TWI818160B - Manufacturing method of bisphenol and manufacturing method of polycarbonate resin - Google Patents

Abstract

The manufacturing method of bisphenol of the present invention includes the following steps: mixing the organic phase 1 of the mixed liquid 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol with a chelating agent to obtain a mixture of the aqueous phase and the organic phase with a pH below 6. The steps of liquid 2; the steps of mixing the obtained mixed liquid 2 with an alkali to obtain a mixed liquid 3 of an aqueous phase with a pH of 8 or more and an organic phase; and removing the aqueous phase with a pH of 8 or more from the obtained mixed liquid 3. The step of organic phase 3A; and the solubility of the chelating agent in the aqueous phase of the mixed liquid 3 is higher than the solubility in the organic phase of the mixed liquid 3.

Description

Manufacturing method of bisphenol and manufacturing method of polycarbonate resin

The present invention relates to a method for producing bisphenol and a method for producing polycarbonate resin using the obtained bisphenol. The bisphenol produced by the method of the present invention can be used as a resin raw material such as polycarbonate resin, epoxy resin, aromatic polyester resin, or a hardener, color developer, anti-fading agent, other bactericides, antibacterial and antifungal agents, etc. Additives are more useful.

Bisphenol is useful as a raw material for polymer materials such as polycarbonate resin, epoxy resin, and aromatic polyester resin. As representative bisphenols, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, etc. are known, for example (Patent Document 1). Furthermore, a method for producing bisphenol containing a fluorine skeleton is also known (Patent Document 2).

[Patent Document 1] Japanese Patent Application Publication No. 2014-40376 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-26349

The industry requires polycarbonate resin, a representative use of bisphenol, to be colorless and transparent. The color tone of polycarbonate resin is greatly affected by the color tone of the raw materials. Therefore, the color tone of bisphenol as a raw material is also required to be colorless. Since it is difficult to directly measure the color of bisphenol, in the present invention, the color difference is quantified by dissolving bisphenol in methanol, and this hue is called "methanol-dissolved color".

In the production of polycarbonate resin, especially in the melting method, bisphenol is melted to produce polycarbonate resin, so it is exposed to high temperatures. Therefore, the stability of the thermal color tone of bisphenol is also required. In the present invention, this hue is called "fusion color difference".

In the production of polycarbonate resin, the polymerization reaction is carried out after melting bisphenol, so thermal color tone stability is also required before the start of polymerization. In the present invention, this color tone is called "thermal color tone stability".

In the production of polycarbonate resin, if bisphenol is thermally decomposed before the start of polymerization, the mass of bisphenol is reduced, and the mass ratio of bisphenol to diphenyl carbonate, which is the raw material, deviates from the predetermined mass ratio, and the desired mass cannot be obtained. A polycarbonate resin with a high molecular weight is required, so the thermal stability of bisphenol is also required. In the present invention, this stability is called "thermal decomposition stability".

Regarding polycarbonate resin, the industry requires a polycarbonate resin with a designed molecular weight and a good color tone. In order to produce such a polycarbonate resin, bisphenol which is a raw material is required to have excellent methanol-soluble color, melt color difference, and thermal hue stability, as well as excellent thermal decomposition stability.

When hydrogen chloride gas or hydrochloric acid is used as a catalyst for the bisphenol production reaction, the hydrogen chloride volatilizes and corrodes the equipment, and the corrosive components are mixed into the bisphenol. Therefore, the quality of the bisphenol is easily deteriorated, and this situation is difficult to avoid. Therefore, in order to obtain bisphenol of good quality, it is important to wash the bisphenol efficiently and recover it efficiently.

As a method for recovering bisphenol, for example, there is known a method in which, like the method described in Patent Document 1, the concentration of the acid catalyst is reduced by supplying water to the reaction solution, and the reaction is completed (stopped), and then recovered. bisphenol. However, if the water phase after the bisphenol generation reaction is heated while recovering the bisphenol in a highly acidic state, the bisphenol will be easily decomposed and other problems such as an increase in by-products will occur. In order to suppress the decomposition of bisphenol, a method is known in which an acid catalyst is neutralized using an alkaline aqueous solution to reduce the acidity of the reaction solution and terminate the reaction (for example, Patent Document 2). However, in this method, the concentration of the aqueous phase after the bisphenol generation reaction becomes pH 4 to 6, and it is difficult to improve the quality of bisphenol that has deteriorated due to 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 equipment corrosion is required.

The object of the present invention is to provide a method for producing good-quality bisphenol and the production of polycarbonate resin using the bisphenol by delving into the recovery steps of bisphenol produced using hydrogen chloride gas or hydrochloric acid as an acid catalyst. method.

The inventors of the present invention have discovered that after the formation reaction of bisphenol, a chelating agent is added to an organic phase containing bisphenol under specific conditions and mixed, and then an alkaline aqueous solution is added and mixed, thereby producing bisphenol of good quality. Furthermore, the present inventors discovered that polycarbonate resin with good color tone can be produced using the produced bisphenol. The gist of the present invention lies in the following [1] to [9].

[1] A method for producing bisphenol, which includes the following steps: mixing the organic phase 1 of the mixed liquid 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol with a chelating agent to obtain an aqueous phase and an organic phase with a pH of below 6. The steps of mixed liquid 2; the steps of mixing the obtained mixed liquid 2 with an alkali to obtain a mixed liquid 3 of an aqueous phase above pH 8 and an organic phase; and removing the aqueous phase above pH 8 from the obtained mixed liquid 3. The step of obtaining organic phase 3A; and the solubility of the chelating agent in the aqueous phase of the mixed liquid 3 is higher than the solubility in the organic phase of the mixed liquid 3 .

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

[3] The method for producing bisphenol as described in [2], wherein the mixing ratio of the aqueous phase after the removal of the aqueous phase and the organic phase 1A becomes 1:700 or less in terms of weight ratio. Remove the water phase from Mixed Solution 1.

[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 liquid 2 is 0.001:100-1000 by weight. :700.

[5] The method for producing bisphenol according to any one of [1] to [4], which includes the step of removing the water phase from the mixed liquid 4 obtained by mixing the above-mentioned organic phase 3A and desalted water, Obtain organic phase 4.

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

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

[9] A method for producing an organic compound, which is a method for producing an organic compound containing a metal coordination property of a partial structure represented by the following formula (I) in the molecule, which includes the following steps: adding the aqueous phase 1' and containing The step of mixing the organic phase 1' of the organic phase 1' of the organic compound with a chelating agent to obtain a mixed liquid 2' of an aqueous phase and an organic phase with a pH below 6; 'The step of mixing with a base to obtain a mixed liquid 3' of an aqueous phase with a pH of 8 or above and an organic phase; and the step of removing the aqueous phase with a pH of 8 or above from the obtained mixed liquid 3' to obtain an organic phase 3A'; The solubility of the organic compound in the organic phase of the mixed liquid 3' is higher than the solubility in the aqueous phase of the mixed liquid 3', and the solubility of the chelating agent in the aqueous phase of the mixed liquid 3' is higher than that in the aqueous phase of the mixed liquid 3'. Solubility of the organic phase.

[Chemical 1]

In formula (I), X and Y are the same or different elements, and are elements selected from the group consisting of trivalent nitrogen, divalent oxygen, trivalent phosphorus and divalent sulfur. The line connecting X and Y is a carbon chain. (Compare the effectiveness of previous technologies)

According to the present invention, bisphenol having excellent methanol-soluble color, melt color difference, thermal tone stability, and thermal decomposition stability can be produced. According to the present invention, the obtained bisphenol can be used to produce a polycarbonate resin with good color tone.

Embodiments of the present invention will be described in detail below. The description of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not exceed the gist of the invention. In this specification, when the expression "～" is used, it is used in a form that includes the numerical or physical property values before and after it.

[Production method of bisphenol] The manufacturing method of bisphenol of the present invention is characterized in that it includes the following steps: mixing the organic phase 1 of the mixed liquid 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol with a chelating agent to obtain an aqueous phase with a pH below 6 and The step of mixing the organic phase liquid 2 (hereinafter, this step may be referred to as the "chelation treatment step"); mixing the obtained mixed liquid 2 with an alkali to obtain a mixed liquid 3 of an aqueous phase and an organic phase with a pH of 8 or above. and a step of removing the aqueous phase with a pH of 8 or higher from the obtained mixed liquid 3 to obtain the organic phase 3A (hereinafter, the step until the organic phase 3A is obtained by mixing alkali may be referred to as the "alkali treatment step") ; And the solubility of the chelating agent in the aqueous phase of the mixed liquid 3 is higher than the solubility in the organic phase of the mixed liquid 3 .

The method for producing bisphenol of the present invention is characterized by mixing a chelating agent into the organic phase 1 of the mixed liquid 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol to obtain a mixed liquid of the aqueous phase and the organic phase with a pH of 6 or less. 2. When mixing the mixed liquid 2 with an alkali to obtain a mixed liquid 3 of an aqueous phase and an organic phase with a pH of 8 or above, use a chelating agent with a higher solubility in the aqueous phase of the mixed liquid 3 than in the organic phase of the mixed liquid 3. , remove the aqueous phase with a pH of above 8 from the mixed liquid 3 and efficiently recover the organic phase 3A containing bisphenol.

As mentioned above, when hydrogen chloride gas or hydrochloric acid is used as a catalyst for the bisphenol production reaction, the volatilization of hydrogen chloride corrodes the equipment and the corrosive components are mixed into the bisphenol, thereby causing the quality of the bisphenol to deteriorate. The corrosive component mixed into the bisphenol is mainly composed of metal components such as iron that constitute the equipment. In the present invention, a chelating agent is added and mixed under the above-mentioned specific pH acidic conditions, and then the pH is adjusted to alkaline conditions by adding an alkaline aqueous solution, thereby chelating metal components such as iron mixed into the bisphenol product. Combine and remove efficiently. Furthermore, the quality of bisphenol can be improved by removing corrosive components.

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

In this case, as a method for obtaining the organic phase 1A by removing the water phase from the mixed liquid 1 of the aqueous phase 1 with a pH of 6 or less and the organic phase 1 containing bisphenol, the following (1) and (2) can be cited. method. (1) After the bisphenol generation reaction, an acidic solution is added to the reaction solution to perform phase separation. (2) After the bisphenol generation reaction, neutralize, wash and crystallize the reaction solution, extract the bisphenol, dissolve the extracted bisphenol in a solvent to obtain a bisphenol solution, and use an acidic solution to wash the bisphenol. Method for phase separation after phenol solution

[Bisphenol generation reaction] The bisphenol production reaction suitably applied to the present invention will be described.

In the bisphenol generation reaction, a ketone or aldehyde and an aromatic alcohol are condensed in the presence of a catalyst to obtain a reaction liquid containing bisphenol.

The reaction of bisphenol is usually carried out according to the reaction formula (1) shown below.

[Chemicalization 2]

R ¹ to R ⁶ in the above reaction formula (1) are as described for R ¹ to R ⁶ in the following general formulas (2) to (3).

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

[Chemical 3]

In the general formula (2), R ¹ to R ⁴ each independently include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and the like. The alkyl group, alkoxy group, aryl group and other substituents may be substituted or unsubstituted. Examples of R ¹ to R ⁴ include a hydrogen atom, a fluorine group, a chlorine group, a bromo group, an iodine group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a third Butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl Alkyl, benzyl, phenyl, tolyl, 2,6-dimethylphenyl, etc.

Among them, if R ² and R ³ have a large three-dimensional volume, condensation reaction is difficult to proceed. Therefore, as an aromatic alcohol, an aromatic alcohol in which R ² and R ³ are hydrogen atoms is preferred. Moreover, as an aromatic alcohol, it is preferable that R ¹ to R ⁴ are each independently a hydrogen atom or an alkyl group, more preferably R ¹ and R ⁴ are each independently a hydrogen atom or an alkyl group, and R ² and R ³ are each independently a hydrogen atom or an alkyl group. Aromatic alcohols with hydrogen atoms.

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

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

＜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 ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or the like. The alkyl group, alkoxy group, aryl group and other substituents may be substituted or unsubstituted. Examples of R ⁵ and R ⁶ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and an n-hexyl group. n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, methoxy, ethoxy, n-propoxy, iso Propoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isopentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n- Decyloxy, n-undecyloxy, n-dodecyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, benzyl, Phenyl, tolyl, 2,6-dimethylphenyl, etc.

