CN113574041B

CN113574041B - Bisphenol production method and polycarbonate resin production method

Info

Publication number: CN113574041B
Application number: CN202080020682.6A
Authority: CN
Inventors: 内山馨; 中岛幸惠; 岸田真; 高见芳惠
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 2019-03-18
Filing date: 2020-02-26
Publication date: 2023-10-13
Anticipated expiration: 2040-02-26
Also published as: WO2020189201A1; TW202039410A; CN113574041A; JPWO2020189201A1; TWI818160B; JP7371682B2

Abstract

A method for producing bisphenol, comprising the steps of: a step of mixing the organic phase 1 of the mixed solution 1 of the aqueous phase 1 and the bisphenol-containing organic phase 1 with a chelating agent to obtain a mixed solution 2 of the aqueous phase and the organic phase having a pH of 6 or less; mixing the obtained mixed solution 2 with a base to obtain a mixed solution 3 of an aqueous phase and an organic phase having a pH of 8 or more; and a step of removing an aqueous phase having a pH of 8 or more from the obtained mixed solution 3 to obtain an organic phase 3A, wherein the chelating agent has a higher solubility in the aqueous phase of the mixed solution 3 than in the organic phase of the mixed solution 3.

Description

Bisphenol production method and polycarbonate resin production method

Technical Field

The present invention relates to a method for producing bisphenol and a method for producing polycarbonate resin using the bisphenol.

The bisphenol produced by the method of the present invention is useful as an additive for a resin material such as a polycarbonate resin, an epoxy resin, an aromatic polyester resin, a curing agent, a color developing agent, an anti-fading agent, other bactericides, an antibacterial and antifungal agent, etc.

Background

Bisphenol is useful as a raw material for a polymer material such as a polycarbonate resin, an epoxy resin, and an aromatic polyester resin. As typical bisphenols, for example, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, and the like are known (patent document 1). In addition, a method for producing bisphenol having fluorene skeleton is also known (patent document 2).

Patent document 1: japanese patent laid-open publication No. 2014-40376

Patent document 2: japanese patent laid-open No. 2000-26349

A polycarbonate resin as a representative use of bisphenol is required to be colorless and transparent. The color tone of the polycarbonate resin is significantly affected by the color tone of the raw material. Therefore, the color tone of bisphenol as a raw material is required to be colorless.

Since it is difficult to directly quantify the color of bisphenol, in the present invention, bisphenol is dissolved in methanol and the color difference is digitized, and this color tone is referred to as "methanol-dissolved color".

In the production of polycarbonate resins, particularly in the melt process, bisphenol is melted to produce polycarbonate resins, and therefore, they are exposed to high temperatures. Bisphenol is therefore also required to have color stability against heat.

In the present invention, this hue is referred to as "melt color difference".

In the production of polycarbonate resins, since the polymerization reaction is carried out after the bisphenol is melted, it is also required to have color stability against heat until the polymerization is started.

In the present invention, this hue is referred to as "thermal hue stability".

In the production of polycarbonate resins, when bisphenol is thermally decomposed before the start of polymerization, the mass ratio of bisphenol decreases, and the mass ratio of bisphenol to diphenyl carbonate as a raw material deviates from a predetermined mass ratio, and a polycarbonate resin having a desired molecular weight cannot be obtained, and therefore, bisphenol is also required to have stability against heat.

In the present invention, this stability is referred to as "thermal decomposition stability".

Regarding polycarbonate resins, polycarbonate resins having a molecular weight conforming to the design and good in color tone are being sought. In order to produce such a polycarbonate resin, bisphenol as a raw material is required to have excellent methanol dissolution color, melt color difference, and thermal tone stability, and also excellent thermal decomposition stability.

When hydrogen chloride gas or hydrochloric acid is used as a catalyst for bisphenol production reaction, hydrogen chloride volatilizes to corrode equipment, and the corroded components are mixed into bisphenol, so that the quality of bisphenol is easily deteriorated, which is not easily avoided.

Therefore, in order to obtain bisphenol of good quality, it is important to clean bisphenol efficiently and recover it efficiently.

As a method for recovering bisphenol, for example, a method is known in which water is supplied to a reaction solution to reduce the concentration of an acid catalyst, thereby ending (stopping) the reaction, as described in patent document 1. However, in the case of heating or the like at the time of recovering bisphenol in a state where the acidity of the aqueous phase after the bisphenol production reaction is high, there are other problems such as easy decomposition of bisphenol and increase of byproducts.

In order to suppress the decomposition of bisphenol, a method is known in which the acidity of a reaction solution is reduced and a reaction is terminated by neutralizing an acid catalyst with an aqueous alkali solution (for example, patent document 2). However, in this method, the concentration of the aqueous phase after the bisphenol formation reaction is pH4 to 6, and it is difficult to improve the quality of bisphenol deteriorated by equipment corrosion.

Under such circumstances, in the production of bisphenol using hydrogen chloride gas or hydrochloric acid as a catalyst, a method for improving the quality of bisphenol deteriorated by corrosion of equipment is being sought.

Disclosure of Invention

The present invention is aimed at providing a method for producing bisphenol of good quality and a method for producing polycarbonate resin using the bisphenol, particularly by studying a recovery process of bisphenol produced by using hydrogen chloride gas or hydrochloric acid as an acid catalyst.

The present inventors have found that bisphenol having good quality can be produced by adding a chelating agent to an organic phase containing specific conditions of bisphenol after a bisphenol production reaction, mixing the mixture, and then adding an alkaline aqueous solution to the mixture, and mixing the mixture. The present inventors have also found that a polycarbonate resin having excellent color properties can be produced using the produced bisphenol.

The gist of the present invention resides in the following [1] to [9].

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

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

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

[4] The method for producing bisphenol according to any one of [1] to [3], wherein the mixing ratio of the aqueous phase and the organic phase in the mixed solution 2 is 0.001:100 to 1000:700 in terms of a weight ratio.

[5] The method for producing bisphenol according to any one of [1] to [4], comprising a step of removing an aqueous phase from a mixed solution 4 obtained by mixing the organic phase 3A with deionized water to obtain the organic phase 4.

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

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

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

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

[ chemical 1]

In the formula (I), X and Y are the same or different elements and are selected from the group consisting of nitrogen of 3 valences, oxygen of 2 valences, phosphorus of 3 valences and sulfur of 2 valences. The line joining X and Y is a carbon chain.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, bisphenol having excellent dissolution color of methanol, melt color difference, thermal tone stability and thermal decomposition stability can be produced. According to the present invention, a polycarbonate resin having good color can be produced using the bisphenol obtained.

Detailed Description

Embodiments of the present invention are described in detail below. The following description of the constituent elements is an example of the embodiment of the present invention, and the present invention is not limited to the following description unless the gist thereof is exceeded.

The expression "to" used in the present specification is used in the form of expression including numerical values before and after the expression or physical property values.

[ method for producing bisphenol ]

The method for producing bisphenol of the present invention is characterized by comprising the steps of: a step of mixing the organic phase 1 of the mixed solution 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol with a chelating agent to obtain a mixed solution 2 of the aqueous phase and the organic phase having a pH of 6 or less (hereinafter, this step may be referred to as a "chelating treatment step"); mixing the obtained mixed solution 2 with a base to obtain a mixed solution 3 of an aqueous phase and an organic phase having a pH of 8 or more; and a step of removing the aqueous phase having a pH of 8 or more from the obtained mixed solution 3 to obtain an organic phase 3A (hereinafter, a step of mixing with a base until the organic phase 3A is obtained is sometimes referred to as an "alkali treatment step"), wherein the chelating agent has a higher solubility in the aqueous phase of the mixed solution 3 than in the organic phase of the mixed solution 3.

The method for producing bisphenol of the present invention is characterized in that: when a chelating agent is mixed with an organic phase 1 of a mixed solution 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol to obtain a mixed solution 2 of the aqueous phase and the organic phase having a pH of 6 or less, and the mixed solution 2 is mixed with a base to obtain a mixed solution 3 of the aqueous phase and the organic phase having a pH of 8 or more, the chelating agent having a higher solubility in the aqueous phase than in the organic phase of the mixed solution 3 is used to remove the aqueous phase having a pH of 8 or more from the mixed solution 3, thereby effectively recovering the organic phase 3A containing bisphenol.

As described above, in the conventional case of using hydrogen chloride gas or hydrochloric acid as a catalyst for bisphenol production reaction, hydrogen chloride volatilizes to corrode equipment, and corrosive components are mixed into bisphenol, thereby having a problem of deterioration of quality of bisphenol. The corrosive component mixed in bisphenol contains a metal component such as iron as a constituent material of the equipment as a main component. In the present invention, a chelating agent is added and mixed under the above specific pH acidic condition, and then the pH alkaline condition is set during the addition of the alkaline aqueous solution, so that the metal components such as iron mixed in the bisphenol product are chelated and effectively removed. Further, the quality of bisphenol can be improved by removing the corrosive components.

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

In this case, examples of the method for obtaining the organic phase 1A by removing the aqueous phase from the mixed solution 1 of the aqueous phase 1 having a pH of 6 or less and the bisphenol-containing organic phase 1 include the following methods (1) and (2).

(1) And a method of adding an acidic solution to the reaction solution after the bisphenol-forming reaction to perform phase separation.

(2) And a method comprising neutralizing, washing and crystallizing the reaction solution after the bisphenol-forming reaction, taking out bisphenol, dissolving the bisphenol in a solvent, washing the bisphenol solution with an acidic solution, and then separating the phases.

[ bisphenol production reaction ]

The bisphenol-forming reaction suitable for use in the present invention will be described.

In the bisphenol-forming reaction, ketone or aldehyde is condensed with an aromatic alcohol in the presence of a catalyst to obtain a reaction solution containing bisphenol.

The bisphenol reaction is usually carried out according to the following reaction formula (1).

[ chemical 2]

R in the above reaction formula (1) ¹ ～R ⁶ R in the following general formulae (2) to (3) ¹ ～R ⁶ Is described in the specification.

< aromatic alcohol >

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

[ chemical 3]

In the general formula (2), R is ¹ ～R ⁴ Examples of the "independently" include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an aryl group. The substituent such as an alkyl group, an alkoxy group, an aryl group, etc. may be any of substituted or unsubstituted substituents. As R ¹ ～R ⁴ Examples thereof include a hydrogen atom, a fluoro group, a chloro group, a bromo group, an iodo group, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a t-butoxy group, a n-pentyloxy group, an isopentyloxy group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group, a n-nonyloxy group, a n-decyloxy group, a n-undecyloxy group, a n-dodecyloxy group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, a benzyl group, a phenyl group, a tolyl group, and a 2, 6-dimethylphenyl group.

Among these, if R ² And R is ³ Because of the difficulty in condensation reaction due to the large steric bulk, R is preferable as the aromatic alcohol ² And R is ³ An aromatic alcohol which is a hydrogen atom.

In addition, R is preferably an aromatic alcohol ¹ ～R ⁴ An aromatic alcohol each independently being a hydrogen atom or an alkyl group, more preferably R ¹ And R is ⁴ Each independently is a hydrogen atom or an alkyl group, R ² And R is ³ An aromatic alcohol which is a hydrogen atom.

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

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

< ketone or aldehyde >

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

[ chemical 4]

In the general formula (3), R is ⁵ And R is ⁶ Examples of the "independently" include a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. The substituent such as an alkyl group, an alkoxy group, an aryl group, etc. may be any of substituted or unsubstituted substituents. As R ⁵ 、R ⁶ Examples thereof include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, n-pentoxy group, isopentoxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, benzyl group, phenyl group, tolyl group, 2, 6-dimethylphenyl group and the like.

R ⁵ And R is ⁶ Can be bonded or crosslinked to each other. R is R ⁵ And R is ⁶ May also be bonded together with adjacent carbon atoms to form a cycloalkylidene group that may contain heteroatoms. A cycloalkylidene group is a 2-valent group obtained by removing 2 hydrogen atoms from one carbon atom of a cycloalkane. At R is ⁵ And R is ⁶ In the case of a cycloalkylidene group formed by bonding with adjacent carbon, the bisphenol obtained has a structure in which an aromatic alcohol is bonded via a cycloalkylidene group.

