Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
  • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
  • C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
  • C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes

Definitions

• the present invention relates to a method for producing bisphenol and a method for producing a polycarbonate resin using the obtained bisphenol.
• the bisphenol produced by the method of the present invention contains resin raw materials such as polycarbonate resin, epoxy resin and aromatic polyester resin, and addition of a curing agent, a color developer, a fading inhibitor, and other bactericidal agents and antibacterial and antifungal agents. It is useful as an agent.
• Bisphenol is useful as a raw material for polymer materials such as polycarbonate resin, epoxy resin, and aromatic polyester resin.
• polymer materials such as polycarbonate resin, epoxy resin, and aromatic polyester resin.
• typical bisphenols for example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and the like are known (Patent Document 1).
• Patent Document 2 A method for producing bisphenol containing a fluorene skeleton is also known (Patent Document 2).
• Polycarbonate resin which is a typical use of bisphenol, is required to be colorless and transparent.
• the color tone of the polycarbonate resin is greatly affected by the color tone of the raw material. Therefore, the color tone of bisphenol, which is a raw material, is also required to be colorless. Since it is difficult to directly quantify the color of bisphenol, in the present invention, bisphenol is dissolved in methanol to quantify the color difference, and this color tone is referred to as "methanol-dissolved color".
• the bisphenol is melted to produce the polycarbonate resin, so that the polycarbonate resin is exposed to a high temperature. Therefore, the thermal color stability of bisphenol is also required. In the present invention, this color tone is referred to as "melt color difference".
• thermal color tone stability In the production of the polycarbonate resin, since the polymerization reaction is carried out after the bisphenol is melted, thermal color stability before the start of the polymerization is also required. In the present invention, this color tone is referred to as "thermal color tone stability”.
• the polycarbonate resin there is a demand for a polycarbonate resin having the molecular weight as designed and having a good color tone.
• bisphenol as a raw material is required to have excellent methanol-dissolved color, melt color difference, and thermal color tone stability, and also have excellent thermal decomposition stability.
• the present invention provides a method for producing high-quality bisphenol and a method for producing a polycarbonate resin using the bisphenol by devising a recovery process for bisphenol produced using hydrogen chloride gas or hydrochloric acid as an acid catalyst.
• the purpose is to provide.
• the present inventor can produce high-quality bisphenol by adding and mixing a chelating agent to an organic phase containing bisphenol under specific conditions after the reaction for producing bisphenol, and then adding and mixing a basic aqueous solution. I found. The present inventor has also found that the produced bisphenol can be used to produce a polycarbonate resin having a good color tone.
• the gist of the present invention lies in the following [1] to [9].
• a method for producing bisphenol which comprises a step of obtaining 3A, wherein the solubility of the chelating agent in the aqueous phase of the mixed solution 3 is higher than the solubility of the mixed solution 3 in the organic phase.
• the bisphenols are 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) dodecane, and 2,2-bis (4-hydroxy-3,
• the solubility of the organic compound in the organic phase of the mixed solution 3' is higher than the solubility of the mixed solution 3'in the aqueous phase, and the solubility of the chelating agent in the aqueous phase of the mixed solution 3'is the mixing.
• X and Y are the same or different elements, and are elements selected from the group consisting of trivalent nitrogen, divalent oxygen, trivalent phosphorus, and divalent sulfur.
• the line connecting X and Y is a carbon chain.
• the present invention it is possible to produce bisphenol having good methanol dissolution color, melt color difference, thermal color tone stability, and thermal decomposition stability. According to the present invention, the obtained bisphenol can be used to produce a polycarbonate resin having a good color tone.
• the method for producing bisphenol of the present invention is a mixed solution of an aqueous phase and an organic phase having a pH of 6 or less by 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.
• a step of obtaining 2 (hereinafter, this step may be referred to as a "chelate treatment step") and a mixed solution of the obtained mixed solution 2 and a base are mixed to obtain a mixed solution of an aqueous phase and an organic phase having a pH of 8 or higher.
• the step of obtaining 3 and the step of removing the aqueous phase having a pH of 8 or more from the obtained mixed solution 3 to obtain the organic phase 3A is the "alkali treatment step”. It is characterized in that the solubility of the chelating agent in the aqueous phase of the mixed solution 3 is higher than the solubility of the mixed solution 3 in the organic phase.
• the feature of the method for producing bisphenol of the present invention is that a chelating agent is mixed with the organic phase 1 of the mixed solution 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol, and the aqueous phase and the organic phase having a pH of 6 or less are mixed.
