阅读说明：本技术 双酚的制造方法以及聚碳酸酯树脂的制造方法 (Method for producing bisphenol and method for producing polycarbonate resin ) 是由 内山馨 中岛幸惠 岸田真 高见芳惠 于 2020-02-26 设计创作，主要内容包括：一种双酚的制造方法,其包括下述工序：将水相1和含有双酚的有机相1的混合液1的有机相1与螯合剂混合,得到pH6以下的水相和有机相的混合液2的工序；将所得到的混合液2与碱混合,得到pH8以上的水相和有机相的混合液3的工序；以及从所得到的混合液3中除去pH8以上的水相,得到有机相3A的工序,该螯合剂相对于该混合液3的水相的溶解度比相对于该混合液3的有机相的溶解度高。(A process for producing bisphenol, which comprises the steps of: mixing an organic phase 1 of a mixed solution 1 of an aqueous phase 1 and an organic phase 1 containing bisphenol with a chelating agent to obtain a mixed solution 2 of an aqueous phase and an organic phase having a pH of 6 or less; mixing the obtained mixed solution 2 with an alkali to obtain a mixed solution 3 of an aqueous phase and an organic phase having a pH of 8 or more; and a step of removing the aqueous phase having a pH of 8 or more from the obtained mixed solution 3 to obtain an organic phase 3A, wherein the chelating agent has a higher solubility in the aqueous phase of the mixed solution 3 than in the organic phase of the mixed solution 3.)

1. A process for producing bisphenol, which comprises the steps of:

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

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

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

the chelating agent has a higher solubility in the aqueous phase of the mixed solution 3 than in the organic phase of the mixed solution 3.

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

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

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

5. The process for producing a bisphenol as defined in any one of claims 1 to 4, comprising a step of removing an aqueous phase from a mixed solution 4 obtained by mixing said organic phase 3A and deionized water to obtain an organic phase 4.

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

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

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

9. A method for producing an organic compound having a metal-coordinating structure, which contains a partial structure represented by the following formula (I) in a molecule, comprising the steps of:

a step of mixing an organic phase 1 'of a mixed liquid 1' with a chelating agent to obtain a mixed liquid 2 'of an aqueous phase and an organic phase having a pH of 6 or less, the mixed liquid 1' being a mixed liquid of the aqueous phase 1 'and the organic phase 1' containing the organic compound;

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

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

the solubility of the organic compound with respect to the organic phase of the mixed liquid 3 'is higher than the solubility with respect to the aqueous phase of the mixed liquid 3',

the chelating agent has a higher solubility in the aqueous phase of the mixed solution 3 'than in the organic phase of the mixed solution 3';

[ solution 1]

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

Technical Field

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 is useful as a raw material for resins such as polycarbonate resins, epoxy resins, and aromatic polyester resins, as a curing agent, a color developer, an anti-fading agent, and as an additive for other bactericides, antibacterial and antifungal agents, and the like.

Background

Bisphenols are useful as a raw material for polymer materials such as polycarbonate resins, epoxy resins, and aromatic polyester resins. As typical bisphenols, for example, 2-bis (4-hydroxyphenyl) propane and 2, 2-bis (4-hydroxy-3-methylphenyl) propane are known (patent document 1). Further, a method for producing a bisphenol having a fluorene skeleton is also known (patent document 2).

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

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

Polycarbonate resins, which are typical uses of bisphenols, are required to be colorless and transparent. The color tone of the polycarbonate resin is significantly affected by the color tone of the raw material. Therefore, it is required that the color tone of bisphenol as a raw material is also colorless.

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

In the production of a polycarbonate resin, particularly in the melting method, bisphenol is melted to produce a polycarbonate resin, and therefore, it is exposed to high temperature. Thus, bisphenols are also required to have color tone stability against heat.

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

In the production of polycarbonate resins, since bisphenol is melted and then subjected to polymerization reaction, it is also required to have color tone stability against heat until the polymerization is started.

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

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

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

As for the polycarbonate resin, a polycarbonate resin having a molecular weight in accordance with design and a good color tone is being sought. In order to produce such a polycarbonate resin, bisphenol as a raw material is required to have excellent methanol dissolution color, color difference in melting, and thermal hue stability, and also excellent thermal decomposition stability.

When hydrogen chloride gas or hydrochloric acid is used as a catalyst for the bisphenol production reaction, hydrogen chloride volatilizes to corrode equipment, and corroded components are mixed into bisphenol, whereby the quality of bisphenol is liable to deteriorate, and this is not easy to avoid.

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

As a method for recovering bisphenol, for example, a method is known in which water is supplied to a reaction solution to reduce the concentration of an acid catalyst, thereby completing (stopping) the reaction and then recovering bisphenol, as described in patent document 1. However, when heating or the like is performed at the time of recovering bisphenol in a state where the acidity of the aqueous phase after the bisphenol production reaction is high, there are other problems such that bisphenol is easily decomposed and by-products are increased.

In order to suppress the decomposition of bisphenol, a method of neutralizing an acid catalyst with an alkaline aqueous solution to reduce the acidity of the reaction solution and terminate the reaction is known (for example, patent document 2). However, in this method, the concentration of the aqueous phase after the bisphenol formation reaction is from 4 to 6, and it is difficult to improve the quality of bisphenol which is deteriorated by corrosion of equipment.

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

Disclosure of Invention

The present invention has an object to provide a method for producing bisphenol with good quality by studying a recovery process of bisphenol produced using hydrogen chloride gas or hydrochloric acid as an acid catalyst, and a method for producing a polycarbonate resin using the bisphenol.

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

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

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

[2] The process for producing a bisphenol as described in [1], wherein the organic phase 1 is an organic phase 1A obtained by removing an aqueous phase from the mixed solution 1.

[3] The process for producing a bisphenol as described in [2], wherein the aqueous phase is removed from the mixed solution 1 so that the mixing ratio of the aqueous phase from which the aqueous phase is removed and the organic phase 1A is 1:700 by weight or less.

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

[5] The process for producing a bisphenol as described in any of [1] to [4], which comprises a step of removing an aqueous phase from a mixed liquid 4 obtained by mixing the organic phase 3A and deionized water to obtain an organic phase 4.

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

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

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

[ solution 1]

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

ADVANTAGEOUS EFFECTS OF INVENTION

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

Detailed Description

The embodiments of the present invention will be described in detail below. The following description of the constituent elements is an example of the embodiment of the present invention, and the present invention is not limited to the following description as long as the elements do not exceed the gist thereof.

In the present specification, the expression "to" is used as an expression including numerical values and physical property values before and after the expression.

[ Process for producing bisphenol ]

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

The process for producing a bisphenol of the present invention is characterized by: when a mixed solution 2 of an aqueous phase and an organic phase having a pH of not more than 6 is obtained by mixing a chelating agent with an organic phase 1 of a mixed solution 1 of an aqueous phase 1 and an organic phase 1 containing bisphenol, and a mixed solution 3 of an aqueous phase and an organic phase having a pH of not less than 8 is obtained by mixing the mixed solution 2 with an alkali, the chelating agent having a higher solubility in the aqueous phase than in the organic phase of the mixed solution 3 is used to remove the aqueous phase having a pH of not less than 8 from the mixed solution 3, thereby efficiently recovering the organic phase 3A containing bisphenol.

As described above, in the case of using hydrogen chloride gas or hydrochloric acid as a catalyst for bisphenol production reaction, hydrogen chloride gas volatilizes to corrode facilities, and corrosive components are mixed into bisphenol, thereby causing a problem of deterioration in quality of bisphenol. The corrosion component mixed in the bisphenol is mainly composed of a metal component such as iron which is a constituent material of the apparatus. In the present invention, the chelating agent is added and mixed under the above-mentioned specific pH acidic condition, and then the pH is brought to the basic condition in the addition of the alkaline aqueous solution, whereby the metal component such as iron mixed in the bisphenol product is chelated and effectively removed. Further, the removal of corrosive components can improve the quality of bisphenol.

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

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

(1) A method of adding an acidic solution to the reaction mixture after the bisphenol formation reaction to separate the phases.