As R ⁵ And R is ⁶ Examples of the cycloalkylidene group bonded to the adjacent carbon atom include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3, 5-trimethylcyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclododecylidene, fluorenylidene, xanthonylidene, and thioxanthonylidene.

Specific examples of the compound represented by the general formula (3) include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, enanthol aldehyde, caprylic aldehyde, pelargonic aldehyde, capric aldehyde, undecanoid and dodecanal; ketones such as acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, etc.; aralkyl ketones such as benzaldehyde, phenyl methyl ketone, phenyl ethyl ketone, phenyl propyl ketone, tolyl methyl ketone, tolyl ethyl ketone, tolyl propyl ketone, xylylmethyl ketone, xylylethyl ketone, xylylpropyl ketone, cyclic alkyl ketones such as cyclic acetone, cyclic butanone, cyclic pentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclic nonanone, cyclic decanone, cyclic undecanone, and cyclic dodecanone; etc. Among them, acetone is preferable.

< bisphenol >

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

[ chemical 5]

In the general formula (4), R ¹ ～R ⁶ The meanings are the same as in the general formulae (2) and (3).

The bisphenol represented by the general formula (4) is, specifically, examples thereof include 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 3-bis (4-hydroxyphenyl) pentane, 3-bis (4-hydroxy-3-methylphenyl) pentane 2, 2-bis (4-hydroxyphenyl) pentane, 2-bis (4-hydroxy-3-methylphenyl) pentane, 3-bis (4-hydroxyphenyl) heptane, 3-bis (4-hydroxy-3-methylphenyl) heptane, 2-bis (4-hydroxyphenyl) heptane, 2-bis (4-hydroxy-3-methylphenyl) heptane, 4-bis (4-hydroxyphenyl) heptane, 4-bis (4-hydroxy-3-methylphenyl) heptane and the like, but are not limited to these materials.

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

< Hydrogen chloride >

In the present invention, hydrogen chloride is preferably used as a catalyst for the reason that the effect according to the present invention can be more remarkably obtained. Examples of the hydrogen chloride include hydrogen chloride gas and hydrochloric acid. Among them, hydrogen chloride gas is preferable.

In the case where the molar ratio of hydrogen chloride to ketone or aldehyde used in the reaction ((mole number of hydrogen chloride/mole number of ketone) or (mole number of hydrogen chloride/mole number of aldehyde)) is small, hydrogen chloride is diluted with water by-produced in the condensation reaction, resulting in a need for a prolonged reaction time. If the molar ratio is large, polymerization of ketone or aldehyde may proceed. For these reasons, the lower limit of the molar ratio of hydrogen chloride to ketone or aldehyde is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 10 or less, more preferably 8 or less, still more preferably 5 or less.

< condensation reaction >

The method for condensing the aromatic alcohol with the ketone or aldehyde in order to obtain the reaction liquid containing bisphenol is not particularly limited, and examples thereof include the following methods.

(i) Method for supplying ketone or aldehyde to mixed solution containing aromatic alcohol and hydrogen chloride and then carrying out reaction for a predetermined time

(ii) Method for supplying hydrogen chloride to mixed solution containing aromatic alcohol and ketone or aldehyde and then performing reaction for predetermined time

The method of supplying the ketone or aldehyde of (i) and the method of supplying the hydrogen chloride of (ii) may be a one-time supply method or a batch supply method. Since the reaction for producing bisphenol is exothermic, a method of dropwise adding the bisphenol to supply the bisphenol in batches is preferable. The method of (i) above is preferable for the reason that self-condensation of ketone or aldehyde can be further suppressed.

In the reaction for condensing an aromatic alcohol with a ketone or aldehyde, if the molar ratio of the aromatic alcohol to the ketone or aldehyde is small (the number of moles of the aromatic alcohol per mole of the ketone) or (the number of moles of the aromatic alcohol per mole of the aldehyde), the ketone or aldehyde tends to be polymerized easily. When the molar ratio is large, the aromatic alcohol is not reacted and is lost. For these reasons, the molar ratio of the aromatic alcohol to the ketone or aldehyde is preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more, preferably 15 or less, more preferably 10 or less, still more preferably 8 or less.

< thiol >

In the present invention, a thiol may be used as a catalyst auxiliary in the condensation reaction of a ketone or aldehyde with an aromatic alcohol.

By using a thiol as a catalyst auxiliary, for example, in the production of 2, 2-bis (4-hydroxy-3-methylphenyl) propane, the production of 24-mer can be suppressed, the selectivity of 44-mer can be improved, the polymerization activity in the production of a polycarbonate resin can be improved, and the color tone of the obtained polycarbonate resin can be improved.

The reason why the effect of improving the polymerization activity and the color tone of the obtained polycarbonate resin is exhibited in the production of the polycarbonate resin is not clear, but it is presumed that the use of thiol suppresses the formation of a blocked product against the polymerization reaction for producing the polycarbonate resin and suppresses the formation of a deteriorated color tone product.

Examples of the thiol used as the catalyst auxiliary include mercaptocarboxylic acids such as thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and 4-mercaptobutyric acid; alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan (decyl mercaptan), undecyl mercaptan (undecyl mercaptan), dodecyl mercaptan (dodecyl mercaptan), tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, and the like; aryl thiols such as mercaptophenols; etc.

When the molar ratio of the thiol catalyst promoter to the ketone or aldehyde used for condensation ((mole number of thiol catalyst promoter/mole number of ketone)) or (mole number of thiol catalyst promoter/mole number of aldehyde)) is small, the effect of improving the selectivity of the reaction of bisphenol by using the thiol catalyst promoter is not obtained. If the molar ratio is too large, the bisphenol may be mixed therein, and the quality may be deteriorated. For these reasons, the molar ratio of the thiol catalyst promoter to the ketone and aldehyde is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more, preferably 1 or less, more preferably 0.5 or less, still more preferably 0.1 or less.

The thiol is preferably premixed with the ketone or aldehyde before being fed to the reaction. Regarding the method of mixing the thiol with the ketone or aldehyde, the ketone or aldehyde may be mixed with the thiol, or the thiol may be mixed with the ketone or aldehyde.

In the method for mixing the mixed solution of the thiol and the ketone or aldehyde with the aromatic alcohol, the aromatic alcohol may be mixed with the mixed solution of the thiol and the ketone or aldehyde, or the mixed solution of the thiol and the ketone or aldehyde may be mixed with the aromatic alcohol, and preferably the mixed solution of the thiol and the ketone or aldehyde is mixed with the aromatic alcohol.

< organic solvent >

In the method for producing bisphenol of the present invention, an organic solvent is generally used for dissolving or dispersing the produced bisphenol.

The organic solvent is not particularly limited insofar as it does not interfere with the bisphenol production reaction, and aromatic hydrocarbons are generally used. Here, the aromatic alcohol as the raw material (the (base)) and the bisphenol as the product are not included in the organic solvent.

Examples of the aromatic hydrocarbon include benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, and trimethylbenzene. These solvents may be used alone or in combination of 2 or more. The aromatic hydrocarbons may be recovered and purified by distillation or the like after being used in the production of bisphenol and reused. In the case of recycling the aromatic hydrocarbon, the boiling point is preferably low. One of the preferred aromatic hydrocarbons is toluene.

If the mass ratio of the organic solvent to the ketone or aldehyde used in the condensation ((mass of ketone/mass of organic solvent) or (mass of aldehyde/mass of organic solvent)) is too large, the ketone or aldehyde is less likely to react with the aromatic alcohol, and a long time is required for the reaction. If the mass ratio is too small, polymerization of ketone or aldehyde is promoted, or the produced bisphenol may be cured. For these reasons, the mass ratio of the organic solvent to the ketone or aldehyde at the time of feeding is preferably 0.5 or more, more preferably 1 or more, and on the other hand, the mass ratio is preferably 100 or less, more preferably 50 or less.

Instead of using an organic solvent, a large amount of the raw aromatic alcohol may be used instead of the organic solvent. In this case, the unreacted aromatic alcohol is lost, but the unreacted aromatic alcohol can be recovered and purified by distillation or the like and reused, thereby reducing the loss.

< reaction conditions >

If the reaction time of the bisphenol-forming reaction is too long, the produced bisphenol may be decomposed, and therefore, the reaction time is preferably 30 hours or less, more preferably 25 hours or less, and still more preferably 20 hours or less. The lower limit of the reaction time is usually 2 hours or more.

The reaction time also includes a mixing time at the time of preparation of the reaction solution. For example, when a ketone or aldehyde is supplied to a mixed solution obtained by mixing an aromatic alcohol and an acid catalyst for 1 hour and then reacted for 1 hour, the reaction time is 2 hours.

Regarding the reaction temperature of the bisphenol-forming reaction, the polymerization of ketone or aldehyde is easily performed at high temperature, and the time required for the reaction becomes long at low temperature. For these reasons, the reaction temperature is preferably-30℃or higher, more preferably-20℃or higher, still more preferably-15℃or higher, preferably 80℃or lower, more preferably 70℃or lower, still more preferably 60℃or lower. The reaction temperature is the average temperature of the period from the start to the end of step 1.

The reaction solution containing bisphenol is preferably obtained as a slurry-like solution in which bisphenol formed is not completely dissolved and dispersed in the reaction solution. The bisphenol-dispersed slurry can be obtained by appropriately adjusting the kind of the acid catalyst, the kind or amount of the organic solvent, the reaction time, and the like.

[ chelating Process ]

The chelating treatment step in the present invention may be performed before the crystallization step described later, after the bisphenol formation reaction step, after the bisphenol formation reaction, after the washing step described later, or after the crystallization step described later.

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

The removal of the aqueous phase is preferably carried out in such a way that the mixing ratio of the aqueous phase after the removal of the aqueous phase to the organic phase 1A is the aqueous phase: the organic phase 1a=1:700 or less, in particular 1:800 or less, in particular 1:900 or less. If the aqueous phase is more than this range, the amount of the alkaline aqueous solution required to reach a pH of 8 or more increases in the alkali treatment step described later.

When the chelating treatment step is performed after the bisphenol production reaction step and after the water washing step described later, if the pH of the aqueous phase obtained by phase separation after washing by adding and mixing water is 6 or less, the organic phase after removing the aqueous phase can be used as the organic phase 1, and the chelating agent can be added and mixed to obtain the mixed solution 2.

When the pH of the aqueous phase after washing exceeds 6, an acidic aqueous solution is added and mixed to the organic phase after removal of the aqueous phase, and the aqueous phase having a pH of 6 or less is subjected to phase separation.

In the case of performing the chelating treatment step after the crystallization step described later, an organic solvent is added to bisphenol which is a solid recovered by crystallization to obtain a bisphenol solution, an acidic aqueous solution is added and mixed to the bisphenol solution, and an aqueous phase having a pH of 6 or less is subjected to phase separation.

The above-mentioned addition and mixing of the acidic aqueous solution and phase separation are performed, and water is added and mixed to the obtained organic phase and phase separation is performed, and if the aqueous phase subjected to phase separation here is pH6 or less, the organic phase obtained by phase separation of the aqueous phase can be regarded as the 1 st organic phase.

In any case, if the pH of the aqueous phase, which is subjected to phase separation when the organic phase 1A is obtained, is greater than 6, the removal of the corrosive component by the chelating agent cannot be sufficiently performed, and bisphenol having good methanol dissolution color, melt color difference, thermal tone stability, and thermal decomposition stability cannot be obtained. The pH of the aqueous phase is particularly preferably 5 or less. If the pH of the aqueous phase is too low, the amount of the alkaline aqueous solution used in the subsequent alkali treatment step is too large, and therefore the pH of the aqueous phase is preferably at least-1.

In the present invention, the pH is measured at room temperature (20 to 30 ℃).

As the acidic substance used for obtaining the aqueous acidic solution having a pH of 6 or less in this way, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid can be used.