• a chelating agent is mixed with the organic phase 1 of the mixed solution 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol, and the aqueous phase and the organic phase having a pH of 6 or less are mixed.
• the solubility of the mixed liquid 3 in the aqueous phase is the organic of the mixed liquid 3.
• the purpose is to remove the aqueous phase having a pH of 8 or higher from the mixed solution 3 by using a chelating agent having a higher solubility in the phase, and to efficiently recover the organic phase 3A containing bisphenol.
• the corrosive component mixed in the bisphenol is mainly composed of a metal component such as iron, which is a constituent material of the equipment.
• a chelating agent is added and mixed under the specific pH acidic conditions, and then a basic aqueous solution is added to make the pH alkaline conditions to chelate metal components such as iron mixed in the bisphenol product. Efficiently remove. Then, the quality of bisphenol can be improved by removing the corrosive component.
• the organic phase 1 to which the chelating agent is added is preferably the organic phase 1A obtained by removing the aqueous phase from the mixed solution 1.
• the aqueous phase 1 contained in the mixed solution 1 of the aqueous phase 1 and the organic phase 1 containing bisphenol is preferably an aqueous phase having a pH of 6 or less.
• the following (1) and (2) Method can be mentioned.
• the reaction of bisphenol is usually carried out according to the reaction formula (1) shown below.
• R 1 - R 6 in the above reaction formula (1) are as described for R 1 - R 6 in the general formula described below (2) - (3).
• the aromatic alcohol used as a raw material for bisphenol is usually a compound represented by the following general formula (2).
• examples of R 1 to R 4 include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group and the like independently of each other. Substituents such as the alkyl group, alkoxy group and aryl group may be substituted or unsubstituted. Examples of R 1 to R 4 include hydrogen atom, fluoro group, chloro group, bromo group, iodo group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group.
• n-pentyl group i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentyloxy group, i-pentyloxy group, n-hexyloxy group, n -Heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclopropyl group, cyclobutyl group, cyclopenty
• R 2 and R 3 are sterically bulky, the condensation reaction is unlikely to proceed. Therefore, as the aromatic alcohol, an aromatic alcohol in which R 2 and R 3 are hydrogen atoms is preferable. Further, as the aromatic alcohol, those in which R 1 to R 4 are independently hydrogen atoms or alkyl groups are preferable, and more preferably, R 1 and R 4 are independently hydrogen atoms or alkyl groups, respectively, and R An aromatic alcohol in which 2 and R 3 are hydrogen atoms.
• aromatic alcohol represented by the general formula (2) examples include phenol, methylphenol (cresol), dimethylphenol (xylenol), ethylphenol, propylphenol, butylphenol, methoxyphenol, ethoxyphenol, and propoxyphenol.
• aromatic alcohol represented by the general formula (2) examples include butoxyphenol, aminophenol, benzylphenol and phenylphenol.
• 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.
• the ketone or aldehyde used as a raw material for bisphenol is usually a compound represented by the following general formula (3).
• examples of R 5 and R 6 include a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group, respectively. Substituents such as the alkyl group, alkoxy group and aryl group may be substituted or unsubstituted. Examples of R 5 and R 6 include hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, and i.
• -Pentyl group n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, methoxy group, ethoxy Group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentyloxy group, i-pentyloxy group, n-hexyloxy group, n-heptyloxy group , N-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohex
• R 5 and R 6 may be bonded or crosslinked with each other between the two groups.
• R 5 and R 6 may be bonded together with adjacent carbon atoms to form a cycloalkylidene group that may contain heteroatoms.
• the cycloalkylidene group is a divalent group obtained by removing two hydrogen atoms from one carbon atom of cycloalkane.
• R 5 and R 6 are cycloalkylidene groups formed by bonding with adjacent carbons, the obtained bisphenol has a structure in which an aromatic alcohol is bonded via a cycloalkylidene group.
• the cycloalkylidene group and R 5 and R 6 are attached form together with the adjacent carbon atoms, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3,3,5-trimethyl Cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclododecylidene, fluorenylidene, xantonilidene, thioxanthonilidene and the like can be mentioned.
• Specific examples of the compound represented by the general formula (3) include formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde, undecylaldehyde, and dodecyl.