R ⁵ and R ⁶ may be bonded or cross-linked between the two groups. R ⁵ and R ⁶ may also be bonded together with adjacent carbon atoms to form a cycloalkylene group that may also contain heteroatoms. The so-called cycloalkylene group is a divalent radical obtained by removing two hydrogen atoms from one carbon atom of a cycloalkane. In the case of a cycloalkylene group formed by bonding R ⁵ and R ⁶ to adjacent carbons, the bisphenol obtained has a structure in which an aromatic alcohol is bonded through the cycloalkylene group.

Examples of the cycloalkylene group formed by R ⁵ and R ⁶ bonded together with adjacent carbon atoms include: cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, 3,3,5 -Trimethylcyclohexylene, cycloheptylene, cyclooctanylene, cyclononylene, cyclodecylene, cycloundecylene, cyclododecylene, benzylidene, base, 9-oxosulfide Key et al.

Specific examples of the compound represented by the general formula (3) include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, heptanal, octanal, nonanal, decanal, and undecanal. , dodecane and other aldehydes; acetone, methyl ethyl ketone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone and other ketones; benzaldehyde, phenyl methyl ketone , phenylethyl ketone, phenylpropyl ketone, tolyl methyl ketone, tolyl ethyl ketone, tolyl propyl ketone, xylyl methyl ketone, xylyl ethyl ketone, xylyl propyl Ketones and other aralkyl ketones, cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, cyclododecanone and other cyclic Alkanes and ketones, etc. Among them, acetone is preferred.

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

[Chemistry 5]

In the general formula (4), R ¹ to R ⁶ have the same meaning as in the general formulas (2) and (3).

Specific examples of the bisphenol represented by the general formula (4) include: 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl) Propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 9,9-bis (4-Hydroxy-3-methylphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxy-3-methylphenyl)pentane, 2 ,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxy-3-methylphenyl)pentane, 3,3-bis(4-hydroxyphenyl)heptane, 3 ,3-bis(4-hydroxy-3-methylphenyl)heptane, 2,2-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxy-3-methylphenyl) ) heptane, 4,4-bis(4-hydroxyphenyl)heptane, 4,4-bis(4-hydroxy-3-methylphenyl)heptane, etc., but are not limited to these.

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

＜Hydrogen chloride＞ In the present invention, it is preferred to use hydrogen chloride as a catalyst because the effects of the present invention can be more significantly obtained. Examples of hydrogen chloride include hydrogen chloride gas and hydrochloric acid. Among them, hydrogen chloride gas is preferred.

If the molar ratio of hydrogen chloride to the ketone or aldehyde used in the reaction is less ((moles of hydrogen chloride/moles of ketone) or (moles of hydrogen chloride/moles of aldehyde)), then hydrogen chloride It is diluted by the water produced during the condensation reaction and requires a longer reaction time. If the mole is relatively large, the polymerization of the ketone or aldehyde may proceed. In view of these circumstances, the lower limit of the molar ratio of hydrogen chloride to the ketone or aldehyde is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and preferably 10 or less, more preferably 8 or less, and further Preferably it is 5 or less.

＜Condensation reaction＞ In order to obtain a reaction liquid containing bisphenol, the method of condensing an aromatic alcohol with a ketone or an aldehyde is not particularly limited, and examples thereof include the following methods. (i) A method in which a ketone or aldehyde is supplied to a mixed solution containing an aromatic alcohol and hydrogen chloride, and then reacted for a predetermined time (ii) A method in which hydrogen chloride is supplied to a mixed solution containing an aromatic alcohol and a ketone or an aldehyde, and then reacted for a predetermined time

When supplying the ketone or aldehyde in the above (i) or the hydrogen chloride in the above (ii), there may be a one-time supply method or a batch supply method. Since the reaction to generate bisphenol is a heat-generating reaction, a batch supply method such as gradually adding a small amount and supplying bisphenol is preferred. The method (i) above is preferred in that it can further suppress the self-condensation of ketones or aldehydes.

In the reaction of condensing an aromatic alcohol with a ketone or an aldehyde, if the molar ratio of the aromatic alcohol to the ketone or aldehyde ((moles of aromatic alcohol/moles of ketone) or (moles of aromatic alcohol) If the number of ears/the molar number of aldehyde) is small, the ketone or aldehyde will easily polymerize. If the mole is relatively large, the aromatic alcohol will be lost in an unreacted state. In view of these circumstances, the molar ratio of the aromatic alcohol to the ketone or aldehyde is preferably 1.5 or more, more preferably 1.6 or more, further preferably 1.7 or more, and preferably 15 or less, more preferably 10 or less, and still more preferably The best value is below 8.

＜thiol＞ In the present invention, mercaptans can be used as co-catalysts in the reaction of condensing ketones or aldehydes with aromatic alcohols.

By using thiol as a cocatalyst, for example, in the production of 2,2-bis(4-hydroxy-3-methylphenyl)propane, the effect of inhibiting the production of 24-mer and improving the selectivity of 44-mer can be obtained , and the effect of improving the polymerization activity during the production of polycarbonate resin and improving the color tone of the obtained polycarbonate resin can be obtained. Although the details of the reason for the effect of improving the polymerization activity during the production of polycarbonate resin and improving the color tone of the obtained polycarbonate resin have not yet been elucidated, it is presumed that the reason is that the use of thiol can suppress the effects on the production of polycarbonate resin. It inhibits the generation of polymerization reaction inhibitors of carbonate resin and inhibits the generation of color tone deteriorating substances.

Examples of mercaptans used as cocatalysts include mercaptocarboxylic acids such as thioglycolic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and 4-mercaptobutyric acid, or methyl mercaptan. Ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan (decyl mercaptan), ten Alkyl mercaptans such as monoalkyl mercaptan (undecyl mercaptan), dodecyl mercaptan (dodecyl mercaptan), tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan Or aryl mercaptans such as mercaptophenol, etc.

If the molar ratio of the thiol cocatalyst to the ketone or aldehyde used in the condensation is ((moles of thiol cocatalyst/moles of ketone) or (moles of thiol cocatalyst/moles) If the molar number of the aldehyde is small, the effect of improving the reaction selectivity of bisphenol caused by using a thiol cocatalyst cannot be obtained. If the mole content is relatively large, it may be mixed into bisphenol and the quality may deteriorate. In view of these circumstances, the molar ratio of the thiol auxiliary catalyst to the ketone and aldehyde is preferably 0.001 or more, more preferably 0.005 or more, further preferably 0.01 or more, and preferably 1 or less, and more preferably 0.5 or less. Furthermore, it is more preferable that it is 0.1 or less.

The thiol is preferably mixed with the ketone or aldehyde in advance and then used for the reaction. The mixing method of thiol and ketone or aldehyde can be to mix ketone or aldehyde into thiol, or to mix thiol into ketone or aldehyde. The method of mixing a mixture of thiols, ketones or aldehydes, and aromatic alcohols is to mix aromatic alcohols into the mixture of thiols, ketones or aldehydes, or to mix thiols, ketones or aldehydes into the aromatic alcohols. Mixture. Preferably, a mixture of a thiol, a ketone or an aldehyde is mixed with an aromatic alcohol.

＜Organic solvent＞ In the production method of bisphenol of the present invention, in order to dissolve or disperse the produced bisphenol, an organic solvent is usually used.

The organic solvent is not particularly limited within a range that does not hinder the production reaction of bisphenol, and aromatic hydrocarbons can usually be used. Here, the aromatic alcohol that becomes the raw material and the bisphenol that is the product are excluded from the organic solvent.

Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, diethylbenzene, cumene, mesitylene, and the like. These solvents may be used alone or in combination of two or more. After being used in the production of bisphenol, aromatic hydrocarbons can be recovered and refined through distillation and reused. When aromatic hydrocarbons are reused, those with a lower boiling point are preferred. One of the preferred aromatic hydrocarbons is toluene.

If the mass ratio of the organic solvent used in the condensation to the ketone or aldehyde ((mass of ketone/mass of organic solvent) or (mass of aldehyde/mass of organic solvent)) is too large, the ketone or aldehyde and the aromatic alcohol will not be easily combined. Reaction, reaction takes a long time. If the mass ratio is too small, polymerization of the ketone or aldehyde may be accelerated, or the generated bisphenol may be solidified. In view of these circumstances, the mass ratio of the organic solvent to the ketone or aldehyde when added is preferably 0.5 or more, and more preferably 1 or more. On the other hand, the mass ratio is preferably 100 or less, and more preferably 50 or less.

Instead of using an organic solvent, a large amount of raw material aromatic alcohol may be used instead of the organic solvent. In this case, the unreacted aromatic alcohol becomes a loss, but the loss can be reduced by recovering, purifying and reusing it by distillation or the like.

＜Reaction conditions＞ If the reaction time of the bisphenol generation reaction is too long, the generated bisphenol may be decomposed, so it is preferably within 30 hours, more preferably within 25 hours, and still more preferably within 20 hours. The lower limit of the reaction time is usually more than 2 hours.

The reaction time also includes the mixing time when preparing the reaction solution. For example, when a ketone or an aldehyde is supplied to a mixed solution of an aromatic alcohol and an acid catalyst for one hour, and then allowed to react for one hour, the reaction time is two hours.

Regarding the reaction temperature of the bisphenol production reaction, polymerization of ketones or aldehydes proceeds easily at high temperatures, and the time required for the reaction becomes longer at low temperatures. In view of these circumstances, the reaction temperature is preferably -30°C or higher, more preferably -20°C or higher, further preferably -15°C or higher, and more preferably 80°C or lower, more preferably 70°C or lower, still more preferably below 60℃. The reaction temperature refers to the average temperature from the beginning to the end of the first step.

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

[Chelation treatment step] The chelating treatment step in the present invention can be carried out before the following crystallization step and after the above-mentioned bisphenol generation reaction step, or after the bisphenol generation reaction and after the following water washing step, or after the following water washing step. Carry out after the crystallization step described above.

When a chelation treatment step is performed after the bisphenol production reaction, water is added to the reaction liquid of the bisphenol production reaction and mixed. If the pH of the aqueous phase obtained by phase separation is 6 or less, the chelation treatment step can be removed. The organic phase 1A after the aqueous phase was set as organic phase 1, and a chelating agent was added and mixed to obtain a mixed liquid 2.

The removal of the water phase is preferably such that the mixing ratio of the water phase and the organic phase 1A after the water phase is removed becomes the water phase in terms of weight ratio: organic phase 1A = 1:700 or less, especially 1:800 or less, especially 1: below 900. If the amount of the aqueous phase exceeds this range, the amount of alkaline aqueous solution required to set the pH to 8 or higher in the alkali treatment step described below increases.

When the chelating treatment step is performed after the following water washing step after the bisphenol production reaction step, the pH of the aqueous phase obtained by phase separation after washing by adding water and mixing is 6 Next, the organic phase after removing the aqueous phase can be used as the organic phase 1, a chelating agent is added and mixed to obtain a mixed liquid 2. When the pH of the washed aqueous phase exceeds 6, it is sufficient to add and mix an acidic aqueous solution to the organic phase after removing the aqueous phase, and phase-separate the aqueous phase with a pH of 6 or lower.

When performing a chelation treatment step after the crystallization step described below, an organic solvent is added to the solid bisphenol recovered by crystallization to obtain a bisphenol solution, and an acidic aqueous solution is added to and mixed with the bisphenol solution. , and the aqueous phase with pH below 6 can be phase separated.

Add and mix the above-mentioned acidic aqueous solution, add and mix water to the organic phase obtained by phase separation, and perform phase separation. Here, if the aqueous phase after phase separation has a pH of 6 or less, the aqueous phase can be phase-separated. The organic phase obtained by separation is referred to as the first organic phase.

In any case, if the pH of the aqueous phase that is phase-separated when obtaining organic phase 1A exceeds 6, the corrosive components cannot be sufficiently removed by the chelating agent, and methanol-soluble color, melt color difference, and thermal color tone stability cannot be obtained. , bisphenol with good thermal decomposition stability. The pH of the aqueous phase is preferably 5 or less. If the pH of the aqueous phase is excessively lowered, the amount of alkaline aqueous solution used in the following alkali treatment step will become too large. Therefore, the pH of the aqueous phase is preferably -1 or above. In the present invention, pH is the measured value at room temperature (20-30°C).

As an acidic substance used to obtain an acidic aqueous solution with a water phase of pH 6 or less, 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 appropriately adjusted according to the acidic substance or alkaline substance remaining in the bisphenol. If the acidic substance concentration of the acidic aqueous solution is too high, bisphenol will decompose, so it is preferably 35 mass% or less, more preferably 30 mass% or less, and more preferably 20 mass% or less. If the acidic substance concentration of the acidic aqueous solution is too low, the amount of the acidic aqueous solution must be increased in order to obtain a water phase with a pH of 6 or less. Therefore, the lower limit of the acidic substance concentration of the acidic aqueous solution is preferably 0.01 mass ppm or more, and more preferably 0.1 mass ppm or more. .