The acidic substance concentration of the acidic aqueous solution is suitably adjusted according to the acidic substance or the basic substance remaining in the bisphenol. When the acidic substance concentration of the acidic aqueous solution is too high, bisphenol is decomposed, and therefore the concentration is preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. If the acidic substance concentration of the acidic aqueous solution is too low, the amount of the acidic aqueous solution needs to be increased to obtain an aqueous phase having a pH of 6 or less, and therefore the lower limit of the acidic substance concentration of the acidic aqueous solution is preferably 0.01 mass ppm or more, more preferably 0.1 mass ppm or more.

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

The chelating agent to be added to the organic phase 1 after separation of the aqueous phase having a pH of 6 or less is not limited as long as it is a substance usually used as a chelating agent, and in the present invention, a chelating agent having a higher solubility (hereinafter referred to as "solubility in aqueous phase") than the solubility (hereinafter referred to as "solubility in organic phase") of the organic phase in the mixed solution 3 with respect to the aqueous phase in the mixed solution 3 obtained in the alkali treatment step described later is used.

If the solubility of the chelating agent to the aqueous phase is not more than the solubility of the chelating agent to the organic phase, the chelating agent remains in the organic phase and remains in bisphenol, and the purity of bisphenol is lowered. The chelating agent may have a higher solubility in the aqueous phase than in the organic phase, and the ratio of solubility in the aqueous phase/solubility in the organic phase is 1.5 times or more, preferably 2 times or more, more preferably 10 times or more.

Examples of the chelating agent include beta-diketones such as acetylacetone and 3, 5-heptanedione; aminocarboxylic acids such as ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentaacetic acid, hydroxyethyl ethylenediamine triacetic acid, or salts thereof; ketoacids such as pyruvic acid or acetoacetic acid, levulinic acid, alpha-ketoglutaric acid, acetone dicarboxylic acid; hydroxy acids such as glycolic acid, glyceric acid, lignanoic acid, gluconic acid, lactic acid, tartronic acid, tartaric acid, xylonic acid, galactaric acid, malic acid, and citric acid; polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; amino acids such as aspartic acid and glutamic acid; polyphosphoric acid such as phytic acid, hydroxyethylidene diphosphate, nitrilotrimethylene phosphate, ethylenediamine tetramethylene phosphate; dimethylglyoxime, benzylglyoxime, dioxime such as 1, 2-cyclohexylglyoxime, and the like.

Among these, as a substance satisfying the above-mentioned solubility in an aqueous phase and solubility in an organic phase, ethylenediamine tetraacetic acid, citric acid, oxalic acid, malonic acid, succinic acid may be mentioned.

Among these, 4-membered carboxylic acids are particularly preferred, and aminocarboxylic acids such as ethylenediamine tetraacetic acid or salts thereof are preferred in view of easy chelation with various metals. Further, from the viewpoint of solubility in an organic solvent and further easiness of binding to corrosive components, a chelating agent composed of only carbon, hydrogen and oxygen atoms is preferable, and examples thereof include β -diketones such as acetylacetone and 3, 5-heptanedione; ketoacids such as pyruvic acid, acetoacetic acid, levulinic acid, alpha-ketoglutaric acid, and acetonedicarboxylic acid; hydroxy acids such as glycolic acid, glyceric acid, lignanoic acid, gluconic acid, lactic acid, tartronic acid, tartaric acid, xylonic acid, galactaric acid, malic acid, and citric acid; polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; etc.

These chelating agents may be used in an amount of 1 or two or more thereof may be used in combination.

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

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

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

[ alkali treatment Process ]

The alkali treatment process in the present invention is the following process: the alkali is preferably added and mixed as an alkaline aqueous solution to the mixed solution 2 obtained in the above-mentioned chelating treatment step to obtain a mixed solution 3 of an aqueous phase having a pH of 8 or more and an organic phase, and the aqueous phase having a pH of 8 or more is removed from the obtained mixed solution 3 to obtain an organic phase 3A.

After the aqueous phase of the mixed solution 2 is removed to form an aqueous phase and an organic phase, the chelating effect by the chelating agent cannot be obtained even if an alkaline aqueous solution is added to the organic phase from which the aqueous phase is removed. Therefore, it is important to add an alkaline aqueous solution to the mixed solution 2 before the complete removal of the aqueous phase. That is, regarding the mixing ratio of the aqueous phase and the organic phase in the mixed liquid 2, the aqueous phase is preferably more than 0.001:700, more preferably more than 0.01:700, particularly preferably more than 0.05:700 in terms of weight ratio. On the other hand, regarding the mixing ratio of the aqueous phase and the organic phase in the mixed liquid 2, the aqueous phase is preferably less than 1000:700 by mass, more preferably less than 500:700 by mass, particularly preferably less than 300:700 by mass. If the amount exceeds this range, the chelating agent dissolved in the aqueous phase is also removed, and therefore the effect of the present invention is not exhibited.

Here, the pH of the aqueous phase subjected to phase separation may be at least 8, at least 10 or at least 11, but is usually about 8 to 9.

As the alkaline substance of the alkaline aqueous solution, sodium bicarbonate, sodium carbonate, or the like can be used.

If the concentration of the alkaline substance in the alkaline aqueous solution used in the alkaline treatment step is too low, the amount of the alkaline aqueous solution used to obtain an aqueous phase having a pH of 8 or more increases, the overall liquid amount increases, and the treatment efficiency deteriorates. Therefore, the alkaline substance concentration of the alkaline aqueous solution is preferably as high as possible, and is preferably a saturated aqueous solution of the alkaline substance.

If the amount of the alkaline aqueous solution to be added and mixed is too large, the amount of the aqueous phase to be phase-separated after the addition and mixing of the alkaline aqueous solution becomes too large relative to the amount of the organic phase, and the phase separation is not easy. Even if the amount of the alkaline aqueous solution is reduced, the amount of the organic phase is too large relative to the amount of the aqueous phase, and phase separation is not easy. For these reasons, the mass ratio of the alkaline aqueous solution to the amount of the mixed solution 2 in the alkaline treatment step (mass of the alkaline aqueous solution/mass of the mixed solution 2) is preferably 0.01 or more, particularly 0.1 or more, 100 or less, particularly 10 or less.

The organic phase 3A obtained in the alkali treatment step is preferably purified by a crystallization step described below after the following washing step as needed, and the purified bisphenol is recovered.

[ washing step ]

The bisphenol production method of the present invention may include a water washing step of washing the reaction solution containing bisphenol obtained in the bisphenol production reaction step or the organic phase 3A after the alkali treatment step with water. By performing such a washing step, the impurity amount can be further reduced.

In the water washing step, deionized water is supplied to the reaction solution or the organic phase 3A, for example, and the reaction solution or the organic phase 3A is washed with deionized water.

When the amount of water to be supplied is large, the stirring efficiency tends to be low due to the increase in the liquid amount, and the washing efficiency tends to be low. When the amount of water to be supplied is small, the volume of the aqueous phase tends to decrease, the stirring efficiency tends to decrease, and the washing efficiency tends to decrease. Therefore, the mass ratio of the water to the amount of the reaction liquid or the organic phase 3A (the mass of water/the mass of the reaction liquid or the organic phase 3A) is preferably 0.01 or more, more preferably 0.05 or more, preferably 2 or less, more preferably 1 or less, and still more preferably 0.5 or less.

The washing process is performed as follows: the reaction solution or the organic phase 3A is washed by supplying water thereto, and thereafter the phases are separated into an organic phase and an aqueous phase, and the aqueous phase is removed, whereby washing is performed.

The water washing process may be performed a plurality of times. In this case, the water supply, washing, phase separation and removal of the aqueous phase are repeatedly performed.

[ alkali cleaning Process ]

The bisphenol production method of the present invention may include an alkali washing step of washing the obtained organic phase with an alkali aqueous solution after the alkali treatment step or the water washing step.

The alkali cleaning step preferably includes the steps of: after the alkali treatment step or the water washing step, the separated organic phase is mixed with an alkaline aqueous solution and then phase-separated into an organic phase and an aqueous phase having a pH of 9 or higher, and the phase-separated aqueous phase is removed to obtain an organic phase.

By washing with an alkaline aqueous solution in this manner, impurities that are easily dissolved under alkaline conditions can be removed.

The alkaline cleaning process may be performed a plurality of times.

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

As the alkaline substance of the alkaline aqueous solution used in the alkaline cleaning step, sodium hydrogencarbonate, sodium carbonate, and the like can be used.

The alkaline substance concentration of the alkaline aqueous solution used in the alkaline cleaning step is appropriately adjusted according to the type of alkaline substance or acid catalyst. If the alkali substance concentration of the alkali aqueous solution is too high, the alkali substance remains in the bisphenol to be finally obtained and the quality is deteriorated, so that the alkali substance concentration is preferably 20 mass% or less, more preferably 15 mass% or less, and still more preferably 10 mass% or less. If the alkali concentration of the alkali aqueous solution is too low, the amount of the alkali aqueous solution needs to be increased to obtain an aqueous phase having a pH of 9 or more, and therefore the alkali concentration of the alkali aqueous solution is preferably 0.1 mass% or more, more preferably 0.5 mass% or more.

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

[ temperature of chelating treatment step, alkali treatment step, washing step, alkali washing step ]

In the above-mentioned chelating treatment step, alkali treatment step, washing step and alkali washing step, the average temperature from the beginning to the end is preferably 50℃or higher, more preferably 55℃or higher, in order to suppress the precipitation of bisphenol. In order to suppress precipitation of bisphenol due to evaporation of the organic solvent, the average temperature is preferably 120 ℃ or less, more preferably 110 ℃ or less. These steps may be performed at the same temperature, for example.

[ crystallization Process ]

The bisphenol production method of the present invention preferably includes a crystallization step. The crystallization step is usually performed after the alkali treatment step, or after the alkali treatment step, the alkali cleaning step, and the subsequent water washing step.

Crystallization may be performed according to a conventional method. For example, any of a method using a poor solubility of bisphenol due to a temperature difference and a method of precipitating a solid by supplying a poor solvent can be applied. In the case of using a method of supplying a poor solvent, the purity of the obtained bisphenol is easily lowered, and therefore, a method of using a poor solubility of bisphenol due to a temperature difference is preferable.

When the aromatic alcohol content in the organic phase is large, the remaining aromatic alcohol may be distilled off before crystallization, and then crystallization may be performed.

For example, bisphenol can be precipitated by cooling the organic phase at 60 to 90℃to-10 to 30 ℃. The bisphenol thus precipitated can be recovered by solid-liquid separation, drying, or the like.

Regarding the organic phase to be used in the crystallization step, the conductivity of the aqueous phase separated in the step immediately before (hereinafter sometimes referred to as "near-before aqueous phase") is preferably 10. Mu.S/cm or less. When the conductivity of the aqueous phase before the reaction is 10. Mu.S/cm or less, particularly 9. Mu.S/cm or less, and particularly 8. Mu.S/cm or less, impurities such as by-products and residual catalyst in the product can be highly removed, and the following bisphenol can be obtained: the color tone is good, the polymerization efficiency is high when bisphenol is used as a raw material of the polycarbonate resin, and the polycarbonate resin with excellent color tone can be manufactured.

Here, the conductivity of the aqueous phase can be measured, for example, by a conductivity meter for the aqueous phase of the phase-separated phase at room temperature (20 to 30 ℃).

The bisphenol thus obtained can be further purified according to a conventional method depending on the use thereof. For example, the purification can be carried out by a simple means such as spray washing, water washing, suspension washing, crystallization or column chromatography. Specifically, the bisphenol obtained is dissolved in an organic solvent such as aromatic hydrocarbon, and then cooled to crystallize, whereby further purification can be performed.

[ Process Structure of bisphenol production method ]

The bisphenol production method of the present invention may be, for example, a production method comprising a chelating treatment step, an alkali treatment step, a water washing step and a crystallization step in this order. The bisphenol production method of the present invention may be a production method comprising a water washing step, a chelating treatment step, an alkali treatment step, a water washing step and a crystallization step in this order.

[ Property of bisphenol ]

The following is a description of suitable physical properties of the bisphenol produced by the process for producing bisphenol of the present invention (hereinafter sometimes referred to as "bisphenol of the present invention").