• Ketones such as aldehydes; ketones such as acetone, butanone, pentanon, hexanone, heptanone, octanon, nonanone, decanone, undecanone, dodecanone; benzaldehyde, phenylmethylketone, phenylethylketone, phenylpropylketone, cresylmethylketone, cleres Arylalkyl Ketones such as Zyrethyl Ketone, Cresylpropyl Ketone, Xylyl Methyl Ketone, Xylyl Ethyl Ketone, Xylylpropyl Ketone, Cyclopropanone, Cyclobutanone, Cyclopentanone, Cyclohexanone, Cycloheptanone, Cyclooctanone, Cyclononanone , Cyclic alcan ketones such as cyclodecanone, cycloundecanone, cyclodo
• 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).
• R 1 to R 6 are synonymous with those in the general formulas (2) and (3).
• bisphenol represented by the general formula (4) examples include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, and 2,2. -Bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 3,3-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxy-3-methylphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4) -Hydroxy-3-methylphenyl) pentane, 3,3-bis (4-hydroxyphenyl) heptane, 3,3-bis (4-hydroxy-3-methylphenyl) heptane, 2,2-bis (4-hydroxyphenyl) ) Heptane, 2,2-bis (4-hydroxy-3-methylphenyl) heptane, 4,4-
• the method for producing bisphenol of the present invention is 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) dodecane, or 2,2-bis (4). It is suitable for the production of -hydroxy-3,5-dimethylphenyl) propane, and is particularly suitable for the production of 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C).
• Hydrochloride As the catalyst because the effect of the present invention can be obtained more remarkably.
• hydrogen chloride include hydrogen chloride gas and hydrochloric acid. Of these, hydrogen chloride gas is preferable.
• the lower limit of the molar ratio of hydrogen chloride to ketones or aldehydes is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 10 or less, more preferably. It is 8 or less, more preferably 5 or less.
• the method for condensing the aromatic alcohol with the ketone or aldehyde in order to obtain the reaction solution containing bisphenol is not particularly limited, and examples thereof include the following methods.
• Examples of the above-mentioned (i) supply of ketone or aldehyde and the above-mentioned (ii) supply of hydrogen chloride include a method of supplying all at once and a method of supplying hydrogen chloride separately. Since the reaction for producing bisphenol is an exothermic reaction, it is preferable to supply the bisphenol in divided amounts, such as by dropping it little by little. The method (i) above is preferable because the self-condensation of ketones or aldehydes can be further suppressed.
• the molar ratio of the aromatic alcohol to the ketone or the aldehyde ((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) If the number of moles)) is small, the amount of ketones or aldehydes tends to increase. If this molar ratio is high, aromatic alcohol is lost unreacted.
• the molar ratio of aromatic alcohol to ketone or aldehyde is preferably 1.5 or more, more preferably 1.6 or more, further preferably 1.7 or more, preferably 15 or less, more preferably 10. Below, it is more preferably 8 or less.
• thiol may be used as a cocatalyst in the reaction of condensing a ketone or aldehyde with an aromatic alcohol.
• thiol as a cocatalyst, for example, in the production of 2,2-bis (4-hydroxy-3-methylphenyl) propane, the production of 24 bodies is suppressed, the selectivity of 44 bodies is increased, and the polycarbonate resin is produced. It is possible to obtain the effect of increasing the polymerization activity at the time and improving the color tone of the obtained polycarbonate resin. Although the details of the reason why the effect of improving the polymerization activity during the production of the polycarbonate resin and the effect of improving the color tone of the obtained polycarbonate resin are exhibited are not clear, the use of thiol produces an inhibitor for the polymerization reaction for producing the polycarbonate resin. It is presumed that this is due to the fact that it is possible to suppress the formation of deteriorating substances as well as
• thiol used as a co-catalyst examples include mercaptocarboxylic acids such as mercaptoacetic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid and 4-mercaptobutyric acid, methyl mercaptan, ethyl mercaptan, propyl mercaptan and butyl.
• mercaptocarboxylic acids such as mercaptoacetic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid and 4-mercaptobutyric acid, methyl mercaptan, ethyl mercaptan, propyl mercaptan and butyl.
• Mercaptan Pentyl mercaptan, Hexyl mercaptan, Heptyl mercaptan, Octyl mercaptan, Nonyl mercaptan, Decyl mercaptan (decane thiol), Undecyl mercaptan (undecanthiolu), Dodecyl mercaptan (dodecane thiol), Tridecyl mercaptan, Tetradecyl mercaptan Examples thereof include alkyl thiols such as decyl mercaptan and aryl thiols such as mercaptophenol.
• the thiol cocatalyst is used.
• the effect of improving the reaction selectivity of bisphenol by using it cannot be obtained. If this molar ratio is large, it may be mixed with bisphenol and the quality may deteriorate.