(2) A method in which after the bisphenol production reaction, the reaction solution is neutralized, washed, crystallized, and then the bisphenol is taken out, the taken-out bisphenol is dissolved in a solvent, and the obtained bisphenol solution is washed with an acidic solution, and then phase separation is performed.

[ bisphenol formation reaction ]

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

In the bisphenol production 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 generally carried out according to the reaction formula (1) shown below.

[ solution 2]

With respect to R in the above reaction formula (1)¹～R⁶R in the following general formulae (2) to (3)¹～R⁶The description of (a).

< aromatic alcohol >

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

[ solution 3]

In the general formula (2), as R¹～R⁴Each independently includes a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and the like. The substituent such as the alkyl group, the alkoxy group, and the aryl group may be either substituted or unsubstituted. As R¹～R⁴Examples thereof include a hydrogen atom, a fluoro group, a chloro group, a bromo group, an iodo group, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a tert-butoxy group, a n-pentyloxy group, an isopentyloxy group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group, a n-nonyloxy groupN-decyloxy, n-undecyloxy, n-dodecyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, benzyl, phenyl, tolyl, 2, 6-dimethylphenyl, and the like.

Of these, if R²And R³The reason why the condensation reaction is difficult when the steric bulk of (A) is large, and R is preferred as the aromatic alcohol²And R³An aromatic alcohol which is a hydrogen atom.

In addition, as the aromatic alcohol, R is preferable¹～R⁴Aromatic alcohols each independently being a hydrogen atom or an alkyl group, more preferably R¹And R⁴Each independently is a hydrogen atom or an alkyl group, R²And R³An aromatic alcohol which is a hydrogen atom.

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

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

< ketones or aldehydes >

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

[ solution 4]

In the general formula (3), as R⁵And R⁶Each independently includes a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and the like. The substituent such as the alkyl group, the alkoxy group, and the aryl group may be either substituted or unsubstituted. As R⁵、R⁶Examples thereof 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 and an n-pentyl groupThe alkyl group includes, for example, an alkyl group, an aryl group, a heteroaryl group, a heteroaryloxy group, a cyclohexylgroup, and the like.

R⁵And R⁶May be bonded or cross-linked to each other. R⁵And R⁶Or may be bonded together with adjacent carbon atoms to form a cycloalkylidene group which may contain heteroatoms. Cycloalkylidene is a 2-valent radical obtained by removing 2 hydrogen atoms from one carbon atom of a cycloalkane. In the formula R⁵And R⁶In the case of a cycloalkylidene group formed by bonding to an adjacent carbon, the bisphenol to be obtained has a structure in which aromatic alcohols are bonded via a cycloalkylidene group.

As R⁵And R⁶Examples of the cycloalkylidene group which is bonded together with the adjacent carbon atom include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3, 5-trimethylcyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclododecylidene, fluorenylidene, xanthonylidene and thioxanthone-ylidene.

Specific examples of the compound represented by the general formula (3) include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, caprylic aldehyde, nonanal, decanal, undecanal, and dodecanal; ketones such as acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, and dodecanone; aralkyl ketones such as benzaldehyde, phenylmethyl ketone, phenylethyl ketone, phenylpropyl ketone, tolylmethyl ketone, tolylethyl ketone, tolylpropyl ketone, ditolyl methyl ketone, ditolyl ethyl ketone, and ditolyl propyl ketone, cyclic alkane ketones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, and cyclododecanone; and so on. Among them, acetone is preferred.

< bisphenol >

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

[ solution 5]

In the general formula (4), R¹～R⁶The same as in the general formulae (2) and (3).

Specific examples of the bisphenol represented by the general formula (4) include 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 3-bis (4-hydroxyphenyl) pentane, 3-bis (4-hydroxy-3-methylphenyl) pentane, 2-bis (4-hydroxyphenyl) pentane, 2-bis (4-hydroxy-3-methylphenyl) pentane, and the like, 3, 3-bis (4-hydroxyphenyl) heptane, 3-bis (4-hydroxy-3-methylphenyl) heptane, 2-bis (4-hydroxyphenyl) heptane, 2-bis (4-hydroxy-3-methylphenyl) heptane, 4-bis (4-hydroxyphenyl) heptane, 4-bis (4-hydroxy-3-methylphenyl) heptane and the like, but are not limited in any way by these substances.

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

< Hydrogen chloride >

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

When the molar ratio of hydrogen chloride to the ketone or aldehyde used in the reaction is small ((the number of moles of hydrogen chloride/the number of moles of ketone) or (the number of moles of hydrogen chloride/the number of moles of aldehyde)), hydrogen chloride is diluted with water by-produced in the condensation reaction, and it is necessary to prolong the reaction time. When the molar ratio is large, polymerization of ketone or aldehyde may proceed. For these reasons, the lower limit of the molar ratio of hydrogen chloride to ketone or aldehyde is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, preferably 10 or less, more preferably 8 or less, further preferably 5 or less.

< condensation reaction >

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

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

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

Examples of the supply of the ketone or aldehyde in the above (i) and the supply of the hydrogen chloride in the above (ii) include a one-shot supply method and a batch supply method. Since the reaction to produce bisphenol is an exothermic reaction, it is preferable to carry out the supply by a batch method such as dropwise addition at a little by little. The method (i) is preferable for the reason that the self-condensation of the ketone or aldehyde can be further suppressed.

In the condensation reaction of an aromatic alcohol and a ketone or an aldehyde, when the molar ratio of the aromatic alcohol to the ketone or the aldehyde is small ((the number of moles of the aromatic alcohol/the number of moles of the ketone) or (the number of moles of the aromatic alcohol/the number of moles of the aldehyde)), the ketone or the aldehyde is likely to be polymerized. When the molar ratio is large, the aromatic alcohol is not reacted and lost. For these reasons, the molar ratio of the aromatic alcohol to the ketone or the aldehyde is preferably 1.5 or more, more preferably 1.6 or more, and further preferably 1.7 or more, and preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

< thiol >

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

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

The reason why the effect of improving the polymerization activity in the production of a polycarbonate resin and improving the color tone of the obtained polycarbonate resin is exerted is not clear in detail, but it is presumed that the use of a thiol can suppress the generation of a blocking substance to the polymerization reaction for producing a polycarbonate resin and the generation of a color tone deterioration product.

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

When the molar ratio of the thiol promoter to the ketone or aldehyde used for condensation is small (the number of moles of the thiol promoter/the number of moles of the ketone or (the number of moles of the thiol promoter/the number of moles of the aldehyde)), the effect of improving the reaction selectivity of bisphenol by using the thiol promoter cannot be obtained. When the molar ratio is large, the bisphenol may be mixed with the bisphenol to deteriorate the quality. For these reasons, the molar ratio of the thiol promoter to the ketone and the aldehyde is preferably 0.001 or more, more preferably 0.005 or more, further preferably 0.01 or more, preferably 1 or less, more preferably 0.5 or less, further preferably 0.1 or less.

The thiol is preferably premixed with the ketone or aldehyde before being supplied to the reaction. As for the method of mixing the thiol with the ketone or the aldehyde, the ketone or the aldehyde may be mixed in the thiol, and the thiol may also be mixed in the ketone or the aldehyde.

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

< organic solvent >

In the process for producing a bisphenol of the present invention, an organic solvent is generally used in order to dissolve or disperse the bisphenol produced.

The organic solvent is not particularly limited insofar as it does not inhibit the bisphenol production reaction, and an aromatic hydrocarbon is usually used. Here, the aromatic alcohol as the raw material (based-pouenin) and the bisphenol as the product are not included in the organic solvent.

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

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

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

< reaction conditions >

Since the bisphenol to be produced may be decomposed if the reaction time of the bisphenol production reaction is too long, the reaction time 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 2 hours or more.

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

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

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

[ chelating treatment Process ]

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

In the case where the chelating treatment step is performed after the bisphenol-producing reaction, if the pH of the aqueous phase obtained by phase separation is 6 or less by adding mixed water to the reaction solution of the bisphenol-producing reaction, the organic phase 1A from which the aqueous phase is removed can be used as the organic phase 1, and a chelating agent can be added and mixed to obtain a mixed solution 2.