< methanol-soluble color of bisphenol >

The methanol-soluble color of bisphenol was used to evaluate the hue of bisphenol at normal temperature. The lower the Hazen color number of the methanol-dissolved color of bisphenol, the better the hue of bisphenol (closer to white). Examples of the cause of deterioration of the methanol-soluble color of bisphenol include the incorporation of an organic coloring component and a metal.

The methanol-solubility color of bisphenol was determined as follows: bisphenol was dissolved in methanol to prepare a homogeneous solution, and then the solution was measured at room temperature (about 20 ℃). The measurement method includes: a method of visually comparing with a standard liquid of Hazen color number; or a method of measuring the Hazen color value by using a color difference meter such as "SE6000" manufactured by Nippon electric color industry Co. The mass ratio of the solvent methanol, bisphenol and solvent used herein is preferably appropriately selected depending on the kind of bisphenol.

The Hazen color of the methanol-soluble color of bisphenol is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less.

< melt color difference of bisphenol >

The melt color difference of bisphenol was used to evaluate the hue of bisphenol at a temperature close to the polymerization temperature of polycarbonate. The measurement temperature of the melt color difference was the melting point +50℃. The lower the Hazen color number of the melt color difference of the bisphenol, the better the hue of the bisphenol (closer to white). As a cause of deterioration of melt color difference of bisphenol, in addition to organic coloring components or metal mixing, components colored by heating are mentioned.

The melt color difference of bisphenol was measured by melting bisphenol at a temperature close to the polymerization temperature and stabilizing the temperature for a predetermined period of time. The measurement method includes: a method of visually comparing with a standard liquid of Hazen color number; or a method of measuring the Hazen color value by using a color difference meter such as "SE6000" manufactured by Nippon electric color industry Co.

The Hazen color number is preferably 40 or less, more preferably 30 or less, particularly preferably 20 or less.

< thermal tone stability of bisphenol >

The thermal stability of bisphenol is used to evaluate the thermal stability of bisphenol color tone by maintaining the same temperature as the polymerization temperature of polycarbonate for a predetermined time as the melt color difference of bisphenol. The measurement temperature of the thermal tone stability of bisphenol is the melting point +50℃.

The lower the Hazen color number of the thermal stability of the bisphenol, the better the thermal stability of the bisphenol. As a cause of deterioration of the thermal tone stability of bisphenol, in addition to mixing of organic coloring components or metals, there are also components colored by heating or acidic substances or basic substances having a concentration of about several ppm.

Regarding the thermal tone stability of bisphenol, bisphenol is melted at a temperature close to the polymerization temperature and measured in advance for a time period at which the temperature is stable. The retention time of the thermal tone stability of the bisphenol was 4 hours. The measurement method includes: a method of visually comparing with a standard liquid of Hazen color number; or a method of measuring the Hazen color value by using a color difference meter such as "SE6000" manufactured by Nippon electric color industry Co.

The Hazen color number is preferably 50 or less, more preferably 45 or less, particularly preferably 35 or less.

< thermal decomposition stability of bisphenol >

The thermal stability of bisphenol was evaluated by maintaining the same as the thermal stability of bisphenol in hue at a temperature similar to the polymerization temperature of polycarbonate for a predetermined period of time. The preferred measurement temperature for the thermal decomposition stability of bisphenol is the melting point +50℃. Regarding the thermal decomposition stability of bisphenol, the smaller the amount of the decomposed product, the more stable bisphenol is.

The decomposition product in the thermal decomposition stability of bisphenol depends on the kind of bisphenol, and examples thereof include an aromatic alcohol as a raw material of the bisphenol, or an adduct of the aromatic alcohol and a ketone or aldehyde as a raw material. As a cause of deterioration of the thermal tone stability of bisphenol, in addition to mixing of organic coloring components or metals, there are also components colored by heating or acidic substances or basic substances having a concentration of about several ppm.

The detection and quantification of the bisphenol decomposition products can be performed using a standard high-speed analytical reverse phase column.

The amount of isopropenylcresol produced, as measured in examples described below, is preferably 200 ppm by mass or less as a decomposition product of bisphenol.

The methanol-soluble color of bisphenol is a method for evaluating the color tone of bisphenol itself. In the case where bisphenol is the final product, it is important that methanol dissolves bisphenol with good color. Since the polycarbonate resin inherits the color tone of the raw material, bisphenol having a good color tone is important in the polycarbonate resin requiring colorless transparency.

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

Further, in the melt polymerization method, bisphenol is maintained in a molten state at a high temperature until the polymerization reaction starts. In this melt polymerization method, when bisphenol is decomposed at a high temperature, the ratio of the bisphenol to the diphenyl carbonate is deviated from a predetermined ratio, and it is difficult to obtain a polycarbonate resin having polymerization activity or a specific molecular weight. Therefore, resistance to thermal decomposition (thermal decomposition stability of bisphenol) is important.

In particular, for producing a polycarbonate resin having a specific molecular weight and a good color tone, the methanol-soluble color of bisphenol, the melt color difference of bisphenol, the thermal tone stability of bisphenol, and the thermal decomposition stability of bisphenol are important.

[ use of bisphenol ]

The bisphenol of the present invention can be used as a constituent component of various thermosetting resins such as polyether resins, polyester resins, polyarylate resins, polycarbonate resins, polyurethane resins, acrylic resins, epoxy resins, unsaturated polyester resins, phenol resins, polybenzoxazine resins, cyanate resins, etc., a curing agent, an additive, or a precursor thereof, etc., which are used for various applications such as optical materials, recording materials, insulating materials, transparent materials, electronic materials, adhesive materials, heat-resistant materials, etc. The bisphenol of the present invention is also useful as a color developer for thermosensitive recording materials and the like, an anti-fading agent, a bactericide, an antibacterial and antifungal agent and the like.

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

[ method for producing polycarbonate resin ]

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

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

The bisphenol of the present invention may be used alone or in combination of 2 or more types to produce a copolymerized polycarbonate resin. The reaction may be carried out in combination with a dihydroxy compound other than bisphenol of the present invention.

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

In the above-mentioned method for producing a polycarbonate resin, diphenyl carbonate is preferably used in an excess amount relative to the bisphenol of the present invention. The amount of diphenyl carbonate used is preferably large relative to bisphenol, since the polycarbonate resin produced has a small number of terminal hydroxyl groups and the polymer has excellent thermal stability. In view of the high rate of transesterification and easiness of production of a polycarbonate resin having a desired molecular weight, the amount of diphenyl carbonate used is preferably small relative to bisphenol. For these reasons, the amount of diphenyl carbonate used is usually 1.001 mol or more, preferably 1.002 mol or more, usually 1.3 mol or less, preferably 1.2 mol or less, based on 1 mol of bisphenol.

The bisphenol and diphenyl carbonate of the present invention may be supplied in solid form as a raw material supply method, but it is preferable to melt one or both of them and supply them in a liquid state.

In the production of polycarbonate resins by transesterification of diphenyl carbonate with bisphenol, a transesterification catalyst is generally used. In the above-mentioned method for producing a polycarbonate resin, an alkali metal compound and/or an alkaline earth metal compound is preferably used as the transesterification catalyst. One kind of them may be used, or two or more kinds may be used in any combination and ratio. In terms of practicality, alkali metal compounds are preferably used.

The catalyst is used in an amount of usually 0.05. Mu. Mol or more, preferably 0.08. Mu. Mol or more, more preferably 0.10. Mu. Mol or more, usually 100. Mu. Mol or less, preferably 50. Mu. Mol or less, more preferably 20. Mu. Mol or less, based on 1 mol of bisphenol or diphenyl carbonate.

When the amount of the catalyst is in the above range, a polycarbonate resin having excellent polymer color tone, no excessive branching of the polymer, and excellent fluidity in molding can be easily obtained, while having polymerization activity required for producing a polycarbonate resin having a desired molecular weight.

In producing a polycarbonate resin by the above method, it is preferable that the above two raw materials are continuously supplied to a raw material mixing tank, and the resulting mixture and the transesterification catalyst are continuously supplied to a polymerization pot.

In the production of a polycarbonate resin by the transesterification method, generally, two raw materials supplied to a raw material mixing tank are uniformly stirred and then supplied to a polymerization reactor to which a transesterification catalyst is added, whereby a polymer is produced.

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

The bisphenol of the present invention can be used to produce a polycarbonate resin having excellent color tone and transparency. For example, a polycarbonate resin having a viscosity average molecular weight (Mv) of 10000 or more, preferably 15000 or more and 100000 or less, preferably 35000 or less, and pellets YI10 or less, and excellent in color tone and transparency can be produced in a short period of time.

[ method for producing organic Compound ]

In the same manner as in the method for producing bisphenol of the present invention, by subjecting to the above-mentioned chelating treatment step and alkali treatment step, not only bisphenol but also high-quality organic compound (I) can be produced in high purity by removing impurities such as metal mixed in the organic compound (I) from a metal-coordinated organic compound (hereinafter sometimes referred to as "organic compound (I)") having a partial structure (hereinafter sometimes referred to as "partial structure (I)") represented by the following formula (I) in a molecule.

The term "metal coordination" as used herein refers to a compound capable of forming a complex by bonding a coordination bond to a metal ion, and the organic compound (I) functions as a ligand for the metal ion by having a partial structure (I).

[ chemical 6]

X, Y in the formula (I) may further have a substituent containing an element selected from the group consisting of nitrogen 3, oxygen 2, phosphorus 3 and sulfur 2, respectively.

The term "carbon chain" refers to a bond in which carbon atoms are bonded to each other by a single bond, a double bond, or a triple bond, and is not limited to a chain such as a straight chain or a branched chain, and may include a cyclic structure, or may be a combination thereof.

The organic compound (I) is a metal complex compound in which a part of the structure (I) functions as a ligand of a metal ion. Therefore, the organic compound (I) is often present in the reaction product as a complex compound coordinated with a metal in the production process thereof due to a metal compound used as a catalyst or impurities mixed in during the production process.

In the use of the organic compound (I), the metal-incorporated product may cause defects such as coloration, decomposition, and deterioration due to the metal contained therein.

By applying the above-described production process of the bisphenol production method of the present invention to the production of the organic compound (I), the metal can be effectively removed from the organic compound (I), and the high-quality organic compound (I) can be produced with high purity.

The method for producing an organic compound according to the present invention is characterized by comprising the steps of: mixing the organic phase 1' of the mixed liquid 1' of the aqueous phase 1' and the organic phase 1' containing the organic compound with a chelating agent to obtain a mixed liquid 2' of the aqueous phase and the organic phase having a pH of 6 or less; mixing the obtained mixed solution 2 'with a base to obtain a mixed solution 3' of an aqueous phase and an organic phase having a pH of 8 or more; and a step of removing the aqueous phase having a pH of 8 or more from the obtained mixed solution 3' to obtain an organic phase 3A ', wherein the solubility of the organic compound (I) in the organic phase of the mixed solution 3' is higher than the solubility of the chelating agent in the aqueous phase of the mixed solution 3' in the organic phase of the mixed solution 3 '.

The process for producing bisphenol can be carried out in the same manner as the process for producing bisphenol described above, except that "bisphenol" is referred to as "organic compound (I)", "organic phase 1" is referred to as "organic phase 1'", "mixed solution 2" is referred to as "mixed solution 2'", and "organic phase 3A" is referred to as "organic phase 3A '".

Examples of the organic compound (I) used in the method for producing an organic compound of the present invention include an amide group, a hydrazide group, an imide group, an amidine group, and a nitrile group each having X and/or Y as a nitrogen element; alcohol group, phenol group and ether group of oxygen element; the structure of the sulfhydryl group and the thioether group of the sulfur element.

When the organic compound (I) is the chelating agent, the chelating agent different from the organic compound (I) is selected. For example, the following combinations are given.

When the organic compound (I) is the carboxylic acid, the β -diketone or the dioxime is selected as the chelating agent.

When the organic compound (I) is the above-mentioned β -diketone, the above-mentioned carboxylic acid or the above-mentioned dioxime is selected as the chelating agent.