If the amount of the acidic aqueous solution used is too large, the amount of the aqueous phase separated after adding the acidic aqueous solution will be too large relative to the amount of the organic phase, making it difficult to perform phase separation. Therefore, the mass ratio of the acidic aqueous solution to the amount of the organic phase (mass of the acidic aqueous solution/mass of the organic phase) to which the acidic aqueous solution is added is preferably 2 or less, more preferably 1 or less, and still more preferably 0.5 or less. The amount of added acidic aqueous solution is too small, and the amount of organic phase is too much relative to the amount of aqueous phase, making it difficult to achieve phase separation. 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.

As a chelating agent added to the organic phase 1 after separating the aqueous phase with a pH of 6 or less, the type is not particularly limited as long as it can be used as a chelating agent. In the present invention, the chelating agent used in the following alkali treatment step is used. The obtained chelate has a higher solubility in the aqueous phase in the mixed liquid 3 (hereinafter referred to as "solubility in the aqueous phase") than in the organic phase in the mixed liquid 3 (hereinafter referred to as "solubility in the organic phase") mixture.

If the solubility of the chelating agent used in the aqueous phase is lower than the solubility in the organic phase, the chelating agent used will remain in the organic phase and remain in the bisphenol, and the purity of the bisphenol will decrease. The chelating agent only needs to have a higher solubility in the aqueous phase than in the organic phase. The ratio of the solubility in the aqueous phase/solubility in the organic phase is 1.5 times or more, preferably 2 times or more, and further preferably 10 times or more. .

Examples of the chelating agent include β-diones such as acetylacetone and 3,5-heptanedione; ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyl Aminocarboxylic acids such as ethylenediaminetriacetic acid or their salts; keto acids such as pyruvic acid or acetoacetic acid, acetopropionic acid, α-ketoglutaric acid, acetone dicarboxylic acid; glycolic acid, glyceric acid, lignin, Gluconic acid, lactic acid, hydroxymalonic acid, tartaric acid, xylaric acid (xylaric acid), galactocarboxylic acid, malic acid, citric acid and other hydroxy acids; oxalic acid or malonic acid, succinic acid, glutaric acid, adipic acid polycarboxylic acids such as acid; amino acids such as aspartic acid or glutamic acid; phytic acid or polyphosphoric acids such as hydroxyethylene diphosphate, nitrilotrimethylene phosphate, ethylenediamine tetramethylene phosphoric acid; Dioximes such as methylglyoxime or benzylglyoxime, 1,2-cyclohexylglyoxime, etc.

Among them, those that satisfy the above-mentioned solubility in the aqueous phase and the solubility in the organic phase include ethylenediaminetetraacetic acid, citric acid, oxalic acid, malonic acid, and succinic acid.

Among these, tetracarboxylic acids are particularly preferred, and aminocarboxylic acids such as ethylenediaminetetraacetic acid or salts thereof are preferred from the viewpoint of being easily chelated with various metals. In addition, chelating agents composed only of carbon, hydrogen, and oxygen atoms are preferred because they have excellent solubility in organic solvents and are easily combined with corrosive components. Examples thereof include acetyl acetone. , 3,5-heptanedione and other β-diketones; keto acids such as pyruvic acid or acetoacetic acid, acetopropionic acid, α-ketoglutaric acid, acetone dicarboxylic acid; glycolic acid, glyceric acid, lignin , gluconic acid, lactic acid, hydroxymalonic acid, tartaric acid, xylosic acid, galactic acid, malic acid, citric acid and other hydroxy acids; oxalic acid or malonic acid, succinic acid, glutaric acid, adipic acid, etc. Carboxylic acids, etc.

Only one type of these chelating agents may be used, or two or more types of chelating agents may be used in combination.

The chelating agent is preferably added to the organic phase 1 in the form of an aqueous solution of about 0.1% by mass or more, especially 0.5% by mass or more and less than 15% by mass, especially about 10% by mass or less. If the concentration of the chelating agent 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 supplying the chelating agent increases.

The amount of the chelating agent aqueous solution added to the organic phase 1 is sufficient to sufficiently chelate and remove the corrosive components in the organic phase 1. The amount depends on the chelating agent concentration or the organic phase 1 to be treated. The amount of corrosive components in it varies. If too much is added to the chelating agent aqueous solution in the organic phase 1, the manufacturing cost will increase. If the amount of the chelating agent aqueous solution added to the organic phase 1 is too small, the corrosive components in the organic phase 1 cannot be sufficiently removed, and the effects of the present invention cannot be fully obtained. Therefore, it is preferable that the mass ratio of the chelating agent aqueous solution to the organic phase 1 (mass of the chelating agent aqueous solution/mass of the organic phase 1) is 0.0001 or more, especially 0.001 or more and 10 or less, especially 1 or less.

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

[Alkali treatment step] The alkali treatment step in the present invention is the following step: adding an alkali, preferably an alkaline aqueous solution, and mixing it into the mixed liquid 2 obtained in the above chelation treatment step to obtain an aqueous phase and an organic phase with a pH of 8 or above. The mixed liquid 3 is obtained, and the aqueous phase with pH above 8 is removed from the obtained mixed liquid 3 to obtain the organic phase 3A. After the aqueous phase of the mixed liquid 2 is removed into an aqueous phase and an organic phase, even if an alkaline aqueous solution is added to the organic phase removed from the aqueous phase, the chelating effect of the chelating agent cannot be obtained. Therefore, it is important to add the alkaline aqueous solution to the mixed liquid 2 before the water phase is completely removed. That is, the mixing ratio of the water phase and the organic phase in the mixed liquid 2 is preferably more than 0.001:700 for the water phase in terms of weight ratio, more preferably more than 0.01:700 for the water phase, and particularly preferably more than 0.05: 700. On the other hand, the mixing ratio of the aqueous phase and the organic phase in the mixed liquid 2 is preferably less than 1000:700 mass ratio of the aqueous phase in terms of weight ratio, further preferably less than 500:700 mass ratio of the aqueous phase, and particularly preferably the aqueous phase. Less than 300:700. If it deviates from this range, the chelating agent dissolved in the water phase will also be removed, so the effect of the present invention will not be exerted.

Here, the pH of the aqueous phase for phase separation only needs to be 8 or more, and may be 10 or more or 11 or more, and usually about 8 to 9 is used.

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

If the alkaline substance concentration of the alkaline aqueous solution used in the alkali treatment step is too low, the amount of alkaline aqueous solution used to obtain an aqueous phase above pH 8 will increase, the overall liquid volume will increase, and the treatment efficiency will deteriorate. Therefore, it is preferable that the concentration of the alkaline substance of the alkaline aqueous solution is as high as possible, and it is preferable that the alkaline aqueous solution is a saturated aqueous solution of the alkaline substance.

If the amount of the alkaline aqueous solution added and mixed is too large, the amount of the aqueous phase that is phase-separated after the addition and mixing of the alkaline aqueous solution is too large relative to the amount of the organic phase, making phase separation difficult. Even if the amount of the alkaline aqueous solution is too small, the amount of the organic phase is too large relative to the amount of the aqueous phase, making phase separation difficult. In view of these circumstances, the mass ratio of the alkaline aqueous solution to the amount of the mixed liquid 2 (mass of the alkaline aqueous solution/mass of the mixed liquid 2) in the alkali treatment step is preferably 0.01 or more, particularly preferably 0.1 or more and 100 or less. , especially preferably below 10.

The organic phase 3A obtained in the alkali treatment step is preferably purified in the following crystallization step after performing the following water washing step if necessary, and the purified bisphenol is recovered.

[Washing steps] In the method for producing bisphenol of the present invention, the following water washing step may be included: using water to wash the reaction liquid containing bisphenol obtained in the bisphenol generation reaction step or the organic phase 3A after the alkali treatment step. By performing this water washing step, the amount of impurities can be further reduced.

In the water washing step, for example, desalted water is supplied to the reaction liquid or organic phase 3A, and the reaction liquid or organic phase 3A is washed with desalted water. Here, when the amount of water supplied is large, the liquid amount increases, so the stirring efficiency tends to decrease and the water washing efficiency tends to decrease. When the amount of water supplied is small, the volume of the water phase decreases, the stirring efficiency decreases, and the water washing efficiency tends to decrease. Therefore, the mass ratio of water to the amount of reaction liquid or organic phase 3A (mass of water/mass of reaction liquid or organic phase 3A) is preferably 0.01 or more, further preferably 0.05 or more, and more preferably 2 or less, More preferably, it is 1 or less, and still more preferably, it is 0.5 or less.

This water washing step is performed by supplying water to the reaction solution or the organic phase 3A for washing, and then separating the phases into an organic phase and an aqueous phase, and removing the aqueous phase. The water washing step can be performed several times. In this case, the supply of water, washing, phase separation, and removal of the water phase are repeatedly performed.

[Alkali cleaning step] In the method for producing bisphenol of the present invention, after the alkali treatment step or the water washing step, there may be an alkali washing step of washing the obtained organic phase with an alkaline aqueous solution.

The alkali cleaning step is preferably after the alkali treatment step or the water washing step, mixing the separated organic phase and the alkaline aqueous solution, and then causing the phase separation into an organic phase and an aqueous phase with a pH of 9 or above, and removing the phase separated aqueous phase to obtain the organic phase.

By washing with an alkaline aqueous solution in this way, easily soluble impurities can be removed under alkaline conditions. The alkali cleaning step can be performed several times.

The pH of the aqueous phase separated in the alkali washing step only needs to be 9 or more, and may be 10 or more or 11 or more. The upper limit of the pH may be below 14 or below 13.

As the alkaline substance of the alkaline aqueous solution used in the alkali cleaning step, sodium bicarbonate, sodium carbonate, etc. can be used.

The alkaline substance concentration of the alkaline aqueous solution used in the alkali cleaning step is appropriately adjusted according to the type of alkaline substance or acid catalyst. If the alkaline substance concentration of the alkaline aqueous solution is too high, it will remain in the bisphenol finally obtained and deteriorate the quality. Therefore, it is preferably 20 mass% or less, more preferably 15 mass% or less, and more preferably 10 mass%. the following. If the alkaline substance concentration of the alkaline aqueous solution is too low, the amount of the alkaline aqueous solution must be increased in order to obtain a water phase with a pH of 9 or above. Therefore, the alkaline substance concentration of the alkaline aqueous solution is preferably 0.1 mass % or more, and more preferably 0.5 mass %. %above.

If the amount of the supplied alkaline aqueous solution is too large, the amount of the aqueous phase to be phase-separated after alkali washing will be too large relative to the amount of the organic phase, making it difficult to phase-separate. Even if the amount of the alkaline aqueous solution supplied is too small, the amount of the organic phase is too large relative to the amount of the aqueous phase, making it difficult to separate the phases. In view of these circumstances, the mass ratio of the alkaline aqueous solution to the amount of the organic phase (mass of the alkaline aqueous solution/mass of the organic phase) in the alkali cleaning step is preferably 2 or less, more preferably 1 or less, and still more preferably It is 0.5 or less, preferably 0.05 or more, more preferably 0.1 or more.

[Temperature of chelating treatment step, alkali treatment step, water washing step, and alkali washing step] In the above-mentioned chelating treatment step, alkali treatment step, water washing step and alkali washing step, in order to suppress the precipitation of bisphenol, the average temperature from the beginning to the end is preferably set to 50°C or above, and more preferably set to Above 55℃. In order to suppress the precipitation of bisphenol due to evaporation of the organic solvent, the average temperature is preferably 120°C or lower, more preferably 110°C or lower. These steps can, for example, be carried out at the same temperature.

[Crystallization step] The method for producing bisphenol 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 washing step and the subsequent water washing step.

Crystallization can be carried out according to conventional methods. For example, either a method utilizing the difference in solubility of bisphenol due to a temperature difference or a method of precipitating a solid by supplying a poor solvent can be applied. In the method of supplying a poor solvent, since the purity of the bisphenol obtained is likely to decrease, a method that utilizes the difference in solubility of bisphenol caused by a temperature difference is preferred. When there is a large amount of aromatic alcohol in the organic phase, the remaining aromatic alcohol can be removed by distillation before crystallization and then the crystallization is carried out.

For example, bisphenol is precipitated by cooling the organic phase at 60 to 90°C to -10 to 30°C. The precipitated bisphenol can be recovered by solid-liquid separation and drying.