The aqueous phase is preferably removed in such a manner that the mixing ratio of the aqueous phase after the aqueous phase removal to the organic phase 1A is the aqueous phase in terms of weight ratio: the organic phase 1A is carried out in a ratio of 1:700 or less, particularly 1:800 or less, and especially 1:900 or less. When the aqueous phase is more than this range, the amount of the alkaline aqueous solution required to reach a pH of 8 or more in the alkali treatment step described later increases.

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

When the pH of the aqueous phase after washing exceeds 6, an acidic aqueous solution may be added to and mixed with the organic phase from which the aqueous phase was removed, and the aqueous phase having a pH of 6 or less may be phase-separated.

When the chelating treatment step is performed after the crystallization step described later, an organic solvent may be added to the bisphenol recovered by crystallization to obtain a bisphenol solution, an acidic aqueous solution may be added to and mixed with the bisphenol solution, and the aqueous phase having a pH of 6 or less may be phase-separated.

The organic phase obtained by phase separation of the aqueous acidic solution described above may be used as the 1 st organic phase if the aqueous phase obtained by phase separation is pH6 or less.

In either case, if the pH of the aqueous phase subjected to phase separation upon obtaining the organic phase 1A is greater than 6, the removal of corrosive components by the chelating agent cannot be sufficiently performed, and thus bisphenol having good methanol dissolution color, difference in melt color, thermal color stability, and thermal decomposition stability cannot be obtained. The pH of the aqueous phase is particularly preferably 5 or less. If the pH of the aqueous phase is too low, the amount of the alkaline aqueous solution used in the following alkaline treatment step becomes too large, and therefore the pH of the aqueous phase is preferably-1 or more.

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

As the acidic substance used for obtaining the acidic aqueous solution of the aqueous phase having a pH of 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 suitably adjusted depending on the acidic substance or the basic substance remaining in the bisphenol. Since bisphenol is decomposed when the acidic substance concentration of the acidic aqueous solution is too high, the concentration is preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. If the acidic substance concentration of the acidic aqueous solution is too low, the amount of the acidic aqueous solution needs to be increased in order to obtain an aqueous phase having a pH of 6 or less, and therefore the lower limit of the acidic substance concentration of the acidic aqueous solution is preferably 0.01 mass ppm or more, more preferably 0.1 mass ppm or more.

If the amount of the acidic aqueous solution used is too large, the amount of the aqueous phase subjected to phase separation after addition of the acidic aqueous solution is too large relative to the amount of the organic phase, and phase separation is not easily performed. Therefore, the mass ratio of the acidic aqueous solution (mass of the acidic aqueous solution/mass of the organic phase) to the amount 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. If the amount of the acidic aqueous solution to be added is too small, the amount of the organic phase is too large relative to the amount of the aqueous phase, and phase separation is not easily performed. Therefore, the mass ratio of the amount of the acidic aqueous solution to the amount of the organic phase is preferably 0.05 or more, more preferably 0.1 or more.

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

If the chelating agent used has a solubility in the aqueous phase or less in the organic phase, the chelating agent used remains in the organic phase and in the bisphenol, and the purity of the bisphenol is lowered. The chelating agent may have a higher solubility in the aqueous phase than in the organic phase, and the ratio of the solubility in the aqueous phase/the solubility in the organic phase is 1.5 times or more, preferably 2 times or more, and more preferably 10 times or more.

Examples of the chelating agent include β -diketones such as acetylacetone and 3, 5-heptanedione; aminocarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, and salts thereof; ketoacids such as pyruvic acid or acetoacetic acid, levulinic acid, alpha-ketoglutaric acid, acetone dicarboxylic acid; hydroxy acids such as glycolic acid, glyceric acid, xylonic acid, gluconic acid, lactic acid, tartronic acid, tartaric acid, xylaric acid (キシラル acid), galactaric acid, malic acid, citric acid; polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid; amino acids such as aspartic acid and glutamic acid; polyphosphoric acids such as phytic acid, hydroxyethylidene diphosphonic acid, nitrilotrimethylene phosphoric acid, and ethylenediaminetetramethylenephosphoric acid; dioximes such as dimethylglyoxime, benzyldiethyldioxime, 1, 2-cyclohexyldiethyldioxime, and the like.

Among these, as the substance satisfying the above solubility in the aqueous phase and solubility in the organic phase, ethylenediaminetetraacetic acid, citric acid, oxalic acid, malonic acid, succinic acid may be mentioned.

Among these, 4-membered carboxylic acids are particularly preferred, and aminocarboxylic acids such as ethylenediaminetetraacetic acid and salts thereof are preferred in view of their easiness of being chelated with various metals. In addition, from the viewpoint of solubility in organic solvents and further easy binding to corrosive components, chelating agents composed of only carbon, hydrogen, and oxygen atoms are preferred, and examples thereof include β -diketones such as acetylacetone and 3, 5-heptanedione; ketoacids such as pyruvic acid, acetoacetic acid, levulinic acid, α -ketoglutaric acid, and acetonedicarboxylic acid; hydroxy acids such as glycolic acid, glyceric acid, xylonic acid, gluconic acid, lactic acid, tartronic acid, tartaric acid, xylaric acid, galactaric acid, malic acid, citric acid; polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid; and the like.

These chelating agents may be used alone in 1 kind, or two or more kinds may be used in combination.

The chelating agent is preferably added to the organic phase 1 as an aqueous solution of about 0.1 mass% or more, particularly 0.5 mass% or more, 15 mass% or less, and particularly 10 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 concentration of the chelating agent is too low, the amount of wastewater generated after the chelating agent is supplied may increase.

The amount of the chelating agent aqueous solution added to the organic phase 1 may be an amount sufficient to chelate and remove the corrosive components in the organic phase 1 sufficiently, and varies depending on the concentration of the chelating agent and the amount of the corrosive components in the organic phase 1 to be treated. If the amount of the chelating agent aqueous solution added to the organic phase 1 is too large, the production cost increases. If the amount of the 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 sufficiently obtained. Therefore, the mass ratio of the aqueous chelating agent solution to the organic phase 1 (mass of the aqueous chelating agent solution/mass of the organic phase 1) is preferably 0.0001 or more, particularly 0.001 or more, 10 or less, particularly 1 or less.

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

[ alkali treatment Process ]

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

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

The pH of the aqueous phase subjected to phase separation may be 8 or more, and may be 10 or more or 11 or more, but is usually about 8 to 9.

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

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

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

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

[ Water washing Process ]

The process for producing bisphenol of the present invention may further comprise a washing step of washing the reaction mixture containing bisphenol obtained in the bisphenol-forming reaction step or the organic phase 3A after the alkali treatment step with water. By performing such a water washing step, the amount of impurities can be further reduced.

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

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

The water washing step was carried out as follows: the reaction solution or the organic phase 3A is washed by supplying water thereto, and thereafter, the reaction solution or the organic phase is separated into an organic phase and an aqueous phase, and the aqueous phase is removed to thereby wash the reaction solution or the organic phase.

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

[ alkaline cleaning Process ]

The process for producing bisphenol of the present invention may further comprise an alkali washing step of washing the obtained organic phase with an alkaline aqueous solution after the alkali treatment step or the water washing step.

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

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

The alkali washing step may be performed a plurality of times.

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

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

The alkali substance concentration of the alkali aqueous solution used in the alkali cleaning step is appropriately adjusted depending on the kind of the alkali substance or the acid catalyst. If the concentration of the alkaline substance in the alkaline aqueous solution is too high, the alkaline substance remains in the finally obtained bisphenol and deteriorates the quality, and therefore, it is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. If the alkaline substance concentration of the alkaline aqueous solution is too low, it is necessary to increase the amount of the alkaline aqueous solution to obtain an aqueous phase having a pH of 9 or more, and therefore the alkaline substance concentration of the alkaline aqueous solution is preferably 0.1 mass% or more, more preferably 0.5 mass% or more.