When the organic compound (I) is the above-mentioned dioxime, the above-mentioned carboxylic acid or β -diketone is selected as the chelating agent.

The organic compound (I) is exemplified by the following, but the organic compound (I) to be used in the method for producing an organic compound of the present invention is not limited to the following.

< organic Compound (I) in which X and Y are the same >

Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid;

diamides such as oxamide, malonic acid diamide, succinic acid diamide, glutaric acid diamide, adipic acid diamide, pimelic acid diamide, suberic acid diamide, azelaic acid diamide, sebacic acid diamide, phthalic acid diamide, isophthalic acid diamide, and terephthalic acid diamide;

dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide;

dinitriles such as succinonitrile, glutaronitrile, adiponitrile, pimelic dinitrile, suberonitrile, nondinitrile and sebaconitrile;

Di-isocyanides such as dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate;

glycols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, cyclopropylene glycol, cyclopropanedimethanol, cyclobutanedimethanol, cyclopentylene glycol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, cycloheptanediol, cycloheptanedimethanol, cyclooctanediol, cyclononylene glycol, cyclononanedimethanol, cyclodecane glycol, and cyclodecane dimethanol;

biphenols such as biphenol, dimethyl biphenol and tetramethyl biphenol;

diamines such as ethylenediamine, propylenediamine, butylenediamine, pentylene diamine, hexamethylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decylenediamine, and phenylenediamine;

diimines such as ethyldiimine, propyldiimine, butyldiimine, pentyldiimine, hexyldiimine, heptyldiimine, suberimide, nonyldiimine, decyldiimine, etc.;

Dihydrazides such as ethyldihydrazide, propyldihydrazide, butyldihydrazide, pentylhydrazide, hexyldihydrazide, heptyldihydrazide, suberoyldihydrazide, nonyldihydrazide, decyldihydrazide, and phenyldihydrazide;

diethoxymethane, dimethoxyethane, dimethoxypropane, dimethoxybutane, dimethoxypentane, dimethoxyhexane, dimethoxyheptane, dimethoxyoctane, dimethoxynonane, dimethoxydecane, dimethoxybenzene, diethoxymethane, diethoxyethane, diethoxypropane, diethoxybutane, diethoxypentane, diethoxyhexane, diethoxyheptane, diethoxyoctane, diethoxynonane, diethoxydecane, diethoxybenzene, dipropoxymethane, dipropoxyethane, dipropoxypropane, dipropoxybutane, dipropoxybentane, dipropoxybutane, dipropoxybeptane, dipropoxybctane, dipropoxybonane, dipropoxybutane, dipropoxybenzene and the like.

And disulfides such as dimethylthiomethane, dimethylthioethane, dimethylthiopropane, dimethylthiobutane, dimethylthiopentane, dimethylthiohexane, dimethylthioheptane, dimethylthiooctane, dimethylthiononane, dimethylthiodecane, dimethylthiobenzene, diethylthiomethane, diethylthioethane, diethylthiopropane, diethylthiobutane, diethylthiopentane, diethylthiohexane, diethylthioheptane, diethylthiooctane, diethylthiononane, diethylthiodecane, diethylthiobenzene, dipropylmethane, dipropylethane, dipropylpropane, dipropylthiobutane, dipropylthiononane, dipropylthiodecane, dipropylbenzene, and dipropylbenzene.

< organic Compound (I) in which X and Y are different >

Nitrile isocyanates such as methylene nitrile isocyanate, ethylene nitrile isocyanate, propylene nitrile isocyanate, butylene nitrile isocyanate, pentylene nitrile isocyanate, hexylene nitrile isocyanate, heptylene nitrile isocyanate, octylene nitrile isocyanate, nonylene nitrile isocyanate, decylene nitrile isocyanate, and phenylene isocyanate;

hydroxy nitriles such as hydroxy methyl nitrile, hydroxy ethyl nitrile, hydroxy propyl nitrile, hydroxy butyl nitrile, hydroxy amyl nitrile, hydroxy hexyl nitrile, hydroxy heptyl nitrile, hydroxy octyl nitrile, hydroxy nonyl nitrile, hydroxy decyl nitrile, and hydroxy phenyl nitrile;

hydroxy benzonitriles such as hydroxy phenyl methyl nitrile, hydroxy phenyl ethyl nitrile, hydroxy phenyl propyl nitrile, hydroxy phenyl butyl nitrile, hydroxy phenyl amyl nitrile, hydroxy phenyl hexyl nitrile, hydroxy phenyl heptyl nitrile, hydroxy phenyl octyl nitrile, hydroxy phenyl nonyl nitrile, hydroxy phenyl decyl nitrile, and hydroxy phenyl nitrile;

amino nitriles such as aminomethyl nitrile, aminoethyl nitrile, aminopropyl nitrile, aminobutyl nitrile, aminopentyl nitrile, aminohexyl nitrile, aminoheptyl nitrile, aminooctyl nitrile, aminononyl nitrile, aminodecyl nitrile, and aminophenyl nitrile;

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

hydrazides such as methylene hydrazine, ethylene hydrazine, propylene hydrazine, butylene hydrazine, pentylene hydrazine, hexylene hydrazine, heptylene hydrazine, octylene hydrazine, nonylene hydrazine, decylene hydrazine, and benzonitrile hydrazine;

methoxymethyl nitrile, methoxyethyl nitrile, methoxypropyl nitrile, methoxybutyl nitrile, methoxypentyl nitrile, methoxyhexyl nitrile, methoxyheptyl nitrile, methoxyoctyl nitrile, methoxynonyl nitrile, methoxydecyl nitrile, methoxyphenyl nitrile, ethoxymethyl nitrile, ethoxyethyl nitrile, ethoxypropyl nitrile, ethoxybutyl nitrile, ethoxypentyl nitrile, ethoxyhexyl nitrile, ethoxyheptyl nitrile, ethoxyoctyl nitrile, ethoxynonyl nitrile, ethoxydecyl nitrile, ethoxyphenyl nitrile, propoxymethyl nitrile, propoxyethyl nitrile, propoxypropyl nitrile, propoxybutyl nitrile, propoxypentyl nitrile, propoxyhexyl nitrile, propoxyheptyl nitrile, propoxyoctyl nitrile, propoxynonyl nitrile, propoxydecyl nitrile, propoxyphenyl nitrile and the like;

Nitrile thioethers such as methylene nitrile sulfide, ethylene nitrile sulfide, propylene nitrile sulfide, butylene nitrile sulfide, pentylene nitrile sulfide, hexylene nitrile sulfide, heptylene nitrile sulfide, octylene nitrile sulfide, nonylene nitrile sulfide, decylene nitrile sulfide, and benzonitrile sulfide;

hydroxy isocyanates such as hydroxy methyl isocyanate, hydroxy ethyl isocyanate, hydroxy propyl isocyanate, hydroxy butyl isocyanate, hydroxy pentyl isocyanate, hydroxy hexyl isocyanate, hydroxy heptyl isocyanate, hydroxy octyl isocyanate, hydroxy nonyl isocyanate, hydroxy decyl isocyanate, and hydroxy phenyl isocyanate;

hydroxyphenyl isocyanates such as hydroxyphenyl methyl isocyanate, hydroxyphenyl ethyl isocyanate, hydroxyphenyl propyl isocyanate, hydroxyphenyl butyl isocyanate, hydroxyphenyl pentyl isocyanate, hydroxyphenyl hexyl isocyanate, hydroxyphenyl heptyl isocyanate, hydroxyphenyl octyl isocyanate, hydroxyphenyl nonyl isocyanate, hydroxyphenyl decyl isocyanate and hydroxyphenyl phenyl isocyanate;

amino isocyanates such as aminomethyl isocyanate, aminoethyl isocyanate, aminopropyl isocyanate, aminobutyl isocyanate, aminopentyl isocyanate, aminohexyl isocyanate, aminoheptyl isocyanate, aminooctyl isocyanate, aminononyl isocyanate, aminodecyl isocyanate, and aminophenyl isocyanate;

Iminoisocyanates such as iminomethyl isocyanate, iminoethyl isocyanate, iminopropyl isocyanate, iminobutyl isocyanate, iminopentyl isocyanate, iminohexyl isocyanate, iminoheptyl isocyanate, iminooctyl isocyanate, iminononyl isocyanate, iminodecyl isocyanate, iminophenyl isocyanate, and the like;

isocyanate hydrazines such as methylene isocyanate hydrazine, ethylene isocyanate hydrazine, propylene isocyanate hydrazine, butylene isocyanate hydrazine, pentylene isocyanate hydrazine, hexylene isocyanate hydrazine, heptylene isocyanate hydrazine, octylene isocyanate hydrazine, nonylene isocyanate hydrazine, decylene isocyanate hydrazine, and phenylisocyanate hydrazine;

methoxy methyl isocyanate, methoxy ethyl isocyanate, methoxy propyl isocyanate, methoxy butyl isocyanate, methoxy pentyl isocyanate, methoxy hexyl isocyanate, methoxy heptyl isocyanate, methoxy octyl isocyanate, methoxy nonyl isocyanate, methoxy decyl isocyanate, methoxy phenyl isocyanate, ethoxy methyl isocyanate, ethoxy ethyl isocyanate, ethoxy propyl isocyanate, ethoxy butyl isocyanate, ethoxy pentyl isocyanate, ethoxy hexyl isocyanate, ethoxy heptyl isocyanate, ethoxy octyl isocyanate, ethoxy nonyl isocyanate, ethoxy decyl isocyanate, ethoxy phenyl isocyanate, propoxy methyl isocyanate, propoxy ethyl isocyanate, propoxy propyl isocyanate, propoxy butyl isocyanate, propoxy pentyl isocyanate, propoxy hexyl isocyanate, propoxy heptyl isocyanate, propoxy octyl isocyanate, propoxy nonyl isocyanate, propoxy decyl isocyanate, propoxy phenyl isocyanate and the like;

Isocyanate thioethers such as methylene isocyanate sulfide, ethylene isocyanate sulfide, propylene isocyanate sulfide, butylene isocyanate sulfide, pentylene isocyanate sulfide, hexylene isocyanate sulfide, heptylene isocyanate sulfide, octylene isocyanate sulfide, nonylene isocyanate sulfide, decylene isocyanate sulfide, and phenyl isocyanate sulfide;

hydroxy alkylphenols such as hydroxy methylphenol, hydroxy ethylphenol, hydroxy propylphenol, hydroxy butylphenol, hydroxy pentylphenol, hydroxy hexylphenol, hydroxy heptylphenol, hydroxy octylphenol, hydroxy nonylphenol, and hydroxy decylphenol;

hydroxyalkylamines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, and the like;

hydroxy alkyl imines such as hydroxy methyl imine, hydroxy ethyl imine, hydroxy propyl imine, hydroxy butyl imine, hydroxy amyl imine, hydroxy hexyl imine, hydroxy heptyl imine, hydroxy octyl imine, hydroxy nonyl imine, and hydroxy decyl imine;

hydroxy alkyl hydrazines such as hydroxy methyl hydrazine, hydroxy ethyl hydrazine, hydroxy propyl hydrazine, hydroxy butyl hydrazine, hydroxy amyl hydrazine, hydroxy hexyl hydrazine, hydroxy heptyl hydrazine, hydroxy octyl hydrazine, hydroxy nonyl hydrazine, and hydroxy decyl hydrazine;