• the molar ratio of the thiol cocatalyst to the ketone and the aldehyde is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more, preferably 1 or less, more preferably 0. It is 5.5 or less, more preferably 0.1 or less.
• the thiol is preferably premixed with a ketone or aldehyde before being subjected to the reaction.
• the method for mixing the thiol with the ketone or aldehyde may be a mixture of the thiol with the ketone or the aldehyde, or a ketone or the aldehyde with the thiol.
• the aromatic alcohol may be mixed with the mixed solution of thiol and ketone or aldehyde, and the aromatic alcohol is mixed with thiol and ketone or aldehyde.
• the mixed solution of the above may be mixed. It is preferable to mix a mixed solution of thiol and a ketone or aldehyde with an aromatic alcohol.
• an organic solvent is usually used to dissolve or disperse the produced bisphenol.
• the organic solvent is not particularly limited as long as it does not inhibit the bisphenol production reaction, but aromatic hydrocarbons are usually used.
• aromatic hydrocarbons are usually used.
• the aromatic alcohol as a substrate and the bisphenol as a product are removed from the organic solvent.
• aromatic hydrocarbons examples include benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, and mesitylene. These solvents may be used alone or in combination of two or more. After using the aromatic hydrocarbon for the production of bisphenol, it can be recovered and purified by distillation or the like and reused. When reusing aromatic hydrocarbons, those having a low boiling point are preferable. One of the preferred aromatic hydrocarbons is toluene.
• the mass ratio of the organic solvent to the ketone or aldehyde used for condensation ((mass of ketone / mass of organic solvent) or (mass of aldehyde / mass of organic solvent)) is too large, the ketone or aldehyde and the aromatic alcohol Is difficult to react and it takes a long time to react. If this mass ratio is too small, the increase in the amount of ketones or aldehydes may be promoted, or the bisphenol produced may solidify. From these facts, the mass ratio of the organic solvent to the ketone or aldehyde at the time of preparation is preferably 0.5 or more, more preferably 1 or more, while this mass ratio is preferably 100 or less, more preferably 50 or less.
• a large amount of the raw material aromatic alcohol may be used instead of the organic solvent instead of the organic solvent.
• the unreacted aromatic alcohol is a loss, but the loss can be reduced by recovering, purifying and reusing it by distillation or the like.
• the reaction time of the bisphenol production reaction is preferably 30 hours or less, more preferably 25 hours or less, still more preferably 20 hours or less because the produced bisphenol may be decomposed if it is too long.
• the lower limit of the reaction time is usually 2 hours or more.
• the reaction time includes the mixing time at the time of preparing the reaction solution. For example, when a mixed solution in which an aromatic alcohol and an acid catalyst are mixed is supplied with a ketone or aldehyde over 1 hour and then reacted for 1 hour, the reaction time is 2 hours.
• the reaction temperature of the bisphenol production reaction is high, the amount of ketone or aldehyde tends to increase, and when the temperature is low, the time required for the reaction becomes long. From these facts, the reaction temperature is preferably -30 ° C or higher, more preferably -20 ° C or higher, further preferably -15 ° C or higher, preferably 80 ° C or lower, more preferably 70 ° C or lower, still more preferably 60 ° C. It is below ° C.
• the reaction temperature means the average temperature from the start to the end of the first step.
• the reaction solution containing bisphenol is preferably obtained as a slurry-like solution in which the produced bisphenol is not completely dissolved in the reaction solution but dispersed.
• a slurry in which bisphenol is dispersed can be obtained.
• the chelate treatment step in the present invention may be carried out before the crystallization step described later and after the bisphenol formation reaction step, or after the bisphenol formation reaction and after the water washing step described later, or the crystals described below. It may be performed after the analysis step.
• the chelate treatment step is performed after the bisphenol production reaction, water is added to and mixed with the reaction solution of the bisphenol production reaction, and if the pH of the aqueous phase obtained by phase separation is 6 or less, the aqueous phase is removed.
• a chelating agent can be added and mixed with the organic phase 1A as the organic phase 1 to obtain a mixed solution 2.
• the chelate treatment step is performed after the bisphenol production reaction step and the water washing step described later, if the pH of the aqueous phase obtained by phase separation after washing by adding or mixing water is 6 or less, this water A chelating agent is added and mixed with the organic phase after removing the phase as the organic phase 1 to obtain a mixed solution 2.
• an acidic aqueous solution may be added and mixed with the organic phase after removing the aqueous phase to separate the aqueous phase having a pH of 6 or less.