The organic phase used in the crystallization step is preferably an aqueous phase that has just been phase-separated in the most recent step (hereinafter referred to as the “most recent aqueous phase”) with a conductivity of 10 μS/cm or less. If the conductivity of the previous aqueous phase is 10 μS/cm or less, especially 9 μS/cm or less, especially 8 μS/cm or less, impurities such as by-products or residual catalysts in the product are highly removed and the color is good. , when bisphenol is used as a raw material for polycarbonate resin, it is preferable because it can obtain bisphenol with high polymerization reaction efficiency and can produce polycarbonate resin with excellent hue.

Here, the conductivity of the most recent water phase can be measured, for example, using a conductivity meter on the most recent water phase that has undergone phase separation at room temperature (20 to 30° C.).

The bisphenol obtained in the above manner can also be further refined by conventional methods depending on its use. For example, it can be purified by simple means such as spray washing, water washing, suspension washing, crystallization or column chromatography. Specifically, the obtained bisphenol is dissolved in an organic solvent such as aromatic hydrocarbons and then cooled to crystallize, thereby further purifying the resulting bisphenol.

[Step composition of the manufacturing method of bisphenol] The manufacturing method of bisphenol of the present invention can be, for example, a manufacturing method including a chelating treatment step, an alkali treatment step, a water washing step, and a crystallization step in this order. Moreover, the manufacturing method of bisphenol of this invention can be set as the manufacturing method which has a water washing step, a chelation treatment step, an alkali treatment step, a water washing step, and a crystallization step in this order.

[Suitable physical properties of bisphenol] Suitable physical properties of bisphenol produced by the method for producing bisphenol of the present invention (hereinafter sometimes referred to as "bisphenol of the present invention") will be described below.

＜Methanol dissolved color of bisphenol＞ The methanol-soluble color system of bisphenol is used to evaluate the color tone of bisphenol at room temperature. The lower the Hazen color value of the methanol-soluble color of bisphenol, the better the color tone of the bisphenol (closer to white). Causes of deterioration of the methanol-dissolved color of bisphenol include the mixing of organic coloring components and metals.

Methanol-soluble color of bisphenol Dissolve bisphenol in methanol to make a uniform solution, and then measure it at room temperature (about 20°C). Examples of measurement methods include: visual inspection and comparison with a Hazen color value standard solution; or a method of measuring the Hazen color value using a colorimeter such as "SE6000" manufactured by Nippon Denshoku Industries Co., Ltd. The mass ratio of the solvent methanol, bisphenol and solvent used here is preferably appropriately selected according to the type of bisphenol.

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

＜Melting color difference of bisphenol＞ The melt color difference of bisphenol is used to evaluate the hue of bisphenol at a temperature close to the polymerization temperature of polycarbonate. The measurement temperature of melting color difference is the melting point of bisphenol + 50℃. Regarding the melt color difference of bisphenol, the lower the Hazen color value, the better the hue of bisphenol (closer to white). Causes that worsen the melt color difference of bisphenol include, in addition to the mixing of organic coloring components and metals, components that cause coloring due to heating.

The melting color difference of bisphenol is measured by melting bisphenol at a temperature close to the polymerization temperature and during a time when the temperature is relatively stable. Examples of measurement methods include: visual inspection and comparison with a Hazen color value standard solution; or a method of measuring the Hazen color value using a colorimeter such as "SE6000" manufactured by Nippon Denshoku Industries Co., Ltd.

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

＜Thermal tone stability of bisphenol＞ The thermal color tone stability of bisphenol is used to evaluate the thermal stability of the color tone of bisphenol by maintaining it at a temperature close to the polymerization temperature of polycarbonate for a predetermined time, just like the melt color difference of bisphenol. The temperature for measuring the thermal color stability of bisphenol is the melting point of bisphenol + 50°C.

Regarding the thermal color stability of bisphenol, the lower the Hazen color value, the better the thermal color stability of bisphenol. Causes of deteriorating the thermal color tone stability of bisphenol include, in addition to the mixing of organic coloring components and metals, components that cause coloring due to heating, and acidic or alkaline substances whose concentration is on the order of several ppm.

The thermal color stability of bisphenol is measured by melting the bisphenol at a temperature close to the polymerization temperature and during a time when the temperature is relatively stable. The thermal color stability of bisphenol is maintained for 4 hours. Examples of measurement methods include: visual inspection and comparison with a Hazen color value standard solution; or a method of measuring the Hazen color value using a colorimeter such as "SE6000" manufactured by Nippon Denshoku Industries Co., Ltd.

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

＜Thermal decomposition stability of bisphenol＞ Thermal decomposition stability of bisphenol is used to evaluate the thermal stability of bisphenol by maintaining it for a predetermined time at a temperature close to the polymerization temperature of polycarbonate, similar to the thermal hue stability of bisphenol. The best measurement temperature for the thermal decomposition stability of bisphenol is the melting point of bisphenol + 50°C. Regarding the thermal decomposition stability of bisphenol, the smaller the amount of decomposition products produced, the more stable the bisphenol is.

The decomposition products of the thermal decomposition stability of bisphenol also depend on the type of bisphenol, and examples include aromatic alcohols that are raw materials for bisphenols, or adducts of aromatic alcohols and ketones or aldehydes that are raw materials. Reasons for deteriorating the thermal decomposition stability of bisphenol include, in addition to the mixing of organic coloring components and metals, components that cause coloring due to heating, and acidic or alkaline substances whose concentration is about several ppm.

The detection and quantification of bisphenol decomposition products can be carried out using a standard reverse-phase column for high-speed analysis. The amount of isopropenylcresol produced as a decomposition product of bisphenol measured in the following examples is preferably 200 ppm by mass or less.

The methanol-soluble color system 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 polycarbonate resin inherits the color tone of the raw material, bisphenol with good color tone is important among polycarbonate resins that require colorless transparency.

In the melt polymerization method, which is one of the manufacturing methods of polycarbonate resin, since the polymerization reaction proceeds at high temperature, what is important is the color tone of bisphenol when melted (the melt color difference of bisphenol) and the color difference of bisphenol in the molten state. Color tone stability (thermal color tone stability of bisphenol).

Furthermore, in this melt polymerization method, the bisphenol is maintained in a molten state at a high temperature until the polymerization reaction starts. In this melt polymerization method, when bisphenol decomposes at high temperature, the mass ratio of bisphenol to diphenyl carbonate deviates from the predetermined mass ratio, and it is difficult to obtain a polycarbonate resin with polymerization activity or a predetermined molecular weight. Therefore, it is important to be resistant to thermal decomposition (thermal decomposition stability of bisphenol).

In particular, in order to produce a polycarbonate resin with a predetermined molecular weight and good color tone, the methanol-soluble color of bisphenol, the melt color difference of bisphenol, the thermal color 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 polyether resin, polyester resin, polyarylate resin for various purposes such as optical materials, recording materials, insulating materials, transparent materials, electronic materials, adhesive materials, heat-resistant materials, etc. , various thermoplastic resins such as polycarbonate resin, polyurethane resin, and acrylic resin, or epoxy resin, unsaturated polyester resin, phenol resin, polybenzo Components, hardeners, additives or precursors of various thermosetting resins such as resins and cyanate ester resins. The bisphenol of the present invention can also be used as a color developer or anti-fading agent, bactericide, antibacterial and antifungal agent and other additives for heat-sensitive recording materials.

The bisphenol of the present invention can impart good mechanical properties, so it is preferably used as a raw material (monomer) for thermoplastic resins and thermosetting resins. Among them, it is more preferably used as a raw material for polycarbonate resins and epoxy resins. The bisphenol of the present invention is also preferably used as a color developer, and is particularly preferably used in combination with a leuco dye and a discoloration temperature regulator.

[Production method of polycarbonate resin] The use of bisphenol in the present invention is as a raw material for manufacturing polycarbonate resin.

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

Only one type of bisphenol or two or more types of bisphenol may be used in the present invention to produce a copolymerized polycarbonate resin. A dihydroxy compound other than the bisphenol of the present invention may be used together to react it.

The above-mentioned transesterification reaction can be carried out by appropriately selecting a known method. An example using the bisphenol and diphenyl carbonate of the present invention as raw materials will be described below.

In the manufacturing method of the polycarbonate resin mentioned above, it is preferable that diphenyl carbonate is used in excess with respect to the bisphenol of this invention. The amount of diphenyl carbonate used relative to the bisphenol is preferably larger because the polycarbonate resin produced has fewer terminal hydroxyl groups and the polymer has excellent thermal stability. In order to easily produce a polycarbonate resin with a fast transesterification reaction speed and a required molecular weight, it is preferable to use a smaller amount of diphenyl carbonate than bisphenol. In view of these circumstances, the amount of diphenyl carbonate used per mole of bisphenol is usually 1.001 mol or more, preferably 1.002 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less. .

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

When producing polycarbonate resin through the transesterification reaction of diphenyl carbonate and bisphenol, transesterification catalysts are usually used. In the above method for producing a polycarbonate resin, it is preferable to use an alkali metal compound and/or an alkaline earth metal compound as the transesterification catalyst. One type of these may be used, and two or more types may be used in combination in any combination and ratio. From a practical point of view, it is preferable to use an alkali metal compound.

The usage amount of the catalyst is usually 0.05 μmol or more, preferably 0.08 μmol or more, further preferably 0.10 μmol or more, and usually 100 μmol relative to 1 mole of bisphenol or diphenyl carbonate. Molar or less, preferably 50 μmol or less, further preferably 20 μmol or less. When the usage amount of the catalyst is within the above range, it is easy to obtain the polymerization activity necessary for producing a polycarbonate resin with a required molecular weight, and the polymer has an excellent hue, and it is easy to obtain branching of the polymer without excessive progress. Polycarbonate resin with excellent fluidity during molding.

When producing polycarbonate resin by the above method, it is preferable to continuously supply the above two raw materials to the raw material mixing tank, and to continuously supply the obtained mixture and the transesterification catalyst to the polymerization tank. In the production of 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 tank in which a transesterification catalyst is added to produce a polymer.

In the production of the polycarbonate resin using the bisphenol of the present invention, the polymerization reaction temperature is preferably 80 to 400°C, and particularly preferably 150 to 350°C. The polymerization time is appropriately adjusted according to the ratio of raw materials, the required molecular weight of the polycarbonate resin, etc. If the polymerization time is long, quality deterioration such as color tone deterioration will be obvious, so it 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.

According to the bisphenol of the present invention, a polycarbonate resin excellent in hue and transparency can be produced. For example, a polycarbonate resin having a viscosity average molecular weight (Mv) of 10,000 or more, preferably 15,000 or more and 100,000 or less, preferably 35,000 or less, and a particle YI of 10 or less, with a hue and excellent transparency can be produced in a short time.

[Production method of organic compounds] By going through the above-mentioned chelation treatment step and alkali treatment step in the same manner as the method for producing bisphenol of the present invention, it is possible to produce not only bisphenol but also a partial structure represented by the following formula (I) in the molecule (hereinafter, there is The metal-coordinating organic compound (hereinafter sometimes referred to as the "organic compound (I)") can also be removed and mixed into the organic compound (I). of impurities such as metals to produce high-quality organic compounds (I) with high purity.

Here, the so-called "metal coordination" refers to a compound that can be bonded to a metal ion through a coordination bond to form a complex. The organic compound (I) has a partial structure (I), thereby acting as a coordination compound for the metal ion. base functions.

[Chemical 6]

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

X and Y in formula (I) may each further have a substituent containing an element selected from the group consisting of trivalent nitrogen, divalent oxygen, trivalent phosphorus and divalent sulfur. The so-called "carbon chain" refers to a connection in which carbon atoms are connected to each other by single bonds, double bonds, or triple bonds. It is not limited to linear or branched chains, and may also include cyclic structures or other structures. A combination of others.

The organic compound (I) is a metal coordination compound in which part of the structure (I) functions as a ligand for metal ions. Therefore, the organic compound (I) is present in the reaction product as a complex compound coordinated to the metal in many cases due to the metal compound used as a catalyst or the impurities mixed during the production process. When the organic compound (I) is used in products containing metal, undesirable conditions such as coloration, decomposition, and deterioration may occur due to the metal contained.

By applying the production sequence of the above-described method for producing bisphenol of the present invention to the production of organic compound (I), metals can be efficiently removed from organic compound (I) and high-quality organic compound (I) can be produced with high purity. ).