Methoxy methanol, methoxy ethanol, methoxy propanol, methoxy butanol, methoxy pentanol, methoxy hexanol, methoxy heptanol, methoxy octanol, methoxy nonanol, methoxy decanol, methoxy benzene alcohol, ethoxy methanol, ethoxy ethanol, ethoxy propanol, ethoxy butanol, ethoxy pentanol, ethoxy hexanol, ethoxy heptanol, ethoxy octanol, ethoxy nonanol, ethoxy decanol, ethoxy benzene alcohol, propoxy methanol, propoxy ethanol, propoxy propanol, propoxy butanol, propoxy pentanol, propoxy hexanol, propoxy heptanol, propoxy octanol, propoxy nonanol, propoxy decanol, propoxy benzene alcohol and the like alkoxy alcohols;

hydroxy alkyl sulfides such as hydroxy methyl sulfide, hydroxy ethyl sulfide, hydroxy propyl sulfide, hydroxy butyl sulfide, hydroxy pentyl sulfide, hydroxy hexyl sulfide, hydroxy heptyl sulfide, hydroxy octyl sulfide, hydroxy nonyl sulfide, and hydroxy decyl sulfide;

hydroxyphenylamines such as hydroxyphenylmethylamine, hydroxyphenylethylamine, hydroxyphenylpropylamine, hydroxyphenylbutylamine, hydroxyphenylpentylamine, hydroxyphenylhexylamine, hydroxyphenylheptylamine, hydroxyphenyloctylamine, hydroxyphenylnonylamine, hydroxyphenyldecylamine, and hydroxyphenylaniline;

Hydroxyphenylimines such as hydroxyphenylmethylimine, hydroxyphenylethylimine, hydroxyphenylpropylimine, hydroxyphenylbutylimine, hydroxyphenylpentylimine, hydroxyphenylhexylimine, hydroxyphenylheptylimine, hydroxyphenyloctylimine, hydroxyphenylnonylimine, hydroxyphenyldecylimine, and hydroxyphenylphenylimine;

hydroxyphenyl hydrazines such as hydroxyphenyl methyl hydrazine, hydroxyphenyl ethyl hydrazine, hydroxyphenyl propyl hydrazine, hydroxyphenyl butyl hydrazine, hydroxyphenyl pentyl hydrazine, hydroxyphenyl hexyl hydrazine, hydroxyphenyl heptyl hydrazine, hydroxyphenyl octyl hydrazine, hydroxyphenyl nonyl hydrazine, hydroxyphenyl decyl hydrazine, and hydroxyphenyl phenyl hydrazine;

methoxypolymethylphenol, methoxypropylphenol, methoxyputylphenol, methoxypentylphenol, methoxypexylphenol, methoxypolyheptylphenol, methoxyoctylphenol, methoxynonylphenol, methoxydecylphenol, methoxyphenylphenol, ethoxymethylphenol, ethoxyethylphenol, ethoxypropylphenol, ethoxybutylphenol, ethoxypentylphenol, ethoxyhexylphenol, ethoxyheptylphenol, ethoxyoctylphenol, ethoxynonylphenol, ethoxydecylphenol, ethoxyphenylphenol, propoxymethylphenol, propoxyethylphenol, propoxypropylphenol, propoxybutylphenol, propoxypentylphenol, propoxyhexylphenol, propoxyheptylphenol, propoxyoctylphenol, propoxynonylphenol, propoxydecylphenol, propoxyphenylphenol, and the like alkoxyphenols;

Hydroxyphenyl thio ethers such as hydroxyphenyl methyl sulfide, hydroxyphenyl ethyl sulfide, hydroxyphenyl propyl sulfide, hydroxyphenyl butyl sulfide, hydroxyphenyl pentyl sulfide, hydroxyphenyl hexyl sulfide, hydroxyphenyl heptyl sulfide, hydroxyphenyl octyl sulfide, hydroxyphenyl nonyl sulfide, hydroxyphenyl decyl sulfide, and hydroxyphenyl phenyl sulfide;

methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, methoxypentylamine, methoxyhexylamine, methoxyheptylamine, methoxyoctylamine, methoxynonylamine, methoxydecylamine, methoxyaniline, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, ethoxypentylamine, ethoxyhexylamine, ethoxyheptylamine, ethoxyoctylamine, ethoxynonylamine, ethoxydecylamine, ethoxyaniline, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, propoxypentylamine, propoxyhexylamine, propoxyheptylamine, propoxyoctylamine, propoxynonylamine, propoxydecylamine, propoxyaniline, and the like.

Examples

The present invention will be described in more detail with reference to examples and comparative examples. The present invention is not limited by the following examples as long as the gist thereof is not exceeded.

[ raw materials and reagents ]

In the following examples and comparative examples, o-cresol, toluene, sodium hydroxide, dodecyl mercaptan, acetone, sodium bicarbonate, cesium carbonate, citric acid, malonic acid, oxalic acid, succinic acid, tartaric acid, disodium ethylenediamine tetraacetate, dodecanal, and heptane were used as reagents manufactured by Fuji film and Wako pure chemical industries, ltd.

Hydrogen chloride gas was used as a product of Sumitomo refining Co.

Diphenyl carbonate was used as a product manufactured by mitsubishi chemical corporation.

Analysis

< composition of bisphenol C production reaction liquid >

The composition analysis of the bisphenol C-forming reaction solution was performed by high performance liquid chromatography in the following order and conditions.

Device: LC-2010A manufactured by Shimadzu corporation "

Imtakt ScherzoSM-C18 3μm 250mm×3.0mmID

Low pressure gradient method

Analysis temperature: 40 DEG C

Eluent composition:

solution a ammonium acetate: acetic acid: deionized water = 3.000g:1mL:1L of solution

Solution B ammonium acetate: acetic acid: acetonitrile: deionized water = 1.500g:1mL:900mL:150mL of solution

At analysis time 0 min, the eluent composition was liquid a: solution B = 60:40 (volume ratio, the same as below.)

The analysis time was 0 to 41.67 minutes, and the analysis time was changed slowly to solution A: solution B = 10:90,

maintaining the solution A for 41.67 to 50 minutes: solution B = 10:90,

The analysis was performed at a flow rate of 0.34 mL/min.

< identification of isopropenylcresol >

The identification of isopropenylcresol was performed using a gas chromatograph mass spectrometer in the following order and conditions.

Device: agilent6890 manufactured by Agilent Technologies company "

Column: "DB-1MS" (inner diameter 0.25 mm. Times.30 m. Times.0.25 μm) manufactured by Agilent Technologies Co., ltd

Carrier gas: helium

Flow rate: 1cm per minute ³

Injection port temperature: 280 DEG C

Interface temperature: 250 DEG C

Ion source temperature: 250 DEG C

Column temperature increase mode: first at 50℃for 3 minutes, then at 10℃per minute to 320℃and at 280℃for 5 minutes

< determination of iron concentration contained in bisphenol C or 1, 1-bis (4-hydroxyphenyl) dodecane >

1g of bisphenol C or 1, 1-bis (4-hydroxyphenyl) dodecane was ashed and dissolved in an acid to prepare a sample. The analysis was performed using the following apparatus.

The device comprises:

ICP-MS: thermo Fisher Scientific company "ELEMENT2"

ICP-OES: agilent (VARIAN) "ICP VISTA-PRO"

< measurement of pH >

In the measurement of pH, a pH METER "pH METER ES-73" manufactured by horiba, inc. was used, and the measurement was performed on the aqueous phase at 25℃taken out of the flask.

< conductivity >

The conductivity was measured using a conductivity METER "COND METER D-71" manufactured by horiba, inc., and the aqueous phase at 25℃taken out of the flask.

< methanol-soluble color of bisphenol C >

Regarding the methanol-dissolved color of bisphenol C, test tubes manufactured by Nitro chemical Co., ltdBisphenol C10g and methanol 10g were added to prepare a homogeneous solution, and the Hazen color number was measured at room temperature (about 20 ℃) using "SE6000" manufactured by the Nippon electric color industry Co., ltd.

< melt color difference of bisphenol C >

Regarding the melt color difference of bisphenol C, test tubes manufactured by Nitro chemical Co., ltdBisphenol C20 g was added thereto, and the mixture was melted at 190℃for 30 minutes, and the Hazen color value thereof was measured by using "SE6000" manufactured by the electric color industry Co., ltd.

< thermal tone stability of bisphenol C >

Regarding the thermal tone stability of bisphenol C, test tubes manufactured by Nitro-chemical Co., ltdBisphenol C20 g was added thereto, and the mixture was melted at 190℃for 4 hours, and the Hazen color value thereof was measured by using "SE6000" manufactured by the electric color industry Co., ltd.

< thermal decomposition stability of bisphenol C >

Regarding the thermal decomposition stability of bisphenol C, test tubes manufactured by Nitro chemical Co., ltd 20g of bisphenol C was added thereto, and the mixture was melted at 190℃for 2 hours, and the amount of isopropenylcresol produced was measured and evaluated in the same manner as in the composition analysis of the bisphenol C-producing reaction solution.

< viscosity average molecular weight >

The polycarbonate resin was dissolved in methylene chloride (concentration: 6.0 g/L), and the specific viscosity (. Eta.sp) at 20℃was measured using a Ubbelohde viscosity tube, and the viscosity average molecular weight (Mv) was calculated from the following formula.

ηsp/C＝[η](1+0.28ηsp)

[η]＝1.23×10 ^-4 Mv ^0.83

< pellet YI >

Regarding the pellets YI (transparency of polycarbonate resin), YI value (yellowness index value) of the polycarbonate resin pellets under reflected light was measured in accordance with ASTM D1925, and the YI was evaluated. The apparatus used was a spectrophotometer "CM-5" manufactured by Konikoku Megawa, and the measurement conditions were selected to measure 30mm and SCE.

The culture dish measuring calibration glass "CM-A212" was inserted into the measuring section, and zero calibration was performed by covering the measuring section with a zero calibration box "CM-A124" from above, followed by white calibration using a built-in white calibration plate. Then, measurement was performed using a white calibration plate "CM-a210", and it was confirmed that L was 99.40±0.05, a was 0.03±0.01, b was-0.43±0.01, and YI was-0.58±0.01.

YI was measured by filling pellets into a cylindrical glass vessel having an inner diameter of 30mm and a height of 50mm to a depth of about 40 mm. The pellet was taken out of the glass container, and then the measurement was performed again, and this operation was repeated 2 times, and an average value of measurement values of 3 total times was used.

Reference example 1

An 500mL eggplant-shaped flask equipped with a stirrer, a thermometer and a distillation apparatus was charged with 85g of bisphenol C and 4.5g of sodium hydroxide, and immersed in an oil bath heated to 195 ℃. After confirming that bisphenol C in the eggplant-shaped flask was melted, the flask was gradually depressurized using a vacuum pump to make it a complete vacuum. After a short period of time, evaporation was started, and distillation under reduced pressure was performed until the end of distillation. The gas chromatograph equipped with a mass spectrometer detector shows that the fraction obtained is a mixture of cresol and isopropenylcresol produced by thermal decomposition of bisphenol C. Using the obtained fraction, the retention time of isopropenylcresol under the condition of the composition analysis of the bisphenol C-forming reaction liquid was confirmed.

Reference example 2

(1) Preparation of the Mixed solution

A separable flask equipped with a hydrogen chloride blowing tube, a thermometer, a jacket, and an anchor stirrer was charged with 510g (4.7 mol) of o-cresol, 104g (1.8 mol) of acetone, 100g of toluene, and 10g of dodecyl mercaptan under a nitrogen atmosphere, and the internal temperature was set at 30℃to prepare a mixed solution.

(2) Reaction

After bubbling hydrogen chloride gas slowly in the above-mentioned mixed solution, the reaction was carried out for 10 hours to obtain a reaction solution.

(3) Coarse refining

To the resulting reaction solution were added 720g of toluene and 900g of deionized water, followed by warming the inner temperature to 80℃with stirring. And standing after the internal temperature reaches 80 ℃, and separating into a 1 st organic phase and a 1 st aqueous phase to obtain the 1 st organic phase.

250g of deionized water was added to the obtained organic phase 1, and after the internal temperature reached 80 ℃, the mixture was allowed to stand, and separated into an organic phase 2 and an aqueous phase 2, and the aqueous phase 2 was extracted, whereby an organic phase 2 was obtained.

To 1400g of the obtained organic phase 2 was added 300g of 5 mass% aqueous sodium hydrogencarbonate, and the mixture was allowed to stand while the internal temperature was being 80℃and then the pH of the lower layer was found to be 9 or more. Thereafter, the 3 rd organic phase and the aqueous sodium hydrogencarbonate solution were subjected to phase separation, and the lower layer was withdrawn to obtain the 3 rd organic phase.