• an organic solvent is added to the solid bisphenol recovered by crystallization to obtain a bisphenol solution, and an acidic aqueous solution is added to and mixed with the bisphenol solution to obtain water having a pH of 6 or less.
• the phases may be separated from each other.
• the above acidic aqueous solution is added and mixed, and water is added to the organic phase obtained by phase separation, and the phase is separated by mixing. If the phase-separated aqueous phase is pH 6 or less, this aqueous phase is used.
• the organic phase obtained by phase separation may be used as the first organic phase.
• the pH of the aqueous phase separated when obtaining the organic phase 1A exceeds 6, the corrosive components cannot be sufficiently removed by the chelating agent, and methanol dissolved color, molten color difference, thermal color stability, etc. It is not possible to obtain bisphenol with good thermal decomposition stability.
• the pH of this aqueous phase is particularly preferably 5 or less. If the pH of the aqueous phase is excessively low, the amount of the basic aqueous solution used in the next alkali treatment step becomes excessive, so the pH of the aqueous phase is preferably -1 or more. In the present invention, the pH is a measured value at room temperature (20 to 30 ° C.).
• hydrochloric acid sulfuric acid, phosphoric acid, an inorganic acid of nitric acid and the like can be used.
• the concentration of acidic substances in the acidic aqueous solution is appropriately adjusted according to the acidic substances and basic substances remaining in bisphenol. If the concentration of the acidic substance in the acidic aqueous solution is too high, bisphenol is decomposed, so that it is preferably 35% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less. If the concentration of the acidic substance in the acidic aqueous solution is too low, it is necessary to increase the amount of the acidic aqueous solution in order to obtain an aqueous phase having a pH of 6 or less. Therefore, the lower limit of the concentration of the acidic substance in the acidic aqueous solution is preferably 0.01 mass ppm or more. , 0.1 mass ppm or more is more preferable.
• the mass ratio of the acidic aqueous solution 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, still more preferably 0.5 or less.
• the mass ratio of the acidic aqueous solution to the amount of the organic phase is preferably 0.05 or more, more preferably 0.1 or more.
• the type of chelating agent to be added to the organic phase 1 after separating the aqueous phase having a pH of 6 or less is not limited as long as it is generally used as a chelating agent, but in the present invention, the alkali treatment step described later
• the solubility in the aqueous phase in the mixed solution 3 (hereinafter referred to as "solubility for the aqueous phase") obtained in 1) is higher than the solubility in the organic phase in the mixed solution 3 (hereinafter referred to as "solubility for the organic phase").
• solubility for the organic phase also use a high chelating agent.
• the solubility of the chelating agent used in the aqueous phase is less than or equal to the solubility in the organic phase, the chelating agent used remains in the organic phase and remains in bisphenol, and the purity of bisphenol decreases.
• the chelating agent may have a higher solubility in the aqueous phase than the solubility in the organic phase, but 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, more preferably more preferably. It is more than 10 times.
• chelating agents include ⁇ -diketones such as acetylacetone and 3,5-heptandione; aminocarboxylic acids such as ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid and hydroxyethylethylenediaminetriacetic acid and salts thereof; pyruvate and acetoacetic acid.
• ketoic acid such as acetonedicarboxylic acid
• hydroxy acids such as glycolic acid, glyceric acid, xylonic acid, gluconic acid, lactic acid, tartronic acid, tartrate acid, xylal acid, galactal acid, malic acid, citric acid
• Polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid; amino acids such as aspartic acid and glutamic acid; polyphosphoric acids such as phytic acid, hydroxyethylidene diphosphate, nitrilotrismethylene phosphate and ethylenediaminetetramethylene phosphate; dimethyl Examples thereof include dioximes such as glyoxime, benzyl diglyoxime, and 1,2-cyclohexyl diglyoxime.
• ethylenediaminetetraacetic acid, citric acid, oxalic acid, malonic acid, and succinic acid are examples of those that satisfy the above-mentioned solubility in aqueous phase and solubility in organic phase.
• a tetravalent carboxylic acid is preferable, and aminocarboxylic acids such as ethylenediaminetetraacetic acid and salts thereof are preferable from the viewpoint of easily chelating with various metals.
• a chelating agent composed of only carbon, hydrogen, and oxygen atoms is preferable because it has excellent solubility in an organic solvent and easily binds to a corrosive component. Examples thereof include acetylacetone and 3,5-heptandione.