The method for producing an organic compound of the present invention is characterized by including the following steps: mixing the organic phase 1' of the mixed liquid 1' of the aqueous phase 1' and the organic phase 1' containing the organic compound (I) with a chelating agent to obtain pH 6 The following steps of the mixed liquid 2' of the aqueous phase and the organic phase; the step of mixing the obtained mixed liquid 2' with an alkali to obtain the mixed liquid 3' of the aqueous phase and the organic phase with a pH of 8 or above; and from the obtained mixture The step of removing the aqueous phase with a pH of above 8 in the liquid 3' to obtain the organic phase 3A'; and the solubility of the organic compound (I) to the organic phase of the mixed liquid 3' is higher than the solubility to the aqueous phase of the mixed liquid 3', chelate The solubility of the mixture in the aqueous phase of the mixed liquid 3' is higher than the solubility in the organic phase of the mixed liquid 3'. "Bisphenol" in the above method for producing bisphenol can be renamed as "organic compound (I)", "organic phase 1" can be renamed as "organic phase 1'", and "mixed liquid 2" can be renamed "Mixed liquid 2'", "organic phase 3A" is renamed as "organic phase 3A'", and is carried out in the same manner as the above-mentioned method for producing bisphenol.

Examples of the organic compound (I) to which the method for producing an organic compound of the present invention is applied include a amide group, a hydrazine group, a amide imine group, and an amidine group having X and/or Y as a nitrogen element as part of the structure (I). group, nitrile group, or alcohol group, phenyl group, ether group where X and/or Y are oxygen elements, or thiol group or thioether group where X and/or Y are sulfur elements.

In the case where the organic compound (I) is the above-mentioned chelating agent, the above-mentioned chelating agent different from the organic compound (I) is selected. Examples include the following combinations. When the organic compound (I) is the above-mentioned carboxylic acid, the above-mentioned β-diketones or the above-mentioned dioximes are selected as the chelating agent. When the organic compound (I) is the above-mentioned β-diketones, the above-mentioned carboxylic acids or the above-mentioned dioximes are selected as the chelating agent. When the organic compound (I) is the above-mentioned dioxime, the above-mentioned carboxylic acid or β-diketones are selected as the chelating agent.

Examples of the organic compound (I) include the following. However, the organic compound (I) to which the method for producing an organic compound of the present invention is applied is not limited to the following.

<Organic compound (I) where X and Y are the same> Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid and other dicarboxylates Acids, Oxalamide, malondiamide, succinyldiamide, glutadiamide, hexamethylenediamide, pimediamide, suberamide, nonanediamide, sebacodiamide, o-phthalamide , isophthalamide, terephthalamide and other diamides,

Ethylenedihydrazine, malondihydrazine, succinihydrazine, glutadihydrazide, adihydrazide, hepadihydrazide, subericonium hydrazine, nonadihydrazide, sebadihydrazide, phthalate Hydrazine, isophthalic acid hydrazine, terephthalic acid hydrazine and other dihydrazide acids, Dinitriles such as succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, azelonitrile, sebaconitrile, etc. dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, jiuya Diisocyanates such as methyl diisocyanate and decamethylene diisocyanate, Ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexylene glycol, heptanediol, octanediol, nonanediol, decanediol, cyclopropylene glycol, cyclopropanediol, cyclobutanediol, cyclobutanediol Methanol, cyclopentanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, cycloheptanediol, cycloheptanediol, cyclooctanediol, cyclooctanedimethanol, cyclononanediol, cyclononanediol Methanol, cyclodecanediol, cyclodecanediol and other glycols,

Diphenols such as diphenol, dimethylbiphenol, and tetramethylbiphenol, Diamines such as ethylenediamine, propylenediamine, butylenediamine, pentyldiamine, hexamethylenediamine, heptanediamine, octyldiamine, nonanediamine, decanediamine, and phenylenediamine, Diimines such as ethylenediimine, propylenediimine, styrenediimine, glutadiimine, hexamethylenediimine, peptodiimine, octodiimine, nonanediimine, and sebacodiimine,

Dihydrazines such as ethylenedihydrazine, malonichydrazine, succinic dihydrazine, glutaric dihydrazine, adipodihydrazine, pimedihydrazine, suberic dihydrazine, azelodihydrazine, decanedihydrazine, benzodihydrazine, etc. Dimethoxymethane, dimethoxyethane, dimethoxypropane, dimethoxybutane, dimethoxypentane, dimethoxyhexane, dimethoxyheptane, dimethoxy Octane, dimethoxynonane, dimethoxydecane, dimethoxybenzene, diethoxymethane, diethoxyethane, diethoxypropane, diethoxybutane, Diethoxypentane, diethoxyhexane, diethoxyheptane, diethoxyoctane, diethoxynonane, diethoxydecane, diethoxybenzene, dipropylene Oxymethane, dipropoxyethane, dipropoxypropane, dipropoxybutane, dipropoxypentane, dipropoxyhexane, dipropoxyheptane, dipropoxyoctane Alkanes, dipropoxynonane, dipropoxydecane, dipropoxybenzene and other diethers,

Dimethylthiomethane, dimethylthioethane, dimethylthiopropane, dimethylthiobutane, dimethylthiopentane, dimethylthiohexane, dimethylthioheptane, dimethylthio Octane, dimethylthiononane, dimethylthiodecane, dimethylthiobenzene, diethylthiomethane, diethylthioethane, diethylthiopropane, diethylthiobutane, Diethylthiopentane, diethylthiohexane, diethylthioheptane, diethylthiooctane, diethylthiononane, diethylthiodecane, diethylthiobenzene, dipropylene Methane thio, dipropylthioethane, dipropylthiopropane, dipropylthiobutane, dipropylthiopentane, dipropylthiohexane, dipropylthioheptane, dipropylthiooctane alkane, dipropylthiononane, dipropylthiodecane, dipropylthiobenzene and other disulfides,

＜Organic compound (I) with different X and Y＞ Methyl nitrile isocyanate, ethyl nitrile isocyanate, propylene nitrile isocyanate, butylene nitrile isocyanate, pentyl nitrile isocyanate, hexylene nitrile isocyanate, heptyl nitrile isocyanate, octyl nitrile isocyanate, nonylene nitrile isocyanate Nitrile isocyanates such as nitrile isocyanate, decyl nitrile isocyanate, benzonitrile isocyanate, etc.

Hydroxymethylnitrile, hydroxyethylnitrile, hydroxypropylnitrile, hydroxybutylnitrile, hydroxypentylnitrile, hydroxyhexylnitrile, hydroxyheptylnitrile, hydroxyoctylnitrile, hydroxynonylnitrile, hydroxydecylnitrile, hydroxyl Phenylnitrile and other hydroxynitriles,

Hydroxyphenylmethylnitrile, hydroxyphenylethylnitrile, hydroxyphenylpropylnitrile, hydroxyphenylbutylnitrile, hydroxyphenylpentylnitrile, hydroxyphenylhexylnitrile, hydroxyphenylheptylnitrile, hydroxybenzene Hydroxyphenyl nitriles such as hydroxyphenyl nitrile, hydroxyphenyl nonyl nitrile, hydroxyphenyl decyl nitrile, hydroxyphenyl phenyl nitrile, etc.

Aminomethylnitrile, aminoethylnitrile, aminopropylnitrile, aminobutylnitrile, aminopentylnitrile, aminohexylnitrile, aminoheptylnitrile, aminooctylnitrile, aminononan Amino nitriles, such as amino nitrile, amino decyl nitrile, and amino phenyl nitrile,

Iminomethylnitrile, iminoethylnitrile, iminopropylnitrile, iminobutylnitrile, iminopentylnitrile, iminohexylnitrile, iminoheptylnitrile, imine Imino nitriles such as octyl nitrile, imino nonyl nitrile, imino decyl nitrile, imino phenyl nitrile, etc.

Methine nitrile hydrazine, ethyl nitrile hydrazine, propyl nitrile hydrazine, butylene nitrile hydrazine, pentyl nitrile hydrazine, hexylene nitrile hydrazine, heptyl nitrile hydrazine, octyl nitrile hydrazine, nonyl nitrile Nitrile hydrazines such as nitrile hydrazine, decyl nitrile hydrazine, phenyl nitrile hydrazine, etc.

Methoxymethylnitrile, methoxyethylnitrile, methoxypropylnitrile, methoxybutylnitrile, methoxypentylnitrile, methoxyhexylnitrile, methoxyheptylnitrile, methoxy Glyoctyl nitrile, methoxynonyl nitrile, methoxydecyl nitrile, methoxyphenyl nitrile, ethoxy methyl nitrile, ethoxy ethyl nitrile, ethoxy propyl nitrile, ethoxy Butyl nitrile, ethoxypentyl nitrile, ethoxyhexyl nitrile, ethoxy heptyl nitrile, ethoxy octyl nitrile, ethoxy nonyl nitrile, ethoxy decyl nitrile, ethoxy phenyl Nitrile, propoxymethylnitrile, propoxyethylnitrile, propoxypropylnitrile, propoxybutylnitrile, propoxypentylnitrile, propoxyhexylnitrile, propoxyheptylnitrile, Alkoxy nitriles such as propoxyoctyl nitrile, propoxy nonyl nitrile, propoxy decyl nitrile, propoxy phenyl nitrile, etc.

Methyl nitrile sulfide, ethyl nitrile sulfide, propylene nitrile sulfide, butylene nitrile sulfide, pentyl nitrile sulfide, hexylene nitrile sulfide, heptyl nitrile sulfide, octyl nitrile sulfide nitrile sulfide such as nonyl nitrile sulfide, nonyl nitrile sulfide, decyl nitrile sulfide, benzonitrile sulfide, etc.

Hydroxymethyl isocyanate, hydroxyethyl isocyanate, hydroxypropyl isocyanate, hydroxybutyl isocyanate, hydroxyamyl isocyanate, hydroxyhexyl isocyanate, hydroxyheptyl isocyanate, isocyanate Hydroxyocyanate isocyanate, hydroxynonyl isocyanate, hydroxydecyl isocyanate, hydroxyphenyl isocyanate and other hydroxyisocyanate esters,

Hydroxyphenyl methyl isocyanate, hydroxyphenyl ethyl isocyanate, hydroxyphenyl propyl isocyanate, hydroxyphenyl butyl isocyanate, hydroxyphenyl amyl isocyanate, hydroxybenzene isocyanate Hexyl isocyanate, hydroxyphenyl heptyl isocyanate, hydroxyphenyl octyl isocyanate, hydroxyphenyl nonyl isocyanate, hydroxyphenyl decyl isocyanate, hydroxyphenyl phenyl isocyanate and other isocyanate Hydroxyphenyl cyanate,

Aminomethyl isocyanate, Aminoethyl isocyanate, Aminopropyl isocyanate, Aminobutyl isocyanate, Aminopentyl isocyanate, Aminohexyl isocyanate, Isocyanate Amino isocyanate esters such as aminoheptyl isocyanate, aminooctyl isocyanate, aminononyl isocyanate, aminodecyl isocyanate, and aminophenyl isocyanate,

Iminomethyl isocyanate, iminoethyl isocyanate, iminopropyl isocyanate, iminobutyl isocyanate, iminopentyl isocyanate, imine isocyanate Hexyl isocyanate, iminoheptyl isocyanate, iminooctyl isocyanate, iminononyl isocyanate, iminodecyl isocyanate, iminophenyl isocyanate, etc. Imide cyanate esters,

Methyl isocyanato hydrazine, ethylidene isocyanato hydrazine, propylene isocyanato hydrazine, butylene isocyanato hydrazine, amyl isocyanate hydrazine, hexylene isocyanato hydrazine Isocyanate groups such as heptyl isocyanato hydrazine, octyl isocyanato hydrazine, nonylene isocyanato hydrazine, decyl isocyanato hydrazine, phenyl isocyanato hydrazine Hydrazines,

Methoxymethyl isocyanate, methoxyethyl isocyanate, methoxypropyl isocyanate, methoxybutyl isocyanate, methoxypentyl isocyanate, methoxy isocyanate Hexyl isocyanate, methoxyheptyl isocyanate, methoxyoctyl isocyanate, methoxynonyl isocyanate, methoxydecyl isocyanate, methoxyphenyl isocyanate, isocyanate Ethoxymethyl isocyanate, ethoxyethyl isocyanate, ethoxypropyl isocyanate, ethoxybutyl isocyanate, ethoxypentyl isocyanate, ethoxy isocyanate Hexyl isocyanate, ethoxyheptyl isocyanate, ethoxyoctyl isocyanate, ethoxynonyl isocyanate, ethoxydecyl isocyanate, ethoxyphenyl isocyanate, isocyanate Propoxymethyl isocyanate, propoxyethyl isocyanate, propoxypropyl isocyanate, propoxybutyl isocyanate, propoxypentyl isocyanate, propoxyhexyl isocyanate Ester, propoxyheptyl isocyanate, propoxyoctyl isocyanate, propoxynonyl isocyanate, propoxydecyl isocyanate, propoxyphenyl isocyanate and other isocyanates alkoxyesters,

