1.7 g (0.1 mol) of methanol was added 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 of 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 addition of acetone was complete, the reaction was allowed to proceed at 40°C for 2 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it was allowed to stand and the aqueous phase was removed. A portion of the obtained organic phase was taken out and analyzed by high-performance liquid chromatography, revealing 2,2-bis(4-hydroxyphenyl)p It was found that bisphenol A (hereinafter referred to as ropane) was being produced. The amount was 73.2% of the area.

[0184] [Example 25] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 8.7 g (0.3 mol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 19.4 g (0.2 mol) of 90 wt% sulfuric acid to generate 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 in 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 addition of dodecanal was complete, the reaction was allowed to proceed at 40°C for 2 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it was allowed to stand and the aqueous phase was removed. A portion of the obtained organic phase was taken out and analyzed by high-performance liquid chromatography, and it was found that 1,1-bis(4-hydroxyphenyl)dodecane had been formed. The obtained organic phase was transferred to a 1-liter round-bottom flask, and toluene, ethyl acetate, and phenol were removed by distillation using an evaporator. Heptane and isopropyl alcohol were supplied to the remaining liquid and crystallized. The obtained slurry was separated into solid and liquid using a vacuum filter equipped with a glass filter to obtain a white solid. This white solid was transferred to a 500 ml round-bottom flask and dried using an evaporator to obtain 30.5 g (0.1 mol, yield 35 mol%) of 1,1-bis(4-hydroxyphenyl)dodecane.

[0185] [Example 26] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 8.7 g (0.3 mol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 19.4 g (0.2 mol) of 90 wt% sulfuric acid to generate monomethyl sulfate. Then, 18.2 g of toluene, 63.8 g (0.6 mol) of ortho-cresol, and 1.8 g (0.01 mol) of dodecanethiol were added, and the temperature in 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 addition of dodecanal was complete, the reaction was allowed to proceed at 40°C for 2 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 381(M) in Negative mode. + -1) was observed, indicating the formation of 1,1-bis(4-hydroxy-3-methylphenyl)dodecane. High-performance liquid chromatography confirmed the formation of 1,1-bis(4-hydroxy-3-methylphenyl)dodecane, which was found to be at 60.7 area %.

[0186] [Example 27] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml, 26 g (0.8 mol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 58.5 g (0.5 mol) of 90 wt% sulfuric acid to generate 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 adjusted. The temperature was raised to 50°C. 136 g (0.8 mol) of fluorenone was added and slowly supplied dropwise to a separable flask over 30 minutes. The reaction was then carried out at 50°C for 2 hours. 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 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 out and measured by high-performance liquid chromatography, which revealed the formation of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. The formation rate was 85.6 area%.

[0187] [Example 28] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 26.2 g (moles) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 58.5 g (0.6 moles) of 92 wt% sulfuric acid to generate a solution of monomethyl sulfate. Subsequently, 58.5 g of toluene, 192 g (1.8 moles) of ortho-cresol, and 5.5 g (0.03 moles) of dodecanethiol were added, and the temperature in the separable flask was raised to 50°C. 71.8 g (0.7 moles) of cyclohexanone was added to the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the addition of cyclohexanone was complete, the reaction was allowed to proceed at 50°C for 5 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 295 (M) in Negative mode. +-1) was observed, indicating the formation of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane. High-performance liquid chromatography was used to confirm the formation rate of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, which was found to be 70.8 area%.

[0188] [Example 29] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 26.2 g (0.8 mol) of methanol was added 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 of monomethyl sulfate. Then, 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 in 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 was complete, the reaction was allowed to proceed at 50°C for 5 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 309 (M) in Negative mode. + -1) was observed, indicating the formation of 1,1-bis(4-hydroxy-3-methylphenyl)cycloheptane. High-performance liquid chromatography was used to confirm the formation rate of 1,1-bis(4-hydroxy-3-methylphenyl)cycloheptane, which was found to be 25.9 area%.