If the amount of the aqueous alkaline solution to be supplied is too large, the amount of the aqueous phase subjected to phase separation after the alkaline washing is too large relative to the amount of the organic phase, and the phase separation is not easily performed. When the amount of the aqueous alkaline solution to be supplied is too small, the amount of the organic phase is too large relative to the amount of the aqueous phase, and phase separation is not easily performed. For these reasons, the mass ratio of the amount of the basic aqueous solution to the amount of the organic phase in the alkali washing step (mass of the basic aqueous solution/mass of the organic phase) is preferably 2 or less, more preferably 1 or less, further preferably 0.5 or less, preferably 0.05 or more, more preferably 0.1 or more.

[ temperatures of chelate treatment step, alkali treatment step, washing step and alkali washing step ]

In the chelate treatment step, the alkali treatment step, the water washing step and the alkali washing step, in order to suppress precipitation of bisphenol, the average temperature from the start to the end is preferably 50 ℃ or higher, more preferably 55 ℃ or higher. The average temperature is preferably 120 ℃ or lower, more preferably 110 ℃ or lower, in order to suppress precipitation of bisphenol due to evaporation of the organic solvent. These processes can be carried out, for example, at the same temperature.

[ crystallization Process ]

The process for producing bisphenol of the present invention preferably has 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.

The crystallization can be carried out according to a conventional method. For example, any of a method utilizing the solubility difference of bisphenol due to the temperature difference and a method of precipitating a solid by supplying a poor solvent can be applied. In the case of using a method of supplying a poor solvent, the purity of the bisphenol to be obtained is liable to decrease, and therefore, a method of using a difference in solubility of bisphenol due to a temperature difference is preferable.

When the content of the aromatic alcohol in the organic phase is large, the remaining aromatic alcohol may be removed by distillation before crystallization, and then crystallization may be performed.

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

The conductivity of the organic phase supplied to the crystallization step is preferably 10. mu.S/cm or less in the aqueous phase separated in the step immediately before (hereinafter, sometimes referred to as "near-front aqueous phase"). When the conductivity of the former aqueous phase is 10. mu.S/cm or less, particularly 9. mu.S/cm or less, particularly 8. mu.S/cm or less, impurities such as by-products and residual catalysts in the product can be removed to a high degree, and the following bisphenols can be obtained: the polycarbonate resin has good color tone, high polymerization efficiency when used as bisphenol which is a raw material of the polycarbonate resin, and can produce a polycarbonate resin with excellent color tone.

The conductivity of the near-front aqueous phase can be measured, for example, by a conductivity meter with respect to the near-front aqueous phase at room temperature (20 to 30 ℃) after phase separation.

The thus-obtained bisphenol can be further purified by a conventional method depending on its use. For example, purification can be carried out by a simple means such as spray washing, water washing, suspension washing, crystallization, or column chromatography. Specifically, the bisphenol obtained can be further purified by dissolving it in an organic solvent such as an aromatic hydrocarbon and then cooling it to crystallize it.

[ Process Structure of Process for producing bisphenol ]

The process for producing bisphenol of the present invention may be a process comprising, for example, a chelate treatment step, an alkali treatment step, a water washing step and a crystallization step in this order. The process for producing bisphenol of the present invention may be a process comprising a water washing step, a chelating 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 the bisphenol produced by the process for producing a bisphenol of the present invention (hereinafter sometimes referred to as "bisphenol of the present invention") will be described below.

< color of bisphenol dissolved in methanol >

The methanol-soluble color of bisphenol was used to evaluate the color tone of bisphenol at ordinary temperature. The lower the Hazen color number of the methanol-soluble color of bisphenol, the better the hue of bisphenol (closer to white). The reason why the methanol-soluble color of bisphenol is deteriorated is that an organic coloring component or a metal is mixed in.

The methanol-soluble color of bisphenol was measured as follows: bisphenol was dissolved in methanol to prepare a homogeneous solution, and then the measurement was carried out at room temperature (about 20 ℃ C.). The measurement method includes: a method of comparing with a standard solution of Hazen color value by visual observation; or a method of measuring the Hazen color value by using a color difference meter such as "SE 6000" manufactured by Nippon Denshoku industries Co., Ltd. The mass ratio of the solvent methanol, bisphenol and solvent used herein is preferably selected as appropriate depending on 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.

< color difference in melt of bisphenol >

The color difference of the bisphenol in melting was evaluated as the color tone of the bisphenol at a temperature close to the polymerization temperature of the polycarbonate. The measurement temperature of the difference in melting point was the melting point of bisphenol +50 ℃. The lower the Hazen color number of the color difference in melting of bisphenol, the better the hue of bisphenol (closer to white). The reason why the difference in color of melting of bisphenol is poor is that a coloring component is colored by heating, in addition to the mixing of an organic coloring component or a metal.

The color difference in melting of bisphenol is measured by melting bisphenol at a temperature close to the polymerization temperature and stabilizing the temperature for a predetermined period of time. The measurement method includes: a method of comparing with a standard solution of Hazen color value by visual observation; or a method of measuring the Hazen color value by using a color difference meter such as "SE 6000" manufactured by Nippon Denshoku industries Co., Ltd.

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

< thermal color tone stability of bisphenol >

The thermal color tone stability of bisphenol was evaluated by keeping the polycarbonate at a temperature close to the polymerization temperature of the polycarbonate for a predetermined time, similarly to the color difference of bisphenol. The temperature at which the thermal color stability of the bisphenol is measured is the melting point of the bisphenol +50 ℃.

The lower the Hazen color number of the thermal hue stability of bisphenol, the better the thermal hue stability of bisphenol. The reasons for the deterioration of thermal color stability of bisphenol include not only the mixing of organic coloring components or metals but also components colored by heating or acidic or basic substances at a concentration of about several ppm.

The thermal color stability of bisphenol is measured by melting bisphenol at a temperature close to the polymerization temperature and stabilizing the temperature for a predetermined period of time. The retention time of the thermal color tone stability of bisphenol was 4 hours. The measurement method includes: a method of comparing with a standard solution of Hazen color value by visual observation; or a method of measuring the Hazen color value by using a color difference meter such as "SE 6000" manufactured by Nippon Denshoku industries Co., Ltd.

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

< thermal decomposition stability of bisphenol >

The thermal decomposition stability of bisphenol and the thermal color tone stability of bisphenol are similarly used to evaluate the thermal stability of bisphenol by holding at a temperature close to the polymerization temperature of polycarbonate for a predetermined time. The preferred measurement temperature for the thermal decomposition stability of bisphenol is the melting point of bisphenol +50 ℃. Regarding the thermal decomposition stability of bisphenol, the smaller the amount of the decomposition product produced, the more stable bisphenol is.

The decomposition product in the thermal decomposition stability of bisphenol depends on the kind of bisphenol, and examples thereof include an aromatic alcohol which is a raw material of the bisphenol, and an adduct of the aromatic alcohol and a ketone or an aldehyde which is a raw material. The reasons for the deterioration of thermal color stability of bisphenol include not only the mixing of organic coloring components or metals but also components colored by heating or acidic or basic substances at a concentration of about several ppm.

Detection and quantification of bisphenol decomposition products can be performed using a standard high-speed analytical reversed-phase column.

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

The methanol-soluble color of bisphenol is a method for evaluating the color tone of bisphenol itself. In the case of bisphenol as a final product, bisphenol having a good methanol solubility color is important. Since polycarbonate resins have the color tone of the raw material, bisphenols having a good color tone are important in polycarbonate resins which are required to have colorless transparency.

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

Further, in this melt polymerization method, the bisphenol is kept 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 a predetermined mass ratio, and it is difficult to obtain a polycarbonate resin having polymerization activity or a specific molecular weight. Therefore, resistance to thermal decomposition (thermal decomposition stability of bisphenol) is important.

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

[ uses of bisphenols ]

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

The bisphenol of the present invention can provide good mechanical properties, and therefore is preferably used as a raw material (monomer) for thermoplastic resins and thermosetting resins, and 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 particularly more preferably used in combination with a leuco dye or a color change temperature adjuster.

[ Process for producing polycarbonate resin ]

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

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

The copolymerized polycarbonate resin may be produced using only one bisphenol of the present invention, or using 2 or more bisphenols. The reaction may be carried out in combination with a dihydroxy compound other than the bisphenol of the present invention.