(4) Refining

The obtained 3 rd organic phase was cooled from 80℃to 10℃and after reaching 10℃was subjected to solid-liquid separation using centrifugation (rotation speed 2500 times per minute, 10 minutes), to obtain a 1 st wet cake. The obtained 1 st wet cake was transferred to a beaker, and 500g of toluene was added thereto for suspension washing. The obtained slurry was subjected to solid-liquid separation again by centrifugation (rotation speed 2500 times per minute, 10 minutes), to obtain 415g of a 2 nd wet cake.

The iron concentration of bisphenol C contained in the obtained 2 nd wet cake was 4.7 mass ppm.

Example 1

To a full-tube type separable flask equipped with a thermometer and a stirrer, 300g of a part of the wet cake 2 of referential example 2 and 420g of toluene were charged, and the temperature was raised to 80 ℃. It was confirmed that the solution was homogeneous, and the 4 th organic phase was obtained. To 700g of the obtained organic phase 4 was added 200g of 5 mass% hydrochloric acid, and the mixture was mixed for 30 minutes, followed by removal of the lower aqueous phase 3 to obtain an organic phase 5. 200g of deionized water was added to the obtained 5 th organic phase, and the mixture was mixed for 30 minutes, followed by removal of the lower 4 th aqueous phase to obtain a 6 th organic phase.

The pH of the 4 th aqueous phase (the pH of the aqueous phase before disodium ethylenediamine tetraacetate was supplied) was confirmed, and as a result, pH2 was obtained.

To 700g of the obtained 6 th organic phase was added 1g of 5 mass% disodium ethylenediamine tetraacetate aqueous solution, and the mixture was mixed for 30 minutes, and the solution was confirmed by a pH test paper, whereby it was confirmed that the aqueous phase was pH2. To this was added a saturated aqueous sodium carbonate (18 mass%) until the aqueous phase showed basicity, and mixing was performed for 30 minutes, and the 5 th aqueous phase was withdrawn to obtain a 7 th organic phase.

The pH of the 5 th aqueous phase (the pH of the aqueous phase after disodium ethylenediamine tetraacetate was extracted) was confirmed, and as a result, pH9 was obtained.

The obtained 7 th organic phase was repeatedly washed with deionized water until the conductivity of the lower aqueous phase became 3.0. Mu.S/cm or less, thereby obtaining an 8 th organic phase.

The 8 th organic phase obtained was cooled from 80 ℃ to 10 ℃. Thereafter, the resultant was filtered using a centrifuge (rotation speed: 3000 times/min, 10 min) to obtain wet purified bisphenol C. The light boiling components were distilled off at 80℃under reduced pressure using an evaporator having an oil bath, whereby 210g of bisphenol C was obtained as white.

The iron concentration of bisphenol C obtained was 16 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 0. The melt color difference of the bisphenol C obtained was measured, and as a result, hazen color number was 10. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 36. The thermal decomposition stability of the bisphenol C obtained was measured, and as a result, the produced amount of isopropenylcresol was 100 mass ppm.

Example 2

The procedure of example 1 was repeated, except that 10g of an aqueous solution of disodium edetate of 5% by mass was added in place of 1g of an aqueous solution of disodium edetate of 5% by mass in example 1.

The aqueous phase before the supply of disodium edetate was pH2 and the aqueous phase from which disodium edetate was withdrawn was pH9.

The iron concentration of bisphenol C obtained was 20 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 0. The melt color difference of the bisphenol C obtained was measured, and as a result, hazen color number was 10. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 34. The thermal decomposition stability of the bisphenol C obtained was measured, and as a result, the produced amount of isopropenylcresol was 95 mass ppm.

Example 3

The procedure of example 1 was repeated, except that 100g of an aqueous solution of disodium edetate of 5% by mass was added in place of 1g of an aqueous solution of disodium edetate of 5% by mass in example 1.

The iron concentration of bisphenol C obtained was 18 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 0. The melt color difference of the bisphenol C obtained was measured, and as a result, hazen color number was 10. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 33. As a result of measurement of the thermal decomposition stability of the bisphenol C obtained, the amount of isopropenylcresol produced was 91 ppm by mass.

Example 4

To a full-tube type separable flask equipped with a thermometer and a stirrer, 300g of a part of the wet cake 2 of referential example 2 and 420g of toluene were charged, and the temperature was raised to 80 ℃. It was confirmed that a homogeneous solution was obtained, and a 4 th organic phase was obtained. To 700g of the obtained organic phase 4 was added 300g of 5% by mass disodium ethylenediamine tetraacetate solution, and the mixture was mixed for 30 minutes, and the solution properties were confirmed by a pH test paper, whereby it was confirmed that the aqueous phase was pH5.

To this was added a saturated aqueous sodium carbonate (18 mass%) until the aqueous phase showed basicity, and mixing was performed for 30 minutes, and the 4 th aqueous phase was withdrawn to obtain a 5 th organic phase.

The pH of the 4 th aqueous phase (pH of the aqueous phase from which disodium ethylenediamine tetraacetate was extracted) was confirmed, and as a result, pH9 was obtained.

The obtained 5 th organic phase was repeatedly washed with deionized water until the conductivity of the lower aqueous phase became 3.0. Mu.S/cm or less, thereby obtaining a 6 th organic phase.

The resulting organic phase 6 was cooled from 80 ℃ to 10 ℃. Thereafter, the mixture was filtered using a centrifuge (3000 rpm, 10 min) to obtain wet purified bisphenol C. The light boiling components were distilled off at 80℃under reduced pressure using an evaporator having an oil bath, whereby 209g of bisphenol C was obtained as white.

The iron concentration of bisphenol C obtained was 54 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 0. The melt color difference of bisphenol C obtained was measured, and as a result, hazen color number was 19. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 38. As a result of measuring the thermal decomposition stability of the obtained bisphenol C, the produced amount of isopropenylcresol was 127 mass ppm.

Comparative example 1

To a full-tube type separable flask equipped with a thermometer and a stirrer, 300g of a part of the wet cake 2 of referential example 2 and 420g of toluene were charged, and the temperature was raised to 80 ℃. It was confirmed that a homogeneous solution was obtained, and a 4 th organic phase was obtained. 200g of deionized water was added to the obtained organic phase 4, and the mixture was mixed for 30 minutes, followed by removal of the lower aqueous phase 3 to obtain an organic phase 5.

As a result of confirming the liquid properties with a pH test paper, the 3 rd aqueous phase (pH of the aqueous phase before supplying disodium ethylenediamine tetraacetate) was set to pH9.

To the obtained 5 th organic phase, 10g of a 5% by mass disodium edetate aqueous solution was added, and the mixture was mixed for 30 minutes, followed by extraction of the 4 th aqueous phase to obtain a 6 th organic phase.

The 4 th aqueous phase (pH of the aqueous phase from which disodium ethylenediamine tetraacetate was withdrawn) was pH9.

The obtained 6 th organic phase was repeatedly washed with deionized water until the conductivity of the lower aqueous phase became 3.0. Mu.S/cm or less, thereby obtaining a 7 th organic phase.

The 7 th organic phase obtained was cooled from 80 ℃ to 10 ℃. Thereafter, the mixture was filtered using a centrifuge (3000 rpm, 10 min) to obtain wet purified bisphenol C. The light boiling components were distilled off at 80℃under reduced pressure using an evaporator having an oil bath, whereby 212g of bisphenol C was obtained as white.

The iron concentration of bisphenol C obtained was 102 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 12. The melt color difference of bisphenol C obtained was measured, and as a result, hazen color number was 42. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 65. As a result of measuring the thermal decomposition stability of the bisphenol C obtained, the amount of isopropenylcresol produced was 250 mass ppm.

Comparative example 2

To a full-tube type separable flask equipped with a thermometer and a stirrer, 300g of a part of the wet cake 2 of referential example 2 and 420g of toluene were charged, and the temperature was raised to 80 ℃. It was confirmed that a homogeneous solution was obtained, and a 4 th organic phase was obtained. 200g of 5% by mass hydrochloric acid was added to the obtained 4 th organic phase, and the mixture was mixed for 30 minutes, followed by removal of the 3 rd aqueous phase as the lower layer, to obtain a 5 th organic phase. 200g of deionized water was added to the obtained 5 th organic phase, and the mixture was mixed for 30 minutes, followed by removal of the lower 4 th aqueous phase to obtain a 6 th organic phase.

The 4 th aqueous phase (the pH of the aqueous phase before disodium edetate was supplied) was pH2.

To the obtained 6 th organic phase, 10g of a 5% by mass disodium edetate aqueous solution was added, and the mixture was mixed for 30 minutes, followed by removal of the 5 th aqueous phase to obtain a 7 th organic phase.

The 5 th aqueous phase was pH2.

To the obtained 7 th organic phase was added a saturated aqueous sodium carbonate solution until the aqueous phase showed basicity, and the mixture was mixed for 30 minutes, and the 6 th aqueous phase was withdrawn to obtain an 8 th organic phase. The obtained 8 th organic phase was repeatedly washed with deionized water until the conductivity of the lower aqueous phase became 3.0. Mu.S/cm or less, thereby obtaining a 9 th organic phase.

The 9 th organic phase obtained was cooled from 80 ℃ to 10 ℃. Thereafter, the mixture was filtered using a centrifuge (3000 rpm, 10 min) to obtain wet purified bisphenol C. The light boiling components were distilled off at 80℃under reduced pressure using an evaporator having an oil bath, whereby 209g of bisphenol C was obtained as white.

The iron concentration of bisphenol C obtained was 89 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 5. The melt color difference of bisphenol C obtained was measured, and as a result, hazen color number was 41. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 80. As a result of measuring the thermal decomposition stability of the bisphenol C obtained, the yield of isopropenylcresol was 210 mass ppm.

Table 1 summarizes the pH of the aqueous phase before disodium ethylenediamine tetraacetate was supplied, the pH of the aqueous phase from which disodium ethylenediamine tetraacetate was extracted, the iron concentration of bisphenol C obtained, the methanol dissolution color, the melt color difference, the thermal tone stability, and the thermal decomposition stability in examples 1 to 4 and comparative examples 1 and 2.

As is clear from table 1, when the aqueous phase before disodium ethylenediamine tetraacetate was supplied had acidic and the aqueous phase from which disodium ethylenediamine tetraacetate was extracted had basic, the iron concentration, methanol dissolution color, melt color difference, thermal tone stability, and thermal decomposition stability of the bisphenol C obtained were improved.

In comparative example 2, after disodium ethylenediamine tetraacetate was added, a saturated aqueous sodium carbonate solution was added to the organic phase after removal of the aqueous phase, and thus the effect of removing iron by the chelating agent was not obtained.

TABLE 1

Example 5

The procedure of example 2 was repeated, except that 10g of 5% by mass of an aqueous solution of citric acid was added instead of 10g of 5% by mass of an aqueous solution of disodium ethylenediamine tetraacetate in example 2.

The iron concentration of bisphenol C obtained was 22 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 0. The melt color difference of the bisphenol C obtained was measured, and as a result, hazen color number was 10. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 32. As a result of measuring the thermal decomposition stability of the bisphenol C obtained, the amount of produced isopropenylcresol was 99 mass ppm.

Example 6

The procedure of example 2 was repeated, except that 10g of 5% by mass of an aqueous oxalic acid solution was added instead of 10g of 5% by mass of an aqueous disodium ethylenediamine tetraacetate solution in example 2.

The iron concentration of bisphenol C obtained was 32 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 0. The melt color difference of the bisphenol C obtained was measured, and as a result, hazen color number was 10. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 35. As a result of measurement of the thermal decomposition stability of the bisphenol C obtained, the produced amount of isopropenylcresol was 98 mass ppm.

Example 7

The procedure of example 2 was repeated, except that 10g of 5% by mass of an aqueous malonic acid solution was added instead of 10g of 5% by mass of an aqueous disodium ethylenediamine tetraacetate solution in example 2.

The iron concentration of bisphenol C obtained was 35 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 0. The melt color difference of the bisphenol C obtained was measured, and as a result, hazen color number was 10. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 33. The thermal decomposition stability of the bisphenol C obtained was measured, and as a result, the produced amount of isopropenylcresol was 95 mass ppm.