[0189] [Example 30] Fully jacketed 1-liter thermometer, stirrer and 100 ml dropping funnel In a Toll separable flask, 26.2 g (0.8 mol) of methanol was added under a nitrogen atmosphere, and then 58.5 g (0.6 mol) of 92 wt% sulfuric acid was slowly added to generate a solution of monomethyl sulfate. Subsequently, 58.5 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 in 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 addition of methyl ethyl ketone was complete, the reaction was allowed to proceed at 50°C for 5 hours. 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. Subsequently, saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 269 (M) in Negative mode. + -1) was observed, indicating the formation of 2,2-bis(4-hydroxy-3-methylphenyl)butane. High-performance liquid chromatography was used to confirm the formation rate of 2,2-bis(4-hydroxy-3-methylphenyl)butane, which was found to be 47.6 area%.

[0190] [Example 31] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 26.2 g (0.8 mol) of methanol was added 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 of monomethyl sulfate. Then, 58.5 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 in 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 addition of methyl isobutyl ketone was complete, the reaction was allowed to proceed at 50°C for 5 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 297(M) in Negative mode. + -1) was observed, indicating the formation of 2,2-bis(4-hydroxy-3-methylphenyl)-4-methylpentane. High-performance liquid chromatography was used to confirm the formation rate of 2,2-bis(4-hydroxy-3-methylphenyl)-4-methylpentane, which was found to be 65.7 area%.

[0191] [Example 32] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 26.2 g (0.8 mol) of methanol was added 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 of monomethyl sulfate. Then, 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 addition of acetone was complete, the reaction was allowed to proceed at 40°C for 2 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it was allowed to stand, and the aqueous phase was removed. A portion of the obtained organic phase was taken out. High-performance liquid chromatography (HCM) analysis confirmed the formation of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane. The formation rate of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane was 41.9 area%.

[0192] [Example 33] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 5.0 g (0.2 mol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 100 g (0.9 mol) of 92 wt% sulfuric acid to generate monomethyl sulfate. Then, 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 in 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 addition of 3,3,5-trimethylcyclohexanone was complete, the reaction was allowed to proceed at 50°C for 2 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 309 (M) in Negative mode. + -1) was observed, indicating the formation of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane. High-performance liquid chromatography was used to confirm the formation rate of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, which was found to be 62.5 area%.

[0193] [Example 34] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 4 g (0.1 mol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 84 g (0.7 mol) of 85 wt% sulfuric acid to generate monomethyl sulfate. Then, 54 g of toluene, 151 g (1.4 mol) of ortho-cresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature in 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 addition of acetophenone was complete, the reaction was allowed to proceed at 40°C for 2 hours. 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. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 317(M) in Negative mode. + -1) was observed, indicating the formation of 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane. High-performance liquid chromatography was used to confirm the formation rate of 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, which was found to be 48.2 area%.

[0194] [Example 35] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 18 g (0.6 mol) of methanol was added under a nitrogen atmosphere, and then 25.8 g (0.2 mol) of 85 wt% sulfuric acid was slowly added to produce a solution of monomethyl sulfate. Subsequently, 24 g of toluene, 75 g (0.4 mol) of 2-phenylphenol, and 2.4 g (0.01 mol) of dodecanethiol were added to the separable flask. The temperature inside the flask was set to 40°C. 10.5 g (0.2 mol) of acetone was placed in the dropping funnel and slowly added dropwise to the separable flask over 30 minutes. After the addition of acetone was complete, the reaction was allowed to proceed at 40°C for 2 hours. 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. Then, saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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 obtained organic phase was taken out and measured using a high-performance liquid chromatograph mass meter, and the mass number was 379 (M) in Negative mode. + -1) was observed, indicating that 2,2-bis(4-hydroxy-3-phenylphenyl)propane was being produced. High-performance liquid chromatography was used to confirm the production rate of 2,2-bis(4-hydroxy-3-phenylphenyl)propane, which was found to be 9.0 area%.