• ⁇ -diketones such as: pyruvate, acetoacetic acid, levulinic acid, ⁇ -ketoglutaric acid, acetone dicarboxylic acid and other keto acids; glycolic acid, glyceric acid, xylonic acid, gluconic acid, lactic acid, tartronic acid, tartrate acid, xylolic acid, galactal Hydroxy acids such as acids, malic acids and citric acids; polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid.
• the chelating agent is preferably added to the organic phase 1 as an aqueous solution of 0.1% by mass or more, particularly 0.5% by mass or more, and 15% by mass or less, particularly about 10% by mass or less. If the concentration of the chelating agent is too high, it may precipitate and the effect of the chelating agent may be reduced. If the concentration of the chelating agent is too low, there is a problem that the amount of wastewater generated after the chelating agent is supplied increases.
• the amount of the aqueous chelating agent added to the organic phase 1 may be an amount that can sufficiently chelate and remove the corrosive components in the organic phase 1, the concentration of the chelating agent, and the organic phase 1 to be treated. It also depends on the amount of corrosive components in. If the amount of the aqueous chelating agent added to the organic phase 1 is too large, the production cost increases. If the amount of the aqueous chelating agent added to the organic phase 1 is too small, the corrosive components in the organic phase 1 cannot be sufficiently removed, and the effects of the present invention cannot be sufficiently obtained.
• the mass ratio of the chelating agent aqueous solution to the organic phase 1 is 0.0001 or more, particularly 0.001 or more, and 10 or less, particularly 1 or less. It is preferable to have.
• the pH of the aqueous phase of the mixed solution 2 after the addition and mixing of the aqueous chelating agent solution is also 6 or less, particularly 5 or less, preferably -1 or more.
• a base is preferably added and mixed as a basic aqueous solution to the mixed solution 2 obtained in the above chelate treatment step to obtain a mixed solution 3 of an aqueous phase having a pH of 8 or higher and an organic phase.
• This is a step of removing an aqueous phase having a pH of 8 or higher from the obtained mixed solution 3 to obtain an organic phase 3A.
• the mixing ratio of the aqueous phase and the organic phase in the mixed solution 2 is preferably more than 0.001: 700 by weight, more preferably more than 0.01: 700, and 0. It is particularly preferable that there are more aqueous phases than .05: 700.
• the mixing ratio of the aqueous phase and the organic phase in the mixed solution 2 is preferably less than 1000: 700 mass ratio by weight, more preferably less than 500: 700, and 300: 700. It is particularly preferable that there is less aqueous phase. If it is out of this range, the chelating agent dissolved in the aqueous phase is also removed, so that the effect of the present invention is not exhibited.
• the pH of the aqueous phase to be phase-separated here may be 8 or more, and may be 10 or more or 11 or more, but usually about 8 to 9 is adopted.
• Sodium hydrogen carbonate, sodium carbonate, etc. can be used as the basic substance of the basic aqueous solution.
• the concentration of the basic substance in the basic aqueous solution used in this alkali treatment step is preferably as high as possible, and is preferably a saturated aqueous solution of the basic substance.
• the mass ratio of the basic aqueous solution to the amount of the mixed solution 2 in the alkali treatment step is 0.01 or more, particularly 0.1 or more, and 100 or less. , Especially preferably 10 or less.
• the organic phase 3A obtained in the alkali treatment step is subjected to the following washing step as necessary and then purified in the crystallization step described later to recover the purified bisphenol.
• the method for producing bisphenol of the present invention may include a water washing step of washing the reaction solution containing bisphenol obtained in the bisphenol production reaction step and the organic phase 3A after the alkali treatment step with water. By performing such a washing step, the amount of impurities can be further reduced.
• the mass ratio of water to the amount of the reaction solution or the organic phase 3A is preferably 0.01 or more, more preferably 0.05 or more, and preferably 2 or less. 1, 1 or less is more preferable, and 0.5 or less is further preferable.
• This water washing step is performed by supplying water to the reaction solution or the organic phase 3A for washing, then separating the organic phase and the aqueous phase, and removing the aqueous phase.
• the washing step may be performed a plurality of times. In this case, the above water supply, washing, phase separation, and removal of the aqueous phase are repeated.
• the method for producing bisphenol of the present invention may include an alkali washing step of washing the obtained organic phase with a basic aqueous solution after the alkali treatment step or the washing step with water.
• this alkaline cleaning step after the alkali treatment step or the water washing step, the separated organic phase and the basic aqueous solution are mixed, and then the organic phase and the aqueous phase having a pH of 9 or more are phase-separated to obtain the phase-separated aqueous phase. It is preferably a step of removing to obtain an organic phase.