The transesterification reaction can be carried out by appropriately selecting a known method. Next, an example of the starting materials of the bisphenol and diphenyl carbonate of the present invention will be described.

In the above-mentioned method for producing a polycarbonate resin, diphenyl carbonate is preferably used in an excess amount relative to the bisphenol of the present invention. In view of the fact that the polycarbonate resin to be produced has fewer terminal hydroxyl groups and the polymer has excellent thermal stability, it is preferable to use a larger amount of diphenyl carbonate relative to bisphenol. From the viewpoint of a high transesterification reaction rate and easy production of a polycarbonate resin having a desired molecular weight, it is preferable to use a small amount of diphenyl carbonate relative to bisphenol. For these reasons, the amount of diphenyl carbonate used is usually 1.001 mol or more, preferably 1.002 mol or more, usually 1.3 mol or less, preferably 1.2 mol or less based on 1 mol of bisphenol.

The bisphenol and diphenyl carbonate of the present invention can be supplied as a solid as well as a method of supplying raw materials, but it is preferable to supply one or both of them in a molten state.

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

The amount of the catalyst to be used is usually 0.05. mu. mol or more, preferably 0.08. mu. mol or more, more preferably 0.10. mu. mol or more, and usually 100. mu. mol or less, preferably 50. mu. mol or less, more preferably 20. mu. mol or less based on 1 mol of bisphenol or diphenyl carbonate.

When the amount of the catalyst used is in the above range, the polymerization activity required for producing a polycarbonate resin having a desired molecular weight can be easily obtained, and a polycarbonate resin having excellent flowability during molding, which is excellent in polymer color tone and in which excessive branching of the polymer does not occur, can be easily obtained.

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

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

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

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

[ method for producing organic Compound ]

As in the method for producing a bisphenol of the present invention, by undergoing the above-described chelate treatment step and alkali treatment step, not only can a bisphenol be produced, but also a high-quality organic compound (I) can be produced with high purity by removing impurities such as metals mixed in the organic compound (I) with respect to a metal-coordinating organic compound (hereinafter, sometimes referred to as "organic compound (I)") having a partial structure represented by the following formula (I) (hereinafter, sometimes referred to as "partial structure (I)") included in the molecule.

Here, "metal coordinatability" refers to a compound capable of forming a complex by bonding to a metal ion via a coordinate bond, and the organic compound (I) has a partial structure (I) and functions as a ligand of the metal ion.

[ solution 6]

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

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

The "carbon chain" refers to a connection structure in which carbon atoms are connected to each other by a single bond, a double bond, or a triple bond, and is not limited to a linear or branched chain structure, and may include a cyclic structure, or a combination thereof.

The organic compound (I) is a metal-coordinating compound having a partial structure (I) that functions as a ligand of a metal ion. Therefore, the organic compound (I) is often present in the reaction product as a complex compound coordinated to the metal in the production process due to the metal compound used as a catalyst or impurities mixed in the production process.

In the application of the organic compound (I), the metal-introduced product may be colored, decomposed, or deteriorated due to the metal contained therein.

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

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

Examples of the partial structure (I) of the organic compound (I) used in the method for producing an organic compound according to the present invention include an amide group, a hydrazide group, an imide group, an amidino group, and a nitrile group, each of which has a nitrogen element as X and/or Y; alcohol group, phenol group and ether group which are oxygen elements; is the structure of sulfydryl and thioether of sulfur element.

When the organic compound (I) is the chelating agent, the chelating agent is selected to be different from the organic compound (I). For example, the following combinations can be mentioned.

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

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

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

Examples of the organic compound (I) include the following, but the organic compound (I) used in the method for producing an organic compound of the present invention is not limited to the following.

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

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

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

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

dinitriles such as succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonanedionitrile and decanedionitrile;

diisocyanates such as dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate;

glycols such as ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclopropane diol, cyclopropane dimethanol, cyclobutane diol, cyclobutane dimethanol, cyclopentanediol, cyclopentane dimethanol, cyclohexane diol, cyclohexane dimethanol, cycloheptane diol, cycloheptane dimethanol, cyclooctane dimethanol, cyclononanediol, cyclononane dimethanol, cyclodecane diol, and cyclodecane dimethanol;

biphenols such as biphenol, dimethyl biphenol, and tetramethyl biphenol;

diamines such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decylenediamine, and phenylenediamine;

diimines such as ethanediimine, propanediimine, butanediimine, pentanediimine, hexanediimine, heptanediimine, octanediimine, nonanediimine and decanediimine;

dihydrazines such as ethanedihydrazine, propanedihydrazine, butanedihydrazine, pentanedihydrazine, hexanedihydrazine, heptanedihydrazine, octanedihydrazine, nonanedihydrazine, decanedihydrazine and benzenedihydrazine;

diethers such as dimethoxymethane, dimethoxyethane, dimethoxypropane, dimethoxybutane, dimethoxypentane, dimethoxyhexane, dimethoxyheptane, dimethoxyoctane, dimethoxynonane, dimethoxydecane, dimethoxybenzene, diethoxymethane, diethoxyethane, diethoxypropane, diethoxybutane, diethoxypentane, diethoxyhexane, diethoxyheptane, diethoxyoctane, diethoxynonane, diethoxydecane, diethoxybenzene, dipropoxymethane, dipropoxyethane, dipropoxypropane, dipropoxybutane, dipropoxypentane, dipropoxyhexane, dipropoxyheptane, dipropoxyoctane, dipropoxynonane, dipropoxydecane, and dipropoxybenzene;

disulfides such as dimethylthiomethane, dimethylthioethane, dimethylthiopropane, dimethylthiobutane, dimethylthiopentane, dimethylthiohexane, dimethylthioheptane, dimethylthiooctane, dimethylthiononane, dimethylthiodecane, dimethylthiobenzene, diethylthiomethane, diethylthioethane, diethylthiopropane, diethylthiobutane, diethylthiopentane, diethylthiohexane, diethylthioheptane, diethylthiooctane, diethylthiononane, diethylthiodecane, diethylthiobenzene, dipropylthiomethane, dipropylthioethane, dipropylthiopropane, dipropylthiobutane, dipropylthiopentane, dipropylthiohexane, dipropylthioheptane, dipropylthiooctane, dipropylthiononane, dipropylthiodecane and dipropylthiobenzene.

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

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

hydroxymethylnitrile, hydroxyethylnitrile, hydroxypropylnitrile, hydroxybutyronitrile, hydroxypentylnitrile, hydroxyhexylnitrile, hydroxyheptylnitrile, hydroxyoctylnitrile, hydroxynonylnitrile, hydroxydecylnitrile, hydroxyphenylnitrile, and other hydroxynitriles;

hydroxyphenyl nitriles such as hydroxyphenyl methylnitrile, hydroxyphenyl ethylnitrile, hydroxyphenyl propylnitrile, hydroxyphenyl butylnitrile, hydroxyphenyl pentylnitrile, hydroxyphenyl hexylnitrile, hydroxyphenyl heptylnitrile, hydroxyphenyl octylnitrile, hydroxyphenyl nonylnitrile, hydroxyphenyl decylnitrile, and hydroxyphenyl benzonitrile;

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

iminonitriles such as iminomethylnitrile, iminoethylnitrile, iminopropylnitrile, iminobutylnitrile, iminopentylnitrile, iminohexylnitrile, iminoheptylnitrile, iminooctylnitrile, iminononylnitrile, iminodecylnitrile, and iminophenylnitrile;

nitrile hydrazines such as methylene nitrile hydrazine, ethylene nitrile hydrazine, propylene nitrile hydrazine, butylene nitrile hydrazine, pentylene nitrile hydrazine, hexylene nitrile hydrazine, heptylene nitrile hydrazine, octylene nitrile hydrazine, nonylene nitrile hydrazine, decylene nitrile hydrazine, benzonitrile hydrazine and the like;

alkoxynitriles such as methoxymethylnitrile, methoxyethylnitrile, methoxypropylnitrile, methoxybutylnitrile, methoxypentylnitrile, methoxyhexylnitrile, methoxyheptylnitrile, methoxyoctylnitrile, methoxynonylnitrile, methoxydecylnitrile, methoxyphenylnitrile, ethoxymethylnitrile, ethoxyethylnitrile, ethoxypropylnitrile, ethoxybutylnitrile, ethoxypentylnitrile, ethoxyhexylnitrile, ethoxyheptylnitrile, ethoxyoctylnitrile, ethoxynonylnitrile, ethoxydecylnitrile, ethoxyphenylnitrile, propoxymethylnitrile, propoxyethylnitrile, propoxypropylnitrile, propoxybutyronitrile, propoxypentylnitrile, propoxyhexylnitrile, propoxyphenylnitrile, propoxytitylnitrile, propoxynonylnitrile, propoxydecyldecylnitrile, propoxyphenylnitrile and the like;