[0195] [Example 36] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 9 g (0.3 mol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 22 g (0.2 mol) of 85 wt% sulfuric acid to generate 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 in 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 addition of acetone was complete, the reaction was allowed to proceed at 40°C for 2 hours. 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 a saturated sodium bicarbonate solution, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 391(M) in Negative mode. + -1) was observed, indicating the formation of 2,2-bis(4-hydroxy-3-cyclohexylphenyl)propane. High-performance liquid chromatography was used to confirm the formation rate of 2,2-bis(4-hydroxy-3-cyclohexylphenyl)propane, which was 22.9 area%.

[0196] [Example 37] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 1.1 g (0.03 mol) of methanol was added 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 of monomethyl sulfate. Then, 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 addition of acetone was complete, the reaction was allowed to proceed at 40°C for 2 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 407 (M) in Negative mode. + -1) was observed, indicating that 2,2-bis(4-hydroxy-3-benzylphenyl)propane was being produced. High-performance liquid chromatography was used to confirm the production rate of 2,2-bis(4-hydroxy-3-benzylphenyl)propane, which was found to be 60.0 area%.

[0197] [Example 38] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 41.6 g (1.3 mol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 100 g (0.8 mol) of 80 wt% sulfuric acid to generate monomethyl sulfate. Then, 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 in 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 was complete, the reaction was allowed to proceed at 30°C for 2 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 297(M) in Negative mode. + -1) was observed, indicating the formation of 1,1-bis(4-hydroxyphenyl)-2-ethylhexane. High-performance liquid chromatography was used to confirm the formation rate of 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, which was found to be 52.4 area%.

[0198] [Example 39] In a fully jacketed 1-liter separable flask equipped with a thermometer, stirrer, and 100 ml dropping funnel, 41.6 g (1.3 mol) of methanol was added under a nitrogen atmosphere, followed by the slow addition of 100 g (0.8 mol) of 80 wt% sulfuric acid to generate monomethyl sulfate. Then, 54.3 g of toluene, 150 g (1.4 mol) of ortho-cresol, and 5.5 g (0.03 mol) of dodecanethiol were added, and the temperature in 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 was complete, the reaction was allowed to proceed at 30°C for 2 hours. 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 aqueous phase at the bottom was removed. Subsequently, a saturated sodium bicarbonate solution was added to the obtained organic phase to neutralize it, and it was confirmed that the pH of the lower aqueous phase was 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, it 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, and the mass number was 325 (M) in Negative mode. + -1) was observed, indicating the formation of 1,1-bis(4-hydroxy-3-methylphenyl)-2-ethylhexane. High-performance liquid chromatography was used to confirm the production rate of 1,1-bis(4-hydroxy-3-methylphenyl)-2-ethylhexane, which was 67.4 area%. Table 8 summarizes the aromatic alcohols, ketones or aldehydes and synthesized bisphenols for Examples 23 to 39. As a result, it became clear that various bisphenols can be synthesized by using monoalkyl sulfate as a catalyst.

[0199] [Table 8a]

[0200] [Table 8b]

[0201] [Example 40] A 1-liter fully jacketed separable flask, equipped with a thermometer, stirrer, and 100 ml dropping funnel, was lined with a -10°C coolant. Under a nitrogen atmosphere, 240 g of toluene, 9 g of methanol, and 172.5 g (1.60 mol) of orthocresol 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 added to the dropping funnel. When the internal temperature of the separable flask reached -5°C, the mixture was slowly added dropwise over 1 hour. After addition, the mixture was stirred at 10°C for 1 hour, and then the temperature was further raised to 45°C. The mixture was heated and stirred at 45°C for 1 hour. 28% by weight of sodium hydroxide was added to the resulting reaction solution. 128 g of aqueous solution was added. While raising the temperature to 80°C, a 28 wt% sodium hydroxide aqueous solution was added to maintain a pH between 5 and 8. After the internal temperature reached 80°C, the aqueous phase was removed and washed with saturated sodium bicarbonate solution and water. A portion of the obtained organic phase was taken out and the amount of bisphenol C produced was confirmed by high-performance liquid chromatography, and the reaction yield based on acetone was 80 mol%.