Methyl isocyanato sulfide, ethyl isocyanate sulfide, propylene isocyanato sulfide, butylene isocyanato sulfide, amyl isocyanato sulfide, Hexylene isocyanato sulfide, hepterythyl isocyanate sulfide, octerylene isocyanate sulfide, nonylene isocyanate sulfide, decyl isocyanate sulfide, benzene Isocyanate sulfides such as isocyanate sulfide,

Hydroxyl methylphenol, hydroxyethylphenol, hydroxypropylphenol, hydroxybutylphenol, hydroxyamylphenol, hydroxyhexylphenol, hydroxyheptylphenol, hydroxyoctylphenol, hydroxynonylphenol, hydroxydecylphenol, etc. Alkylphenols,

Hydroxymethylamine, hydroxyethylamine, hydroxypropylamine, hydroxybutylamine, hydroxypentylamine, hydroxyhexylamine, hydroxyheptylamine, hydroxyoctylamine, hydroxynonylamine, hydroxydecylamine and other hydroxyl groups Alkylamines,

Hydroxymethylimine, hydroxyethylimine, hydroxypropylimine, hydroxybutylimine, hydroxypentylimine, hydroxyhexylimine, hydroxyheptylimine, hydroxyoctylimine, hydroxynonyl Hydroxyalkyl imines such as imine and hydroxydecyl imine,

Hydroxymethylhydrazine, hydroxyethylhydrazine, hydroxypropylhydrazine, hydroxybutylhydrazine, hydroxypentylhydrazine, hydroxyhexylhydrazine, hydroxyheptylhydrazine, hydroxyoctylhydrazine, hydroxynonylhydrazine, hydroxydecylhydrazine and other hydroxyl groups Alkyl hydrazines,

Methoxymethanol, methoxyethanol, methoxypropanol, methoxybutanol, methoxypentanol, methoxyhexanol, methoxyheptanol, methoxyoctanol, methoxynonanol Alcohol, methoxydecanol, methoxyphenyl alcohol, ethoxymethanol, ethoxyethanol, ethoxypropanol, ethoxybutanol, ethoxypentanol, ethoxyhexanol, ethoxy Heptanol, ethoxyoctanol, ethoxynonanol, ethoxydecanol, ethoxyphenyl alcohol, propoxymethanol, propoxyethanol, propoxypropanol, propoxybutanol, Alkoxy alcohols such as propoxypentanol, propoxyhexanol, propoxyheptanol, propoxyoctanol, propoxynonanol, propoxydecanol, propoxyphenylol, etc.

Hydroxymethyl sulfide, hydroxyethyl sulfide, hydroxypropyl sulfide, hydroxybutyl sulfide, hydroxypentyl sulfide, hydroxyhexyl sulfide, hydroxyheptyl sulfide, hydroxyoctyl sulfide, hydroxynonyl Hydroxyalkyl sulfides such as thioether and hydroxydecyl sulfide,

Hydroxyphenylmethylamine, hydroxyphenylethylamine, hydroxyphenylpropylamine, hydroxyphenylbutylamine, hydroxyphenylpentylamine, hydroxyphenylhexylamine, hydroxyphenylheptylamine, hydroxyphenylamine Hydroxyphenylamines such as hydroxyphenylamine, hydroxyphenylnonylamine, hydroxyphenyldecylamine, hydroxyphenylphenylamine, etc.

Hydroxyphenylmethylimine, hydroxyphenylethylimine, hydroxyphenylpropylimine, hydroxyphenylbutylimine, hydroxyphenylpentylimine, hydroxyphenylhexylimine, hydroxyphenyl Heptyl imine, hydroxyphenyl octyl imine, hydroxyphenyl nonyl imine, hydroxyphenyl decyl imine, hydroxyphenyl phenyl imine and other hydroxyphenyl imines,

Hydroxyphenylmethylhydrazine, hydroxyphenylethylhydrazine, hydroxyphenylpropylhydrazine, hydroxyphenylbutylhydrazine, hydroxyphenylpentylhydrazine, hydroxyphenylhexylhydrazine, hydroxyphenylheptylhydrazine, hydroxybenzene Hydroxyphenyl hydrazines such as hydroxyphenylhydrazine, hydroxyphenylnonylhydrazine, hydroxyphenyldecylhydrazine, hydroxyphenylphenylhydrazine, etc.

Methoxymethylphenol, methoxyethylphenol, methoxypropylphenol, methoxybutylphenol, methoxypentylphenol, methoxyhexylphenol, methoxyheptylphenol, methoxy Glyoctylphenol, methoxynonylphenol, methoxydecylphenol, methoxyphenylphenol, ethoxymethylphenol, ethoxyethylphenol, ethoxypropylphenol, ethoxy Butylphenol, ethoxypentylphenol, ethoxyhexylphenol, ethoxyheptylphenol, ethoxyoctylphenol, ethoxynonylphenol, ethoxydecylphenol, ethoxyphenyl Phenol, propoxymethylphenol, propoxyethylphenol, propoxypropylphenol, propoxybutylphenol, propoxypentylphenol, propoxyhexylphenol, propoxyheptylphenol, Alkoxyphenols such as propoxyoctylphenol, propoxynonylphenol, propoxydecylphenol, and propoxyphenylphenol,

Hydroxyphenyl methyl sulfide, hydroxyphenylethyl sulfide, hydroxyphenyl propyl sulfide, hydroxyphenyl butyl sulfide, hydroxyphenyl pentyl sulfide, hydroxyphenylhexyl sulfide, hydroxyphenyl sulfide Heptyl sulfide, hydroxyphenyl octyl sulfide, hydroxyphenyl nonyl sulfide, hydroxyphenyl decyl sulfide, hydroxyphenyl phenyl sulfide and other hydroxyphenyl sulfides,

Methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, methoxypentylamine, methoxyhexylamine, methoxyheptylamine, methoxy Octylamine, methoxynonylamine, methoxydecylamine, methoxyphenylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxy Butylamine, ethoxypentylamine, ethoxyhexylamine, ethoxyheptylamine, ethoxyoctylamine, ethoxynonylamine, ethoxydecylamine, ethoxyphenyl Amine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, propoxypentylamine, propoxyhexylamine, propoxyheptylamine, Alkoxyamines such as propoxyoctylamine, propoxynonylamine, propoxydecylamine, propoxyphenylamine, etc. [Example]

Hereinafter, the present invention will be explained more specifically through Examples and Comparative Examples. The present invention is not limited to the following examples unless the gist thereof is 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, ethylene glycol Disodium aminetetraacetate, dodecane, and heptane were reagents manufactured by FUJIFILM Wako Pure Chemical Co., Ltd. The hydrogen chloride system uses products from Sumitomo Seika Co., Ltd. As diphenyl carbonate, a product manufactured by Mitsubishi Chemical Co., Ltd. was used.

[analyze] ＜Composition of bisphenol C production reaction liquid＞ The composition analysis of the bisphenol C-generated reaction solution was carried out by high-performance liquid chromatography under the following sequence and conditions. ・Device: "LC-2010A" manufactured by Shimadzu Corporation Imtakt Scherzo SM-C18 3 μm 250 mm×3.0 mmID ・Low pressure gradient method ・Analysis temperature: 40℃ ・Eluent composition: Solution A ammonium acetate: acetic acid: desalted water = 3.000 g: 1 mL: 1 L solution Solution B ammonium acetate: acetic acid: acetonitrile: desalted water = 1.500 g: 1 mL: 900 mL: 150 mL solution ・Within 0 minutes of analysis time, the composition of the eluent is liquid A: liquid B = 60:40 (volume ratio, the same below) The analysis time from 0 to 41.67 minutes changes slowly as liquid A: liquid B = 10:90. The analysis time of 41.67 to 50 minutes is maintained as liquid A: liquid B = 10:90. And analyzed at a flow rate of 0.34 mL/min.

<Identification of isopropenylcresol> Identification of isopropenylcresol was carried out using a gas chromatography mass spectrometer under the following sequence and conditions.・Device: "Agilent6890" manufactured by Agilent Technology Co., Ltd. ・Column: "DB-1MS" manufactured by Agilent Technology Co., Ltd. (inner diameter 0.25 mm×30 m×0.25 μm) ・Carrier gas: Helium flow rate: 1 per minute cm ³・Injection port temperature: 280℃ ・Transfer temperature: 250℃ ・Ion source temperature: 250℃ ・Column heating mode: first, keep at 50℃ for 3 minutes, then increase the temperature to 320℃ at 10℃ per minute. And keep at 280℃ for 5 minutes

<Measurement of iron concentration contained in bisphenol C or 1,1-bis(4-hydroxyphenyl)dodecane> A sample was prepared by ashing 1 g of bisphenol C or 1,1-bis(4-hydroxyphenyl)dodecane and dissolving it in acid. The following equipment was used in the analysis system. Device: ICP-MS: "ELEMENT2" manufactured by Thermo Fisher Scientific ICP-OES: "ICP VISTA-PRO" manufactured by Agilent (VARIAN)

＜Measurement of pH＞ The pH was measured using a pH meter "pH METER ES-73" manufactured by Horiba Manufacturing Co., Ltd., and the water phase at 25°C was taken from a flask.

＜Conductivity＞ The electrical conductivity was measured using a conductivity meter "COND METER D-71" manufactured by Horiba Manufacturing Co., Ltd., and was performed on a 25°C aqueous phase taken from a flask.

＜Methanol-soluble color of bisphenol C＞ Methanol-soluble color system of bisphenol C. Add 10 g of bisphenol C and 10 g of methanol to a test tube "P-24" (24 mmϕ×200 mm) manufactured by NICHIDEN RIKA GLASS Co., Ltd. to prepare a uniform solution. 20°C) using "SE6000" manufactured by Nippon Denshoku Industries Co., Ltd., the Hazen color value was measured and evaluated.

＜Melting Color Difference of Bisphenol C＞ The melt color difference of bisphenol C was measured by adding 20 g of bisphenol C to a test tube "P-24" (24 mmϕ×200 mm) manufactured by NICHIDEN RIKA GLASS Co., Ltd. and melting it at 190°C for 30 minutes. Nippon Denshoku Industries Co., Ltd. The Hazen color value of "SE6000" manufactured by the company was measured and evaluated.

＜Thermal tone stability of bisphenol C＞ Thermal color stability of bisphenol C is achieved by adding 20 g of bisphenol C to a test tube "P-24" (24 mmϕ×200 mm) manufactured by NICHIDEN RIKA GLASS, and melting it at 190°C for 4 hours. "SE6000" manufactured by Color Industry Co., Ltd. was used to measure and evaluate the Hazen color value.

＜Thermal Decomposition Stability of Bisphenol C＞ Thermal decomposition stability of bisphenol C is determined by adding 20 g of bisphenol C to a test tube "P-24" (24 mmϕ×200 mm) manufactured by NICHIDEN RIKA GLASS, melting it at 190°C for 2 hours, and mixing it with the above bisphenol The composition analysis of the C production reaction liquid was carried out in the same manner, and the amount of isopropenylcresol produced was measured and evaluated.

<Viscosity average molecular weight> Dissolve polycarbonate resin in methylene chloride (concentration 6.0 g/L), measure the specific viscosity (ηsp) at 20°C using an Ubbelohde viscosity tube, and calculate the viscosity average molecular weight from the following formula (Mv). ηsp/C＝[η](1＋0.28ηsp) [η]＝1.23×10 ^-4 Mv ^0.83

＜Particle YI＞ Particle YI (transparency of polycarbonate resin) is based on ASTM (American Society for Testing Materials, American Society for Testing Materials) D1925. The YI value (yellow index value) of reflected light of polycarbonate resin particles is measured and evaluated. The device uses a spectrophotometer "CM-5" manufactured by Konica Minolta Co., Ltd., and the measurement conditions are selected to measure a diameter of 30 mm and SCE (Specular Component Excluded, excluding specular reflected light). Insert the calibration glass "CM-A212" for petri dish measurement into the measurement part, cover it with the zero-point calibration box "CM-A124" to perform zero-point calibration, and then use the built-in white calibration plate to perform white calibration. Then, measurement was performed using the white calibration plate "CM-A210", and it was confirmed that L* became 99.40±0.05, a* became 0.03±0.01, b* became -0.43±0.01, and YI became -0.58±0.01. YI is measured by filling particles into a cylindrical glass container with an inner diameter of 30 mm and a height of 50 mm to a depth of approximately 40 mm. Repeat the operation of taking out the particles from the glass container and measuring again twice, and use the average of the three measured values.