• the alkaline cleaning step may be performed a plurality of times.
• the pH of the aqueous phase separated in the alkaline cleaning step may be 9 or more, and may be 10 or more or 11 or more.
• the upper limit of this pH may be 14 or less or 13 or less.
• sodium hydrogen carbonate, sodium carbonate or the like can be used as the basic substance of the basic aqueous solution used in the alkaline cleaning step.
• the concentration of the basic substance in the basic aqueous solution used in the alkaline cleaning step is appropriately adjusted according to the type of the basic substance and the acid catalyst. If the concentration of the basic substance in the basic aqueous solution is too high, it will remain in the finally obtained bisphenol and deteriorate the quality. Therefore, it is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass. The following is more preferable. If the concentration of the basic substance in the basic aqueous solution is too low, it is necessary to increase the amount of the basic aqueous solution in order to obtain an aqueous phase having a pH of 9 or higher. Therefore, the concentration of the basic substance in the basic aqueous solution is 0.1% by mass. The above is preferable, and 0.5% by mass or more is more preferable.
• the mass ratio of the basic aqueous solution to the amount of the organic phase in the alkaline washing step is preferably 2 or less, more preferably 1 or less, still more preferably 0.5 or less. , 0.05 or more, more preferably 0.1 or more.
• the average temperature from the start to the end is preferably 50 ° C. or higher, preferably 55 ° C. or higher. Is more preferable.
• the average temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, in order to suppress the precipitation of bisphenol due to evaporation of the organic solvent.
• the method for producing bisphenol of the present invention preferably includes a crystallization step.
• the crystallization step is usually carried out after an alkali treatment step or an alkali treatment step, an alkali washing step and a subsequent washing step with water.
• Crystallization can be performed according to a conventional method. For example, both a method of utilizing the difference in solubility of bisphenol due to a temperature difference and a method of precipitating a solid by supplying a poor solvent can be applied. Since the purity of the obtained bisphenol tends to decrease in the method of supplying the poor solvent, the method of utilizing the difference in the solubility of the bisphenol due to the temperature difference is preferable. When the content of aromatic alcohol in the organic phase is high, excess aromatic alcohol may be distilled off before crystallization before crystallization.
• bisphenol is precipitated by cooling the organic phase at 60 to 90 ° C. to ⁇ 10 to 30 ° C.
• the precipitated bisphenol can be separated into solid and liquid and recovered by drying or the like.
• the organic phase used in this crystallization step preferably has an electrical conductivity of 10 ⁇ S / cm or less of the aqueous phase (hereinafter, may be referred to as “immediately preceding aqueous phase”) phase-separated in the immediately preceding step. ..
• the electrical conductivity of the immediately preceding aqueous phase is 10 ⁇ S / cm or less, particularly 9 ⁇ S / cm or less, particularly 8 ⁇ S / cm or less, impurities such as by-products and residual catalyst in the product are highly removed, and the hue
• bisphenol having high polymerization reaction efficiency and capable of producing a polycarbonate resin having an excellent hue can be obtained, which is preferable.
• the electric conductivity of the immediately preceding aqueous phase can be measured with an electric conductivity meter, for example, for the immediately preceding aqueous phase at room temperature (20 to 30 ° C.) separated from each other.
• the bisphenol thus obtained may be further purified by a conventional method depending on its use.
• it can be purified by simple means such as sprinkle washing, water washing, suspension washing, crystallization and column chromatography.
• the obtained bisphenol can be further purified by dissolving it in an organic solvent such as an aromatic hydrocarbon, cooling it, and crystallizing it.
• the method for producing bisphenol of the present invention can be, for example, a production method having a chelate treatment step, an alkali treatment step, a washing step, and a crystallization step in this order. Further, the method for producing bisphenol of the present invention can be a production method having a water washing step, a chelate treatment step, an alkali treatment step, a water washing step, and a crystallization step in this order.
• bisphenol of the present invention suitable physical properties of bisphenol produced by the method for producing bisphenol of the present invention
• ⁇ Methanol-dissolved color of bisphenol The methanol-dissolved color of bisphenol is used to evaluate the color tone of bisphenol at room temperature. The lower the number of Hazen colors of the methanol-dissolved color of bisphenol, the better the color tone of bisphenol (close to white). As a cause of deteriorating the methanol-dissolved color of bisphenol, there is an inclusion of an organic coloring component or a metal.
• the methanol-dissolved color of bisphenol is measured at room temperature (about 20 ° C) after dissolving bisphenol in methanol to make a uniform solution.