Example 8

The procedure of example 2 was repeated, except that 10g of 5% by mass of an aqueous succinic acid solution was added instead of 10g of 5% by mass of an aqueous disodium ethylenediamine tetraacetate solution in example 2.

The iron concentration of bisphenol C obtained was 23 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 0. The melt color difference of the bisphenol C obtained was measured, and as a result, hazen color number was 10. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 32. As a result of measuring the thermal decomposition stability of the bisphenol C obtained, the amount of produced isopropenylcresol was 90 mass ppm.

Example 9

The procedure of example 2 was repeated, except that 10g of 5% by mass of an aqueous solution of tartaric acid was added instead of 10g of 5% by mass of an aqueous solution of disodium ethylenediamine tetraacetate in example 2.

The iron concentration of bisphenol C obtained was 21 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 0. The melt color difference of the bisphenol C obtained was measured, and as a result, hazen color number was 10. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 31. The thermal decomposition stability of the bisphenol C obtained was measured, and as a result, the produced amount of isopropenylcresol was 85 mass ppm.

Comparative example 3

The procedure of comparative example 2 was repeated, except that 10g of 5% by mass of an aqueous solution of citric acid was added instead of 10g of 5% by mass of an aqueous solution of disodium ethylenediamine tetraacetate in comparative example 2.

The iron concentration of bisphenol C obtained was 102 ppb by mass.

The methanol-soluble color of bisphenol C obtained was measured, and as a result, hazen color number was 10. The melt color difference of bisphenol C obtained was measured, and as a result, hazen color number was 39. The thermal tone stability of the bisphenol C obtained was measured, and as a result, the Hazen color number was 77. As a result of measuring the thermal decomposition stability of the bisphenol C obtained, the amount of isopropenylcresol produced was 310 ppm by mass.

Table 2 summarizes the chelating agents used in examples 5 to 9 and comparative example 3, the iron concentration of bisphenol C obtained, the methanol dissolution color, the melt color difference, the thermal tone stability and the thermal decomposition stability.

As is clear from table 2, even when other chelating agents are used in the same manner as disodium ethylenediamine tetraacetate, the iron concentration, methanol dissolution color, melt color difference, thermal tone stability, and thermal decomposition stability of the bisphenol C obtained can be improved.

TABLE 2

Example 10

A glass reaction vessel having a stirrer and a condenser and containing 150mL of the content was charged with 100.00g (0.39 mol) of bisphenol C obtained in example 2, 86.49g (0.4 mol) of diphenyl carbonate and 479. Mu.L of a 400-mass ppm cesium carbonate aqueous solution. The glass reaction vessel was depressurized to about 100Pa, then repressed to atmospheric pressure with nitrogen gas, and the operation was repeated 3 times to replace the inside of the reaction vessel with nitrogen gas. Thereafter, the reaction vessel was immersed in an oil bath at 200℃to dissolve the contents.

The stirring speed was set to 100 times per minute, and the pressure in the reaction vessel was reduced from 101.3kPa to 13.3kPa in 40 minutes while phenol produced by the oligomerization reaction of bisphenol C and diphenyl carbonate in the reaction vessel was distilled off. Then, the pressure in the reaction vessel was kept at 13.3kPa, and the transesterification was carried out for 80 minutes while further distilling off phenol. Thereafter, the temperature outside the reaction tank was raised to 250℃and the pressure in the reaction tank was reduced from 13.3kPa to 399Pa in 40 minutes, whereby distilled phenol was discharged out of the system.

Thereafter, the outside temperature of the reaction tank was raised to 280℃and the absolute pressure of the reaction tank was reduced to 30Pa to carry out polycondensation. When the stirrer of the reaction tank reaches a preset stirring power, the polycondensation reaction is ended. The time after the temperature was raised to 280℃until the polymerization was completed (the latter polymerization time) was 210 minutes.

Then, the reaction vessel was repressed with nitrogen to an absolute pressure of 101.3kPa, and then, the pressure was increased to a gauge pressure of 0.2MPa, and the polycarbonate resin was withdrawn in a strand form from the bottom of the reaction vessel to obtain a polycarbonate resin in a strand form.

The strands were then pelletized using a rotary cutter to obtain a pellet-like polycarbonate resin.

The obtained polycarbonate resin had a viscosity average molecular weight (Mv) of 24700 and a pellet YI of 7.7, and a polycarbonate resin having a good color tone was obtained.

Reference example 3

In a full-tube type detachable flask equipped with a thermometer and a stirrer, 237g (2.5 moles) of phenol was heated to 40℃and 3.2g of hydrochloric acid was added. A mixture of 92.0g (0.5 mol) of dodecanol and 55.2g of toluene was added dropwise thereto over 4 hours. After the dropwise addition, the mixture was stirred at 40℃for 1 hour, and then a 5% by mass aqueous sodium hydrogencarbonate solution was added. Toluene and phenol were then distilled off under reduced pressure to give a residue. To the residue, 450g of toluene was added and dissolved to obtain an organic phase. The organic phase was washed 4 times with deionized water 230 g. Toluene was then distilled off to obtain a residue. To the resulting residue, 330g of toluene and 330g of heptane were added, and the mixture was heated to 70℃to dissolve the mixture. And then cooling to 5 ℃ to precipitate solids, thus obtaining slurry liquid. The resulting slurry was filtered to give a solid. The obtained solid was put into a eggplant-shaped bottle and dried at 70℃and 20Torr for 1 hour using a rotary evaporator to obtain 45g of 1, 1-bis (4-hydroxyphenyl) dodecane. The iron concentration of the obtained 1, 1-bis (4-hydroxyphenyl) dodecane was 570 ppb by mass.

Example 11

10g of 1, 1-bis (4-hydroxyphenyl) dodecane obtained in referential example 3 and 14g of toluene were charged into an eggplant-shaped flask equipped with a magnetic rotor, and the mixture was dissolved at 80℃to obtain a toluene solution. 7g of 5 mass% hydrochloric acid was added thereto and stirred. After the obtained mixture was allowed to stand for 30 minutes, the aqueous phase was removed to obtain the 1 st organic phase. The pH of the removed aqueous phase is less than 1.

After adding 7g of deionized water to the obtained 1 st organic phase, the mixture was shaken for 10 minutes by a separating funnel, and then allowed to stand for 30 minutes, after which the aqueous phase was removed to obtain a 2 nd organic phase. To the obtained organic phase, 0.3g of 5% by mass of disodium ethylenediamine tetraacetate aqueous solution was added, followed by shaking for 10 minutes, and 2g of 5% by mass of sodium hydrogencarbonate aqueous solution was further added, followed by shaking for 10 minutes. After standing for 30 minutes, the aqueous phase was removed to give the 3 rd organic phase. The pH of the removed aqueous phase was 9.

The 3 rd organic phase thus obtained was repeatedly washed 3 times with 7g of deionized water, thereby obtaining a 4 th organic phase. The 4 th organic phase obtained was cooled to 10℃to obtain a slurry. The resulting slurry was filtered, and the resulting cake was dried at 70℃under reduced pressure, whereby 7.5g of 1, 1-bis (4-hydroxyphenyl) dodecane was obtained. The iron concentration of the obtained 1, 1-bis (4-hydroxyphenyl) dodecane was 100 ppb by mass.

Comparative example 4

10g of 1, 1-bis (4-hydroxyphenyl) dodecane obtained in referential example 3 and 14g of toluene were placed in an eggplant-shaped flask equipped with a nuclear magnetic rotor, and dissolved at 80℃to obtain a toluene solution. To the toluene solution thus obtained, 0.3g of a 5% by mass aqueous solution of disodium ethylenediamine tetraacetate was added, and the mixture was shaken for 10 minutes. After the obtained mixture was allowed to stand for 30 minutes, the aqueous phase was removed to obtain the 1 st organic phase. The obtained 1 st organic phase was repeatedly washed 3 times with 7g of deionized water, thereby obtaining 2 nd organic phase. The obtained 2 nd organic phase was cooled to 10℃to obtain a slurry. The resulting slurry was filtered, and the resulting cake was dried at 70℃under reduced pressure, whereby 7.5g of 1, 1-bis (4-hydroxyphenyl) dodecane was obtained. The iron concentration of the obtained 1, 1-bis (4-hydroxyphenyl) dodecane was 400 ppb by mass.

Table 3 summarizes the iron concentrations of 1, 1-bis (4-hydroxyphenyl) dodecane obtained by changing the pH before and after adding the 5% by mass disodium ethylenediamine tetraacetate aqueous solution in example 11 and comparative example 4.

As is clear from table 3, the iron concentration of 1, 1-bis (4-hydroxyphenyl) dodecane can be reduced by changing the pH before and after the addition of the 5 mass% disodium ethylenediamine tetraacetate aqueous solution.

TABLE 3

Although the present application has been described in detail with particular reference to the specific embodiments thereof, it will be apparent to one skilled in the art that various modifications can be made therein without departing from the spirit and scope thereof.

The present application is based on Japanese patent applications 2019-049991 filed on 3 months 18 in 2019 and Japanese patent applications 2019-238265 filed on 12 months 27 in 2019, the entire contents of which are incorporated by reference.

Claims

1. A method for producing bisphenol, comprising the steps of:

a step of mixing the organic phase 1 of the mixed solution 1 with a chelating agent to obtain a mixed solution 2 of an aqueous phase having a pH of 6 or less and the organic phase, wherein the mixed solution 1 is a mixed solution of the aqueous phase 1 and the bisphenol-containing organic phase 1;

mixing the obtained mixed solution 2 with a base to obtain a mixed solution 3 of an aqueous phase and an organic phase having a pH of 8 or more; and

removing the aqueous phase having a pH of 8 or more from the obtained mixed solution 3 to obtain an organic phase 3A,

the chelating agent has a higher solubility in the aqueous phase of the mixed liquor 3 than in the organic phase of the mixed liquor 3,

the chelating agent is one or more selected from the group consisting of acetylacetone, 3, 5-heptanedione, ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentaacetic acid, hydroxyethyl ethylenediamine triacetic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid salt, diethylenetriamine pentaacetic acid, hydroxyethyl ethylenediamine triacetic acid, pyruvic acid, acetoacetic acid, levulinic acid, alpha-ketoglutaric acid, acetone dicarboxylic acid, glycolic acid, glyceric acid, lignoic acid, gluconic acid, lactic acid, tartronic acid, tartaric acid, xylose diacid, galactose diacid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, aspartic acid, glutamic acid, phytic acid, hydroxyethylenediphosphate, nitrilotrimethylene phosphoric acid, ethylenediamine tetramethylene phosphoric acid, dimethylglyoxime, benzyl glyoxime and 1, 2-cyclohexyl glyoxime.

2. The method for producing bisphenol according to claim 1, wherein said organic phase 1A is an organic phase 1A obtained by removing an aqueous phase from said mixed solution 1.

3. The method for producing bisphenol according to claim 2, wherein the aqueous phase is removed from the mixed solution 1 so that a mixing ratio of the aqueous phase after removal of the aqueous phase and the organic phase 1A is 1:700 or less by weight.

4. The method for producing bisphenol according to any one of claims 1 to 3, wherein a mixing ratio of the aqueous phase and the organic phase in the mixed solution 2 is 0.001:100 to 1000:700 in terms of a weight ratio.

5. The method for producing bisphenol according to any one of claims 1 to 3, comprising a step of removing an aqueous phase from a mixed solution 4 obtained by mixing the organic phase 3A with deionized water to obtain the organic phase 4.

6. The method according to any one of claims 1 to 3, wherein the bisphenol is obtained by condensing a ketone or aldehyde with an aromatic alcohol in the presence of hydrogen chloride.

7. The method for producing bisphenol according to any one of claims 1 to 3, wherein the bisphenol is any one selected from the group consisting of 2, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) dodecane, and 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) methane.

8. A method for producing a polycarbonate resin using the bisphenol produced by the method for producing a bisphenol according to any one of claims 1 to 7, wherein the method for producing a polycarbonate resin includes the method for producing a bisphenol according to any one of claims 1 to 7.