[Reference example 1] Add 85 g of bisphenol C and 4.5 g of sodium hydroxide to a 500 mL eggplant-shaped flask equipped with a stirrer, thermometer, and distillation device, and immerse it in an oil bath heated to 195°C. After confirming that the bisphenol C in the eggplant-shaped flask is melted, use a vacuum pump to slowly depressurize the flask to achieve a full vacuum. Evaporation begins after a while, and distillation under reduced pressure is carried out until the distillation is complete. From a gas chromatograph equipped with a mass meter detector, it was found that the obtained fraction was a mixture of cresol and isopropenylcresol produced by thermal decomposition of bisphenol C. The obtained fraction was used to confirm the retention time of isopropenylcresol under the composition analysis conditions of the bisphenol C production reaction liquid.

[Reference example 2] (1) Preparation of mixed solution To a detachable flask equipped with a hydrogen chloride injection tube, a thermometer, a sleeve and an anchor stirring blade, add 510 g (4.7 mol) of o-cresol, 104 g (1.8 mol) of acetone, and 100 g of toluene under a nitrogen atmosphere. and 10 g of dodecanethiol, and set the internal temperature to 30°C to prepare a mixed solution.

(2)Reaction After slowly passing hydrogen chloride gas into the above mixed liquid, the mixture was reacted for 10 hours to obtain a reaction liquid.

(3) Rough refining After adding 720 g of toluene and 900 g of desalted water to the obtained reaction liquid, the internal temperature was raised to 80°C while stirring. After the internal temperature reached 80° C., the mixture was left to stand and separated into a first organic phase and a first aqueous phase to obtain a first organic phase. Add 250 g of desalted water to the obtained first organic phase, let it stand after the internal temperature reaches 80°C, separate it into a second organic phase and a second aqueous phase, and extract the second aqueous phase to obtain the second organic phase. Mutually. To 1,400 g of the obtained second organic phase, 300 g of a 5% by mass sodium bicarbonate aqueous solution was added, and the mixture was allowed to stand until the internal temperature reached 80°C while mixing. It was confirmed that the pH of the lower phase reached 9 or higher. Thereafter, the third organic phase and the sodium bicarbonate aqueous solution were phase-separated, and the lower phase was extracted to obtain the third organic phase.

(4)Refined The obtained third organic phase was cooled from 80°C to 10°C. After reaching 10°C, solid-liquid separation was performed using centrifugal separation (rotating at 2500 rpm for 10 minutes) to obtain the first wet cake. The first wet filter cake obtained was transferred to a beaker, 500 g of toluene was added thereto, and suspended and washed. The obtained slurry liquid was solid-liquid separated again using centrifugal separation (rotation speed 2500 rpm, 10 minutes), and 415 g of the second wet cake was obtained. The iron concentration of bisphenol C contained in the obtained second wet cake was 4.7 ppm by mass.

[Example 1] To a full-tube separable flask equipped with a thermometer and a stirrer, 300 g of a portion of the second wet cake of Reference Example 2 and 420 g of toluene were added, and the temperature was raised to 80°C. It was confirmed that it became a homogeneous solution, and the 4th organic phase was obtained. To 700 g of the obtained fourth organic phase, 200 g of 5 mass % hydrochloric acid was added, mixed for 30 minutes, and the third aqueous phase of the lower phase was removed to obtain the fifth organic phase. Add 200 g of desalted water to the obtained fifth organic phase, mix for 30 minutes, remove the fourth removed aqueous phase of the lower phase, and obtain the sixth organic phase. The pH of the fourth aqueous phase (pH of the aqueous phase before supply of disodium ethylenediaminetetraacetate) was confirmed and found to be pH 2.

1 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added to 700 g of the obtained sixth organic phase, and the mixture was mixed for 30 minutes. The pH test paper was used to confirm the acidity and alkalinity, and it was confirmed that the pH of the aqueous phase was 2. A saturated sodium carbonate (18% by mass) aqueous solution was added thereto until the aqueous phase showed alkalinity, and the mixture was mixed for 30 minutes, and the fifth aqueous phase was extracted to obtain the seventh organic phase. The pH of the fifth aqueous phase (pH of the aqueous phase after extracting disodium ethylenediaminetetraacetate) was confirmed, and the result was pH 9. The obtained seventh organic phase was repeatedly washed with desalted water until the conductivity of the lower aqueous phase became 3.0 μS/cm or less, thereby obtaining the eighth organic phase.

The obtained 8th organic phase was cooled from 80°C to 10°C. Thereafter, a centrifuge (3000 rotations per minute, 10 minutes) was used for filtration to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, the light boiling fraction is distilled under reduced pressure at an oil bath temperature of 80°C to obtain 10 g of white bisphenol C.

The iron concentration of the obtained bisphenol C was 16 ppb by mass. The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color value was 0. The melt color difference of the obtained bisphenol C was measured, and the result was that the Hazen color value was 10. The thermal color tone stability of the obtained bisphenol C was measured, and the result was that the Hazen color value was 36. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 100 ppm by mass.

[Example 2] In Example 1, the same procedure as Example 1 was performed except that 10 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added instead of 1 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution. The aqueous phase before supplying disodium edetate is pH 2, and the aqueous phase after extracting disodium edetate is pH 9.

The iron concentration of the obtained bisphenol C was 20 ppb by mass. The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color value was 0. The melt color difference of the obtained bisphenol C was measured, and the result was that the Hazen color value was 10. The thermal color tone stability of the obtained bisphenol C was measured, and the Hazen color value was 34. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 95 ppm by mass.

[Example 3] In Example 1, the same procedure as Example 1 was performed except that 100 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added instead of 1 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution. The aqueous phase before supplying disodium edetate is pH 2, and the aqueous phase after extracting disodium edetate is pH 9.

The iron concentration of the obtained bisphenol C was 18 ppb by mass. The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color value was 0. The melt color difference of the obtained bisphenol C was measured, and the result was that the Hazen color value was 10. The thermal color tone stability of the obtained bisphenol C was measured, and the Hazen color value was 33. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 91 ppm by mass.

[Example 4] To a full-tube separable flask equipped with a thermometer and a stirrer, 300 g of a portion of the second wet cake of Reference Example 2 and 420 g of toluene were added, and the temperature was raised to 80°C. It was confirmed that it became a homogeneous solution, and the 4th organic phase was obtained. To 700 g of the obtained fourth organic phase, 300 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, and the mixture was mixed for 30 minutes. The acidity and alkalinity of the aqueous phase was confirmed using pH test paper to be pH 5. A saturated sodium carbonate (18% by mass) aqueous solution was added thereto until the aqueous phase showed alkalinity, and the mixture was mixed for 30 minutes, and the fourth aqueous phase was extracted to obtain a fifth organic phase. The pH of the fourth aqueous phase (pH of the aqueous phase after extracting disodium ethylenediaminetetraacetate) was confirmed, and the result was pH 9. Using desalted water, the obtained fifth organic phase was repeatedly washed until the conductivity of the lower aqueous phase became 3.0 μS/cm or less, thereby obtaining the sixth organic phase.

The obtained 6th organic phase was cooled from 80°C to 10°C. Thereafter, a centrifuge (3000 rotations per minute, 10 minutes) was used for filtration to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, the light boiling fraction is distilled under reduced pressure at an oil bath temperature of 80°C to obtain white bisphenol C209 g.

The iron concentration of the obtained bisphenol C was 54 ppb by mass. The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color value was 0. The melt color difference of the obtained bisphenol C was measured, and the result was that the Hazen color value was 19. The thermal color tone stability of the obtained bisphenol C was measured, and the result was that the Hazen color value was 38. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 127 ppm by mass.

[Comparative example 1] To a full-tube separable flask equipped with a thermometer and a stirrer, 300 g of a portion of the second wet cake of Reference Example 2 and 420 g of toluene were added, and the temperature was raised to 80°C. It was confirmed that it became a homogeneous solution, and the 4th organic phase was obtained. Add 200 g of desalted water to the obtained fourth organic phase, mix for 30 minutes, remove the third aqueous phase of the lower phase, and obtain the fifth organic phase. The acidity and alkalinity of the third aqueous phase (pH of the aqueous phase before supply of disodium ethylenediaminetetraacetate) was found to be pH 9 using pH test paper. To the obtained fifth organic phase, 10 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, mixed for 30 minutes, and the fourth aqueous phase was extracted to obtain the sixth organic phase. The fourth aqueous phase (the pH of the aqueous phase after extracting disodium ethylenediaminetetraacetate) is pH 9. Using desalted water, the obtained sixth organic phase was repeatedly washed until the conductivity of the lower aqueous phase became 3.0 μS/cm or less, thereby obtaining the seventh organic phase.

The obtained seventh organic phase was cooled from 80°C to 10°C. Thereafter, a centrifuge (3000 rotations per minute, 10 minutes) was used for filtration to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, the light boiling fraction is distilled under reduced pressure at an oil bath temperature of 80°C to obtain 12 g of white bisphenol C2.

The iron concentration of the obtained bisphenol C was 102 mass ppb. The methanol-soluble color of the obtained bisphenol C was measured, and the result was that the Hazen color value was 12. The melt color difference of the obtained bisphenol C was measured, and the Hazen color value was 42. The thermal color tone stability of the obtained bisphenol C was measured, and the Hazen color value was 65. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 250 ppm by mass.

[Comparative example 2] To a full-tube separable flask equipped with a thermometer and a stirrer, 300 g of a portion of the second wet cake of Reference Example 2 and 420 g of toluene were added, and the temperature was raised to 80°C. It was confirmed that it became a homogeneous solution, and the 4th organic phase was obtained. 200 g of 5 mass % hydrochloric acid was added to the obtained fourth organic phase, mixed for 30 minutes, and the third aqueous phase of the lower phase was removed to obtain the fifth organic phase. Add 200 g of desalted water to the obtained fifth organic phase, mix for 30 minutes, remove the fourth aqueous phase of the lower phase, and obtain the sixth organic phase. The fourth aqueous phase (pH of the aqueous phase before supply of disodium ethylenediaminetetraacetate) is pH 2. To the obtained sixth organic phase, 10 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, mixed for 30 minutes, and the fifth aqueous phase was removed to obtain the seventh organic phase. The fifth aqueous phase is pH 2. A saturated sodium carbonate aqueous solution was added to the obtained seventh organic phase until the aqueous phase showed alkalinity, mixed for 30 minutes, and the sixth aqueous phase was extracted to obtain the eighth organic phase. Using desalted water, the obtained eighth organic phase was repeatedly washed until the conductivity of the lower aqueous phase became 3.0 μS/cm or less, thereby obtaining the ninth organic phase.

The obtained ninth organic phase was cooled from 80°C to 10°C. Thereafter, a centrifuge (3000 rotations per minute, 10 minutes) was used for filtration to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, the light boiling fraction is distilled under reduced pressure at an oil bath temperature of 80°C to obtain white bisphenol C209 g.

The iron concentration of the obtained bisphenol C was 89 ppb by mass. The methanol-soluble color of the obtained bisphenol C was measured, and the result was that the Hazen color value was 5. The melt color difference of the obtained bisphenol C was measured, and the result was that the Hazen color value was 41. The thermal color tone stability of the obtained bisphenol C was measured, and the Hazen color value was 80. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 210 ppm by mass.

The pH of the aqueous phase before supplying disodium ethylenediaminetetraacetate in Examples 1 to 4 and Comparative Examples 1 and 2, the pH of the aqueous phase after extracting disodium ethylenediaminetetraacetate, and the obtained bisphenol C The iron concentration, methanol dissolved color, melting color difference, thermal hue stability, and thermal decomposition stability are summarized in Table 1.

According to Table 1, it can be seen that if the acidity and alkalinity of the water phase before supplying disodium ethylenediaminetetraacetate is acidic, and the acidity and alkalinity of the water phase after extracting disodium ethylenediaminetetraacetate is alkaline, then the obtained The iron concentration, methanol-soluble color, melt color difference, thermal hue stability, and thermal decomposition stability of bisphenol C. In Comparative Example 2, after adding disodium ethylenediaminetetraacetate, a saturated sodium carbonate aqueous solution was added to the organic phase from which the aqueous phase was removed. Therefore, the iron removal effect by the chelating agent could not be obtained.

[Table 1] pH of the aqueous phase before adding EDTA・2Na After adding EDTA・2Na, the pH of the aqueous phase when the aqueous phase is extracted Iron concentration (mass ppb) Methanol dissolving color (APHA) Melt color difference (APHA) Thermal Hue Stability (APHA) Thermal decomposition stability (mass ppm) Example 1 pH2 pH9 16 0 10 36 100 Example 2 pH2 pH9 20 0 10 34 95 Example 3 pH2 pH9 18 0 10 33 91 Example 4 pH5 pH9 54 0 19 38 127 Comparative example 1 pH9 pH9 102 12 42 65 250 Comparative example 2 pH2 pH2 89 5 41 80 210

[Example 5] In Example 2, the same procedure as Example 2 was carried out except that 10 g of 5 mass % citric acid aqueous solution was added instead of 10 g of 5 mass % disodium ethylenediaminetetraacetate aqueous solution.