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

hydroxyl isocyanates such as hydroxymethyl isocyanate, hydroxyethyl isocyanate, hydroxypropyl isocyanate, hydroxybutyl isocyanate, hydroxypentyl isocyanate, hydroxyhexyl isocyanate, hydroxyheptyl isocyanate, hydroxyoctyl isocyanate, hydroxynonyl isocyanate, hydroxydecyl isocyanate, and hydroxyphenyl isocyanate;

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

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

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

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

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

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

hydroxyalkyl phenols such as hydroxymethylphenol, hydroxyethylphenol, hydroxypropylphenol, hydroxybutylphenol, hydroxypentylphenol, hydroxyhexylphenol, hydroxyheptylphenol, hydroxyoctylphenol, hydroxynonylphenol and hydroxydecylphenol;

hydroxyalkylamines such as hydroxymethylamine, hydroxyethylamine, hydroxypropylamine, hydroxybutylamine, hydroxypentylamine, hydroxyhexylamine, hydroxyheptylamine, hydroxyoctylamine, hydroxynonylamine, and hydroxydecylamine;

hydroxyalkylimines such as hydroxymethylimine, hydroxyethylimine, hydroxypropylimine, hydroxybutylimine, hydroxypentylimine, hydroxyhexylimine, hydroxyheptylimine, hydroxyoctylimine, hydroxynonylimine, and hydroxydecylimine;

hydroxyalkyl hydrazines such as hydroxymethyl hydrazine, hydroxyethyl hydrazine, hydroxypropyl hydrazine, hydroxybutyl hydrazine, hydroxypentylhydrazine, hydroxyhexyl hydrazine, hydroxyheptyl hydrazine, hydroxyoctyl hydrazine, hydroxynonyl hydrazine, hydroxydecyl hydrazine, etc.;

alkoxy alcohols such as methoxy methanol, methoxy ethanol, methoxy propanol, methoxy butanol, methoxy pentanol, methoxy hexanol, methoxy heptanol, methoxy octanol, methoxy nonanol, methoxy decanol, methoxy benzenealcohol, ethoxy methanol, ethoxy ethanol, ethoxy propanol, ethoxy butanol, ethoxy pentanol, ethoxy hexanol, ethoxy heptanol, ethoxy octanol, ethoxy nonanol, ethoxy decanol, ethoxy benzenealcohol, propoxy methanol, propoxy ethanol, propoxy propanol, propoxy butanol, propoxy pentanol, propoxy hexanol, propoxy heptanol, propoxy octanol, propoxy nonanol, propoxy decanol, and propoxy benzenealcohol;

hydroxyalkyl sulfides such as hydroxymethyl sulfide, hydroxyethyl sulfide, hydroxypropyl sulfide, hydroxybutyl sulfide, hydroxypentyl sulfide, hydroxyhexyl sulfide, hydroxyheptyl sulfide, hydroxyoctyl sulfide, hydroxynonyl sulfide, and hydroxydecyl sulfide;

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

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

hydroxyphenylhydrazines such as hydroxyphenylmethylhydrazine, hydroxyphenylethylhydrazine, hydroxyphenylpropylhydrazine, hydroxyphenylbutylhydrazine, hydroxyphenylpentylhydrazine, hydroxyphenylhexylhydrazine, hydroxyphenylheptylhydrazine, hydroxyphenyloctylhydrazine, hydroxyphenylnonylhydrazine, hydroxyphenyldecylhydrazine and hydroxyphenylphenylhydrazine;

methoxymethylphenol, methoxyethylphenol, methoxypropylphenol, methoxybutylphenol, methoxypentylphenol, methoxyhexylphenol, methoxyheptylphenol, methoxyoctylphenol, methoxynonylphenol, methoxydecylphenol, methoxyphenylphenol, ethoxymethylphenol, ethoxyethylphenol, ethoxypropylphenol, ethoxybutylphenol, ethoxypentylphenol, ethoxyhexylphenol, alkoxyphenols such as ethoxyheptyl phenol, ethoxyoctyl phenol, ethoxynonyl phenol, ethoxydecyl phenol, ethoxyphenyl phenol, propoxymethyl phenol, propoxyethyl phenol, propoxypropyl phenol, propoxybutyl phenol, propoxypentyl phenol, propoxyhexyl phenol, propoxypheptyl phenol, propoxyctyl phenol, propoxyponyl phenol, propoxydecyl phenol, and propoxyphenyl phenol;

hydroxyphenyl sulfides such as hydroxyphenylmethyl sulfide, hydroxyphenylethyl sulfide, hydroxyphenylpropyl sulfide, hydroxyphenylbutyl sulfide, hydroxyphenylpentyl sulfide, hydroxyphenylhexyl sulfide, hydroxyphenylheptyl sulfide, hydroxyphenyloctyl sulfide, hydroxyphenylnonyl sulfide, hydroxyphenyldecyl sulfide, and hydroxyphenylphenyl sulfide;

alkoxyamines such as methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, methoxypentylamine, methoxyhexylamine, methoxyheptylamine, methoxyoctylamine, methoxynonylamine, methoxydecylamine, methoxyaniline, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, ethoxypentylamine, ethoxyhexylamine, ethoxyheptylamine, ethoxyoctylamine, ethoxynonylamine, ethoxydecylamine, ethoxyaniline, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, propoxypentylamine, propoxyhexylamine, propoxyetylamine, propoxyectylamine, propoxyponylamine, propoxypdecylamine, and propoxyaniline.

Examples

The present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited to the following examples as long as it does not exceed the gist thereof.

[ starting materials and reagents ]

In the following examples and comparative examples, reagents manufactured by fuji film and wako pure chemical industries were used for o-cresol, toluene, sodium hydroxide, dodecanethiol, acetone, sodium bicarbonate, cesium carbonate, citric acid, malonic acid, oxalic acid, succinic acid, tartaric acid, disodium ethylenediaminetetraacetate, dodecanal, and heptane.

The hydrogen chloride gas was obtained from Sumitomo Seiko Seisakusho Co.

Diphenyl carbonate was produced by Mitsubishi chemical corporation.

[ analysis ]

< composition of bisphenol C formation reaction solution >

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

An apparatus: "LC-2010A" manufactured by Shimadzu corporation "

Imtakt ScherzoSM-C18 3μm 250mm×3.0mmID

Low pressure gradient method

Analysis temperature: 40 deg.C

Eluent composition:

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

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

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

When the analysis time is 0-41.67 minutes, the reaction is slowly changed into liquid A: solution B is 10: 90,

and when the analysis time is 41.67-50 minutes, maintaining the conditions of the solution A: solution B is 10: 90,

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

< identification of isopropenylcresol >

The identification of isopropenylcresol was carried out using a gas chromatography mass spectrometer in the following order and conditions.

An apparatus: "Agilent 6890" manufactured by Agilent Technologies Inc "

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

Carrier gas: helium

Flow rate: 1cm per minute³

Injection port temperature: 280 deg.C

Interface temperature: 250 deg.C

Ion source temperature: 250 deg.C

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

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

A sample was prepared by ashing 1g of bisphenol C or 1, 1-bis (4-hydroxyphenyl) dodecane and dissolving it in an acid. The analysis was performed using the following apparatus.