[0202] [Example 41] In a 150 mL glass reaction vessel equipped with a stirrer and a distillation tube, 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 400 ppm by mass cesium carbonate aqueous solution were placed. The glass reaction vessel was reduced to approximately 100 Pa, and then the pressure was restored to atmospheric pressure with nitrogen, a process that was repeated three times to replace the inside of the reaction vessel with nitrogen. After that, the reaction vessel was immersed in an oil bath at 200°C to dissolve the contents. The stirrer was set to rotate at 100 revolutions per minute, and the pressure inside the reaction vessel was reduced from 101.3 kPa to 13.3 kPa absolute pressure over 40 minutes while distilling off the phenol produced as a by-product of the oligomerization reaction between bisphenol C and diphenyl carbonate. Subsequently, the pressure inside the reaction vessel was maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off the phenol. Subsequently, the external temperature of the reaction vessel was raised to 250°C, and the internal pressure of the reaction vessel was reduced from 13.3 kPa to 399 Pa in absolute pressure over 40 minutes to remove the distilled phenol from the system. Then, the external temperature of the reaction vessel was raised to 280°C, and the absolute pressure of the reaction vessel was reduced to 30 Pa to carry out the polycondensation reaction. The polycondensation reaction was terminated when the stirrer in the reaction vessel reached a predetermined stirring power. Next, the reaction vessel was repressurized to 101.3 kPa in absolute pressure using nitrogen, and then increased to 0.2 MPa in gauge pressure. Polycarbonate was extracted from the bottom of the reaction vessel in strand form to obtain strand-shaped polycarbonate resin. Subsequently, the strands were pelletized using a rotary cutter to obtain pellet-shaped 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 the production of polycarbonate resin and a method for producing the same. Furthermore, because the bisphenol composition of the present invention contains an aromatic alcohol sulfonate, it efficiently promotes the melt polymerization reaction with diester carbonate, enabling the production of a polycarbonate resin with excellent color tone.

Claims

1. A bisphenol composition is produced by reacting a ketone or aldehyde with an aromatic alcohol in the presence of sulfuric acid. The composition contains 95.0% by mass or more of bisphenol represented by general formula (3), The 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% by mass or less relative to the bisphenol. A method for producing a bisphenol composition. 【Chemistry 1】 (In the formula, R 11 to R 14 each independently represent one of the groups 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 one of the groups selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. R 15 and R 16 may be bonded or bridged to each other.) 【Chemistry 2】 (In the formula, R1 to R4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. X represents a metal atom.) 【Transformation 3】 (In the formula, R5 to R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. X represents a metal atom.)

2. A method for producing a bisphenol composition according to claim 1, wherein the molar ratio of diphenyl carbonate to bisphenol is 1.1, and the mixture of bisphenol and diphenyl carbonate is heated for 90 minutes in an aluminum block heater heated to 194°C, and the phenol production rate in the reaction solution obtained is 0.3 area % or more.

3. A method for producing a bisphenol composition according to claim 1 or 2, wherein X in the general formula (1) and / or general formula (2) is a sodium atom or a potassium atom.

4. A method for producing a polycarbonate resin, comprising producing a bisphenol composition by the method for producing a bisphenol composition described in any one of claims 1 to 3, and reacting the obtained bisphenol composition to produce a polycarbonate resin.

5. A polycarbonate resin containing 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% by mass or less. 【Chemistry 4】 (In the formula, R1 to R4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. X represents a metal atom.) 【Transformation 5】 (In the formula, R5 to R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. X represents a metal atom.)

6. The polycarbonate resin according to claim 5, obtained by reacting with bisphenol represented by general formula (3). 【Transformation 6】 (In the formula, R 11 to R 14 each independently represent one of the groups 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 one of the groups selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. R 15 and R 16 may be bonded or bridged to each other.)

7. The polycarbonate resin according to claim 5 or 6, wherein the YI measured according to ASTM D1925 is 50 or less.

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