The iron concentration of the obtained bisphenol C was 22 ppb by mass. The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color value was 0. The melt color difference of the obtained bisphenol C was measured, and the result was that the Hazen color value was 10. The thermal color tone stability of the obtained bisphenol C was measured, and the Hazen color value was 32. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 99 ppm by mass.

[Example 6] In Example 2, the same procedure as Example 2 was performed except that 10 g of 5 mass% oxalic acid aqueous solution was added instead of 10 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution.

The iron concentration of the obtained bisphenol C was 32 ppb by mass. The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color value was 0. The melt color difference of the obtained bisphenol C was measured, and the result was that the Hazen color value was 10. The thermal color tone stability of the obtained bisphenol C was measured, and the result was that the Hazen color value was 35. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 98 ppm by mass.

[Example 7] In Example 2, the same procedure as Example 2 was carried out except that 10 g of 5 mass % malonic acid aqueous solution was added instead of 10 g of 5 mass % disodium ethylenediaminetetraacetate aqueous solution.

The iron concentration of the obtained bisphenol C was 35 ppb by mass. The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color value was 0. The melt color difference of the obtained bisphenol C was measured, and the result was that the Hazen color value was 10. The thermal color tone stability of the obtained bisphenol C was measured, and the Hazen color value was 33. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 95 ppm by mass.

[Example 8] In Example 2, the same procedure as Example 2 was performed except that 10 g of 5 mass% succinic acid aqueous solution was added instead of 10 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution.

The iron concentration of the obtained bisphenol C was 23 ppb by mass. The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color value was 0. The melt color difference of the obtained bisphenol C was measured, and the result was that the Hazen color value was 10. The thermal color tone stability of the obtained bisphenol C was measured, and the Hazen color value was 32. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 90 ppm by mass.

[Example 9] In Example 2, the same procedure as Example 2 was performed except that 10 g of 5 mass% tartaric acid aqueous solution was added instead of 10 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution. The iron concentration of the obtained bisphenol C was 21 ppb by mass.

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

[Comparative example 3] In Comparative Example 2, the procedure was carried out in the same manner as Comparative Example 2 except that 10 g of 5 mass % citric acid aqueous solution was added instead of 10 g of 5 mass % disodium ethylenediaminetetraacetate aqueous solution.

The iron concentration of the obtained bisphenol C was 102 mass ppb. The methanol-soluble color of the obtained bisphenol C was measured, and the result was that the Hazen color value was 10. The melt color difference of the obtained bisphenol C was measured, and the Hazen color value was 39. The thermal color tone stability of the obtained bisphenol C was measured, and the Hazen color value was 77. The thermal decomposition stability of the obtained bisphenol C was measured, and the result was that the amount of isopropenylcresol produced was 310 ppm by mass.

Table 2 summarizes the chelating agent used in Examples 5 to 9 and Comparative Example 3, the iron concentration of the obtained bisphenol C, methanol dissolution color, melt color difference, thermal color tone stability, and thermal decomposition stability.

From Table 2, it can be seen that when other chelating agents are used in the same manner as disodium ethylenediaminetetraacetate, the iron concentration, methanol-soluble color, melt color difference, thermal tone stability, and thermal decomposition of the obtained bisphenol C are improved. Stability.

[Table 2] Types of chelating agents Alkali treatment step Iron concentration (mass ppb) Methanol dissolving color (APHA) Melt color difference (APHA) Thermal Hue Stability (APHA) Thermal decomposition stability (mass ppm) Example 5 citric acid Example 2 twenty two 0 10 32 99 Example 6 oxalic acid Example 2 32 0 10 35 98 Example 7 Malonate Example 2 35 0 10 33 95 Example 8 succinic acid Example 2 twenty three 0 10 32 90 Example 9 tartaric acid Example 2 twenty one 0 10 31 85 Comparative example 3 citric acid Comparative example 2 102 10 39 77 310

[Example 10] To a glass reaction tank with an internal capacity of 150 mL equipped with a stirrer and a distillation tube, 100.00 g (0.39 mol) of bisphenol C and 86.49 g (0.4 mol) of diphenyl carbonate obtained in Example 2 were added. and 479 μL of 400 mass ppm cesium carbonate aqueous solution. The pressure of the glass reaction tank was reduced to about 100 Pa, and then the operation of returning the pressure to atmospheric pressure using nitrogen was repeated three times to replace the inside of the reaction tank with nitrogen. Thereafter, the reaction tank was immersed in an oil bath at 200° C. to dissolve the contents.

Set the number of revolutions of the mixer to 100 times per minute, while distilling and removing the phenol produced by the oligomerization reaction of bisphenol C and diphenyl carbonate in the reaction tank, while increasing the pressure in the reaction tank for 40 minutes. Decrease the pressure from 101.3 kPa to 13.3 kPa using an absolute pressure gauge. Then, while maintaining the pressure in the reaction tank at 13.3 kPa, the transesterification reaction was performed for 80 minutes while further distilling off the phenol. Thereafter, the external temperature of the reaction tank was raised to 250°C, and the pressure inside the reaction tank was reduced from 13.3 kPa to 399 Pa in absolute pressure over 40 minutes, and the distilled phenol was removed from the system.

Thereafter, the external temperature of the reaction tank was raised to 280°C, the absolute pressure of the reaction tank was reduced to 30 Pa, and the polycondensation reaction was carried out. When the stirrer in the reaction tank reaches the predetermined stirring power, the polycondensation reaction is completed. The time from raising the temperature to 280° C. to the end of polymerization (post-stage polymerization time) was 210 minutes.

Then, after using nitrogen gas to restore the absolute pressure to 101.3 kPa, the pressure was raised to 0.2 MPa using a gauge pressure gauge, and the polycarbonate resin was pulled out in a rope shape from the bottom of the reaction tank to obtain a rope-shaped polycarbonate resin. Thereafter, a rotary cutter is used to pellet the strands to obtain granular polycarbonate resin.

The obtained polycarbonate resin has a viscosity average molecular weight (Mv) of 24,700 and a particle YI of 7.7. A polycarbonate resin with good hue can be obtained.

[Reference example 3] Heat 237 g (2.5 mol) of phenol to 40°C in a fully sleeved detachable flask equipped with a thermometer and a stirrer, and add 3.2 g of hydrochloric acid. Add a mixture of 92.0 g (0.5 mol) of dodecaldehyde and 55.2 g of toluene. After the dropwise addition, the mixture was stirred at 40° C. for 1 hour, and then a 5% by mass sodium bicarbonate aqueous solution was added. Thereafter, toluene and phenol were distilled off under reduced pressure to obtain a residue. To this residue, 450 g of toluene was added and dissolved to obtain an organic phase. The organic phase was washed 4 times with 230 g of desalted water. Thereafter, toluene was distilled off to obtain a residue. To the obtained residue were added 330 g of toluene and 330 g of heptane, and heated to 70°C to dissolve them. Thereafter, the temperature was lowered to 5° C., solid was precipitated, and a slurry liquid was obtained. The obtained slurry liquid was filtered to obtain a solid. The obtained solid was put into a round-bottomed flask, and dried using a rotary evaporator at 70° C. and 20 Torr for 1 hour to obtain 45 g 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] To an eggplant-shaped flask equipped with a magnetic rotor, 10 g of 1,1-bis(4-hydroxyphenyl)dodecane obtained in Reference Example 3 and 14 g of toluene were added and dissolved at 80°C to obtain Toluene solution. 7 g of 5 mass% hydrochloric acid was added thereto and stirred. After the obtained mixed solution was allowed to stand for 30 minutes, the aqueous phase was removed to obtain the first organic phase. The pH of the removed aqueous phase is less than 1.

After adding 7 g of desalted water to the obtained first organic phase, the mixture was shaken for 10 minutes using a separatory funnel, and then left to stand for 30 minutes, and then the aqueous phase was removed to obtain the second organic phase. To the obtained organic phase, 0.3 g of 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, and the mixture was shaken for 10 minutes, and then 2 g of 5 mass% sodium bicarbonate aqueous solution was added, and the mixture was shaken for 10 minutes. After standing for 30 minutes, the aqueous phase was removed to obtain the third organic phase. The pH of the removed aqueous phase was 9.

The obtained third organic phase was washed three times with 7 g of desalted water to obtain a fourth organic phase. The obtained fourth organic phase was cooled to 10°C to obtain a slurry liquid. The obtained slurry liquid was filtered, and the obtained filter cake was dried at 70° C. under reduced pressure, thereby obtaining 7.5 g of 1,1-bis(4-hydroxyphenyl)dodecane. The iron concentration of the obtained 1,1-bis(4-hydroxyphenyl)dodecane was 100 ppb by mass.

[Comparative example 4] To an eggplant-shaped flask equipped with a nuclear magnetic rotor, 10 g of 1,1-bis(4-hydroxyphenyl)dodecane obtained in Reference Example 3 and 14 g of toluene were added and dissolved at 80°C to obtain toluene. solution. To the obtained toluene solution, 0.3 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, and the mixture was shaken for 10 minutes. After the obtained mixed solution was allowed to stand for 30 minutes, the aqueous phase was removed to obtain the first organic phase. The obtained first organic phase was washed three times with 7 g of desalted water to obtain a second organic phase. The obtained second organic phase was cooled to 10°C to obtain a slurry liquid. The obtained slurry liquid was filtered, and the obtained filter cake was dried at 70° C. under reduced pressure, thereby obtaining 7.5 g of 1,1-bis(4-hydroxyphenyl)dodecane. The iron concentration of the obtained 1,1-bis(4-hydroxyphenyl)dodecane was 400 ppb by mass.

The iron concentration of the 1,1-bis(4-hydroxyphenyl)dodecane obtained in Example 11 and Comparative Example 4 before and after the pH change with or without the addition of 5 mass% disodium ethylenediaminetetraacetate aqueous solution summarized in Table 3.

As can be seen from Table 3, the iron concentration of 1,1-bis(4-hydroxyphenyl)dodecane can be reduced by changing the pH before and after adding 5% by mass of disodium ethylenediaminetetraacetate aqueous solution.

[table 3] pH changes before and after adding EDTA-2Na Iron concentration (mass PPb) Example 11 have 100 Comparative example 4 without 400

The present invention has been described in detail using specific aspects. However, it is obvious to those skilled in the art that various changes can be made without departing from the intention and scope of the present invention. This application is based on Japanese Patent Application 2019-049991 filed on March 18, 2019 and Japanese Patent Application 2019-238265 filed on December 27, 2019, the entirety of which are incorporated by reference.

Claims (8)

A method for manufacturing bisphenol, which includes the following steps: mixing the organic phase 1 of the mixed liquid 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol with a chelating agent to obtain a mixture of the aqueous phase and the organic phase with a pH below 6 The steps of liquid 2; the steps of mixing the obtained mixed liquid 2 with an alkali to obtain a mixed liquid 3 of an aqueous phase with a pH of 8 or above and an organic phase; and removing the aqueous phase with a pH of 8 or more from the obtained mixed liquid 3, and The step of obtaining the organic phase 3A; the solubility of the chelating agent in the aqueous phase of the mixed liquid 3 is higher than the solubility in the organic phase of the mixed liquid 3 . The method for producing bisphenol according to claim 1, wherein the organic phase 1 is the organic phase 1A obtained by removing the water phase from the mixed liquid 1. The method for producing bisphenol according to claim 2, wherein water is removed from the mixed liquid 1 in such a way that the mixing ratio of the aqueous phase after the removal of the aqueous phase and the organic phase 1A becomes 1:700 or less in terms of weight ratio. Mutually. The manufacturing method of bisphenol according to any one of claims 1 to 3, wherein the mixing ratio of the aqueous phase and the organic phase in the above-mentioned mixed liquid 2 is 0.001:100~1000:700 based on the weight ratio. The manufacturing method of bisphenol according to any one of claims 1 to 3, which includes the following steps: removing the water phase from the mixed liquid 4 obtained by mixing the above-mentioned organic phase 3A and desalted water to obtain the organic phase 4. The method for producing bisphenol 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. The method for producing bisphenol according to any one of claims 1 to 3, wherein the bisphenol is composed of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4 Any one of the group consisting of -hydroxyphenyl)dodecane and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)methane. A method for producing polycarbonate resin using bisphenol produced by the method for producing bisphenol according to any one of claims 1 to 7.