The device comprises the following steps:

ICP-MS: "ELEMENT 2" manufactured by Thermo Fisher Scientific Inc "

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

< measurement of pH >

The pH was measured by using a pH METER "pH METER ES-73" manufactured by horiba, Ltd., and measuring the 25 ℃ aqueous phase taken out from the flask.

< conductivity >

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

< color of bisphenol C dissolved in methanol >

Test tube made of Nippon Nitrosum for the color of bisphenol C dissolved in methanolBisphenol C10g and methanol 10g were added to the mixture to prepare a homogeneous solution, and then a "SE 6000" pair manufactured by Nippon Denshoku industries Co., Ltd was used at room temperature (about 20 ℃ C.)The Hazen color value was measured for evaluation.

< color difference in melting of bisphenol C >

Test tube made of Nippon Nitrosum for the color difference of melting of bisphenol CTo this was added 20g of bisphenol C, and the mixture was melted at 190 ℃ for 30 minutes, and its Hazen color value was measured by using "SE 6000" manufactured by Nippon Denshoku industries Co., Ltd.

< thermal hue stability of bisphenol C >

Test tube manufactured by Nippon Nitrosum for thermal hue stability of bisphenol CTo this was added 20g of bisphenol C, and the mixture was melted at 190 ℃ for 4 hours, and the Hazen color value was measured by using "SE 6000" manufactured by Nippon Denshoku industries Co., Ltd.

< thermal decomposition stability of bisphenol C >

Test tube manufactured by Nippon Nitrosum for thermal decomposition stability of bisphenol C20g of bisphenol C was added thereto, and the mixture was melted at 190 ℃ for 2 hours, and the amount of isopropenylcresol formed was measured and evaluated in the same manner as in the composition analysis of the bisphenol C formation reaction liquid.

< viscosity average molecular weight >

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

ηsp/C＝[η](1+0.28ηsp)

[η]＝1.23×10^-4Mv^0.83

< pellet YI >

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

The petri dish measurement calibration glass "CM-a 212" was inserted into the measurement portion, and the zero calibration cassette "CM-a 124" was covered from above to perform zero calibration, and then white calibration was performed using a built-in white calibration plate. Then, the measurement was performed using a white calibration plate "CM-A210", and it was confirmed that L was 99.40. + -. 0.05, a was 0.03. + -. 0.01, b was-0.43. + -. 0.01, and YI was-0.58. + -. 0.01.

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

[ reference example 1]

85g of bisphenol C and 4.5g of sodium hydroxide were put into a 500mL eggplant-shaped flask equipped with a stirrer, a thermometer and a distillation apparatus, and the flask was immersed in an oil bath heated to 195 ℃. After confirming that bisphenol C in the eggplant-shaped flask was melted, the pressure in the flask was gradually reduced using a vacuum pump to complete the vacuum. After a short time, evaporation was started and distillation was carried out under reduced pressure until the end of distillation. The obtained fraction was a mixture of cresol and isopropenylcresol, which were produced by thermal decomposition of bisphenol C, as seen by gas chromatography using a mass spectrometer detector. Using the obtained fraction, the retention time of isopropenylcresol was confirmed under the condition of composition analysis of the bisphenol C formation reaction liquid.

[ reference example 2]

(1) Preparation of the Mixed solution

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

(2) Reaction of

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

(3) Coarse purification

720g of toluene and 900g of deionized water were added to the resulting reaction solution, and then the internal temperature was raised to 80 ℃ with stirring. After the internal temperature reached 80 ℃, the mixture was allowed to stand and separated into a1 st organic phase and a1 st aqueous phase to obtain a1 st organic phase.

To the obtained 1 st organic phase was added 250g of deionized water, and after the internal temperature reached 80 ℃, the mixture was allowed to stand, and separated into a2 nd organic phase and a2 nd aqueous phase, and the 2 nd aqueous phase was withdrawn, thereby obtaining a2 nd organic phase.

To 1400g of the obtained 2 nd organic phase was added 300g of a 5 mass% aqueous sodium bicarbonate solution, and the mixture was allowed to stand until the internal temperature reached 80 ℃ while mixing, whereby it was confirmed that the pH of the lower layer reached 9 or more. Thereafter, the 3 rd organic phase and the aqueous sodium bicarbonate solution were subjected to phase separation, and the lower layer was extracted to obtain a 3 rd organic phase.

(4) Refining

The resulting 3 rd organic phase was cooled from 80 ℃ to 10 ℃ and then subjected to solid-liquid separation by centrifugation (10 minutes at 2500 rpm) to obtain 1 st wet cake. The resultant 1 st wet cake was transferred to a beaker, to which 500g of toluene was added and subjected to suspension washing. The resulting slurry was subjected to solid-liquid separation again by centrifugal separation (10 minutes at 2500 rpm), to obtain 415g of the 2 nd wet cake.

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

[ example 1]

A part of 300g of the 2 nd wet cake of reference example 2 and 420g of toluene were charged into an all-in-one separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ℃. It was confirmed to be a homogeneous solution, and the 4 th organic phase was obtained. To 700g of the obtained 4 th organic phase, 200g of 5 mass% hydrochloric acid was added and mixed for 30 minutes, and the lower layer 3 rd aqueous phase was removed to obtain a 5 th organic phase. To the resulting 5 th organic phase was added 200g of deionized water, and mixed for 30 minutes to remove the lower 4 th aqueous phase and obtain 6 th organic phase.

The pH of the 4 th aqueous phase (the pH of the aqueous phase before feeding disodium ethylenediaminetetraacetate) was confirmed, and as a result, the pH was 2.

To 700g of the obtained 6 th organic phase, 1g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, mixed for 30 minutes, and liquidity was confirmed by a pH paper, and it was confirmed that the aqueous phase was pH 2. Saturated aqueous sodium carbonate (18 mass%) was added thereto until the aqueous phase showed basicity, mixed for 30 minutes, and the 5 th aqueous phase was withdrawn to obtain the 7 th organic phase.

The pH of the 5 th aqueous phase (pH of the aqueous phase after extraction of disodium ethylenediaminetetraacetate) was confirmed, and as a result, the pH was 9.

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

The resulting 8 th organic phase was cooled from 80 ℃ to 10 ℃. Thereafter, the filtrate was filtered by a centrifuge (at a rotation speed of 3000 times per minute for 10 minutes) to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, light boiling components were distilled off under reduced pressure at an oil bath temperature of 80 ℃ to obtain 210g of white bisphenol C.

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

The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color number was 0. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 10. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 36. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 100 mass ppm.

[ example 2]

The procedure of example 1 was repeated except that 10g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added instead of 1g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution in example 1.

The aqueous phase before feeding the disodium ethylenediaminetetraacetate was at pH2, and the aqueous phase from which the disodium ethylenediaminetetraacetate was withdrawn was at 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 number was 0. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 10. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 34. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 95 mass ppm.

[ example 3]

The procedure of example 1 was repeated except that 100g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added instead of 1g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution in example 1.

The aqueous phase before feeding the disodium ethylenediaminetetraacetate was at pH2, and the aqueous phase from which the disodium ethylenediaminetetraacetate was withdrawn was at pH 9.

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

The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color number was 0. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 10. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 33. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 91 mass ppm.

[ example 4]

A part of 300g of the 2 nd wet cake of reference example 2 and 420g of toluene were charged into an all-in-one separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ℃. It was confirmed to be a homogeneous solution, and the 4 th organic phase was obtained. To 700g of the obtained 4 th organic phase, 300g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, mixed for 30 minutes, and liquidity was confirmed by a pH paper, and it was confirmed that the aqueous phase was pH 5.

Saturated aqueous sodium carbonate (18 mass%) was added thereto until the aqueous phase showed basicity, mixed for 30 minutes, and the 4 th aqueous phase was withdrawn to obtain the 5 th organic phase.

The pH of the 4 th aqueous phase (pH of the aqueous phase from which disodium ethylenediaminetetraacetate had been extracted) was confirmed, and as a result, the pH was 9.

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

The resulting 6 th organic phase was cooled from 80 ℃ to 10 ℃. Thereafter, the filtrate was filtered by a centrifuge (3000 rpm, 10 minutes) to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, light boiling components were distilled off under reduced pressure at an oil bath temperature of 80 ℃ to obtain 209g of white bisphenol C.

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 number was 0. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 19. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 38. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 127 mass ppm.

Comparative example 1

A part of 300g of the 2 nd wet cake of reference example 2 and 420g of toluene were charged into an all-in-one separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ℃. It was confirmed to be a homogeneous solution, and the 4 th organic phase was obtained. To the resulting 4 th organic phase was added 200g of deionized water, and mixed for 30 minutes to remove the lower 3 rd aqueous phase and obtain 5 th organic phase.

The liquid properties were confirmed by pH paper, and as a result, the 3 rd aqueous phase (the pH of the aqueous phase before supply of disodium ethylenediaminetetraacetate) was pH 9.

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

The 4 th aqueous phase (pH of the aqueous phase from which the disodium ethylenediaminetetraacetate was withdrawn) was pH 9.

The 6 th organic phase thus obtained was repeatedly washed with deionized water until the conductivity of the lower aqueous phase reached 3.0. mu.S/cm or less, whereby a 7 th organic phase was obtained.

The resulting 7 th organic phase was cooled from 80 ℃ to 10 ℃. Thereafter, the filtrate was filtered by a centrifuge (3000 rpm, 10 minutes) to obtain wet purified bisphenol C. 212g of white bisphenol C was obtained by removing light boiling components by distillation under reduced pressure at an oil bath temperature of 80 ℃ using an evaporator equipped with an oil bath.

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 Hazen color number was 12. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 42. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 65. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 250 mass ppm.

Comparative example 2

A part of 300g of the 2 nd wet cake of reference example 2 and 420g of toluene were charged into an all-in-one separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ℃. It was confirmed to be a homogeneous solution, and the 4 th organic phase was obtained. To the obtained 4 th organic phase, 200g of 5 mass% hydrochloric acid was added, and mixed for 30 minutes, and the lower 3 rd aqueous phase was removed to obtain a 5 th organic phase. To the resulting 5 th organic phase was added 200g of deionized water, and mixed for 30 minutes to remove the lower 4 th aqueous phase and obtain 6 th organic phase.

The 4 th aqueous phase (the pH of the aqueous phase before feeding the disodium edetate) was pH 2.

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

The 5 th aqueous phase was at pH 2.

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

The resulting organic phase 9 was cooled from 80 ℃ to 10 ℃. Thereafter, the filtrate was filtered by a centrifuge (3000 rpm, 10 minutes) to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, light boiling components were distilled off under reduced pressure at an oil bath temperature of 80 ℃ to obtain 209g of white bisphenol C.

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 Hazen color number was 5. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 41. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 80. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 210 mass ppm.

The pH of the aqueous phase before feeding disodium ethylenediaminetetraacetate, the pH of the aqueous phase after extracting disodium ethylenediaminetetraacetate, the iron concentration of the obtained bisphenol C, the methanol dissolution color, the melt color difference, the thermal color tone stability, and the thermal decomposition stability in examples 1 to 4, comparative examples 1 and 2 are summarized in table 1.

As is clear from table 1, when the liquid property of the aqueous phase before feeding disodium ethylenediaminetetraacetate was acidic and the liquid property of the aqueous phase after extracting disodium ethylenediaminetetraacetate was basic, the iron concentration, methanol dissolution color, melt color difference, thermal hue stability, and thermal decomposition stability of the obtained bisphenol C were improved.

In comparative example 2, after disodium ethylenediaminetetraacetate was added, a saturated sodium carbonate aqueous solution was added to the organic phase from which the aqueous phase was removed, and thus an iron removal effect by the chelating agent was not obtained.

[ Table 1]

[ example 5]

The procedure of example 2 was repeated except that 10g of a 5 mass% citric acid aqueous solution was added instead of 10g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution in example 2.

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

The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color number was 0. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 10. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 32. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 99 mass ppm.

[ example 6]

The procedure of example 2 was repeated except that 10g of a 5 mass% oxalic acid aqueous solution was added instead of 10g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution in example 2.

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 number was 0. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 10. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 35. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 98 mass ppm.

[ example 7]

The procedure of example 2 was repeated except that 10g of a 5 mass% malonic acid aqueous solution was added instead of 10g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution in example 2.

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 number was 0. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 10. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 33. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 95 mass ppm.

[ example 8]

The procedure of example 2 was repeated except that 10g of a 5 mass% succinic acid aqueous solution was added instead of 10g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution in example 2.

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 number was 0. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 10. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 32. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 90 mass ppm.

[ example 9]

The procedure of example 2 was repeated except that 10g of a 5 mass% aqueous solution of tartaric acid was added instead of 10g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate in example 2.

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

The methanol-soluble color of the obtained bisphenol C was measured, and the Hazen color number was 0. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 10. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 31. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 85 mass ppm.

Comparative example 3

The procedure of comparative example 2 was repeated except that 10g of a 5 mass% citric acid aqueous solution was added instead of 10g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution in comparative example 2.

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 Hazen color number was 10. The resulting bisphenol C was measured for color difference in melting, and found to have a Hazen color number of 39. The thermal hue stability of the obtained bisphenol C was measured, and the Hazen color number was 77. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenylcresol formed was 310 mass ppm.

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

As is clear from table 2, when other chelating agents were used as in the case of disodium ethylenediaminetetraacetate, the iron concentration, methanol dissolution color, color difference of fusion, thermal hue stability, and thermal decomposition stability of the obtained bisphenol C were also improved.

[ Table 2]

[ example 10]

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

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

Thereafter, the temperature outside the reaction vessel was raised to 280 ℃ and the absolute pressure in the reaction vessel was reduced to 30Pa to conduct polycondensation reaction. When the stirrer in the reaction tank reaches a predetermined stirring power, the polycondensation reaction is terminated. The time (latter polymerization time) from the completion of the polymerization after the temperature had risen to 280 ℃ was 210 minutes.

Then, the reaction vessel was repressed to an absolute pressure of 101.3kPa using nitrogen, and then, the pressure was increased to a gage pressure of 0.2MPa, and the polycarbonate resin was taken out from the bottom of the reaction vessel in a strand form, to obtain a strand-form polycarbonate resin.

Thereafter, the strands were pelletized using a rotary cutter to obtain a polycarbonate resin in pellet form.

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

[ reference example 3]

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

[ example 11]

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

After 7g of deionized water was added to the obtained 1 st organic phase, it was shaken with a separatory funnel for 10 minutes, and then allowed to stand for 30 minutes, after which the aqueous phase was removed to obtain a2 nd organic phase. To the obtained organic phase, 0.3g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, followed by shaking for 10 minutes, and 2g of a 5 mass% sodium hydrogencarbonate aqueous solution was further added, followed by shaking for 10 minutes. After standing for 30 minutes, the aqueous phase was removed to give a 3 rd organic phase. The pH of the removed aqueous phase was 9.

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

Comparative example 4

10g of 1, 1-bis (4-hydroxyphenyl) dodecane obtained in reference example 3 and 14g of toluene were put in an eggplant-shaped flask equipped with a nuclear magnetic rotor and dissolved at 80 ℃ to obtain a toluene solution. To the obtained toluene solution, 0.3g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, and shaken for 10 minutes. The resulting mixture was allowed to stand for 30 minutes, and then the aqueous phase was removed to obtain an organic phase 1. The resulting 1 st organic phase was repeatedly washed with 7g of deionized water 3 times, thereby obtaining a2 nd organic phase. The resulting 2 nd organic phase was cooled to 10 ℃ to obtain a slurry solution. The resulting slurry liquid was filtered, and the resulting filter cake was dried under reduced pressure at 70 ℃ to obtain 7.5g of 1, 1-bis (4-hydroxyphenyl) dodecane. The iron concentration of the obtained 1, 1-bis (4-hydroxyphenyl) dodecane was 400 mass ppb.

The iron concentrations of 1, 1-bis (4-hydroxyphenyl) dodecane obtained by adding 5 mass% disodium ethylenediaminetetraacetate aqueous solution before and after the change in pH in example 11 and comparative example 4 are summarized in table 3.

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

[ Table 3]

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

The present application is based on japanese patent application 2019-.