• the measuring method include a method of visually comparing with a standard solution having a Hazen color number, or a method of measuring the Hazen color number using a color difference meter such as "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd.
• SE6000 color difference meter
• the mass ratio of the solvent methanol and bisphenol used here to the solvent is preferably selected as appropriate depending on the type of bisphenol.
• the number of Hazen colors of the methanol-dissolved color of bisphenol is preferably 20 or less, more preferably 10 or less, and particularly preferably 5 or less.
• melt color difference of bisphenol is used to evaluate the color tone of bisphenol at a temperature close to the polymerization temperature of polycarbonate.
• the measurement temperature of the melt color difference is the melting point of bisphenol + 50 ° C.
• the melt color difference of bisphenol indicates that the lower the number of Hazen colors, the better the color tone of bisphenol (closer to white).
• causes of exacerbating the melt color difference of bisphenol include components that are colored by heating, in addition to organic coloring components and metal contamination.
• the melt color difference of bisphenol is measured in advance by melting bisphenol at a temperature close to the polymerization temperature and measuring the time when the temperature is stable.
• Examples of the measuring method include a method of visually comparing with a standard solution having a Hazen color number, or a method of measuring the Hazen color number using a color difference meter such as "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd.
• the number of Hazen colors is preferably 40 or less, more preferably 30 or less, and particularly preferably 20 or less.
• the thermal color stability of bisphenol is used to evaluate the thermal stability of bisphenol color tone by holding it at a temperature close to the polymerization temperature of polycarbonate for a predetermined time, similar to the melt color difference of bisphenol.
• the measurement temperature of the thermal color stability of bisphenol is the melting point of bisphenol + 50 ° C.
• the thermal color stability of bisphenol As for the thermal color stability of bisphenol, the lower the number of Hazen colors, the better the thermal color stability of bisphenol.
• the causes of deteriorating the thermal color stability of bisphenol include components that are colored by heating and acidic substances and basic substances having a concentration of about several ppm.
• the thermal color stability of bisphenol is measured in advance by melting bisphenol at a temperature close to the polymerization temperature and at a time when the temperature is stable.
• the retention time for thermal color stability of bisphenol is 4 hours.
• Examples of the measuring method include a method of visually comparing with a standard solution having a Hazen color number, or a method of measuring the Hazen color number using a color difference meter such as "SE6000" manufactured by Nippon Denshoku Kogyo Co., Ltd.
• the number of Hazen colors is preferably 50 or less, more preferably 45 or less, and particularly preferably 35 or less.
• thermo decomposition stability of bisphenol is used to evaluate the thermal stability of bisphenol by holding it 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 ° C.
• the thermal decomposition stability of bisphenol indicates that the smaller the amount of decomposition product produced, the more stable the bisphenol is.
• the decomposition product in the thermal decomposition stability of bisphenol includes an aromatic alcohol which is a raw material of the bisphenol, or an addition of a ketone or an aldehyde which is a raw material of the aromatic alcohol, although it depends on the type of the bisphenol.
• the causes of deteriorating the thermal decomposition stability of bisphenol include components that are colored by heating and acidic substances and basic substances having a concentration of about several ppm.
• Detection and quantification of bisphenol degradation products can be performed using standard reverse phase columns for fast analysis.
• the amount of isopropenyl cresol produced as a decomposition product of bisphenol as measured in Examples described later is preferably 200 mass ppm or less.
• the methanol-dissolved color of bisphenol is a method for evaluating the color tone of bisphenol itself.
• bisphenol is the final product, bisphenol with good methanol dissolution color is important. Since the polycarbonate resin inherits the color tone of the raw material, bisphenol having a good color tone is important for the polycarbonate resin that is required to be colorless and transparent.
• the melt polymerization method which is one of the methods for producing a polycarbonate resin
• the color tone of bisphenol at the time of melting (melt color difference of bisphenol)
• the color tone stability of bisphenol in the molten state (of bisphenol). Thermal color stability) is important.
• the bisphenol is kept melted at a high temperature until the start of the polymerization reaction.
• the substance amount ratio with diphenyl carbonate deviates from a predetermined substance amount ratio, and it becomes difficult to obtain a polycarbonate resin having polymerization reaction activity and a predetermined molecular weight. Therefore, resistance to thermal decomposition (thermal decomposition stability of bisphenol) is important.
• the methanol-dissolved color of bisphenol the melt color difference of bisphenol, the thermal color stability of bisphenol, and the thermal decomposition stability of bisphenol are important.
• the bisphenol of the present invention is a polyether resin, polyester resin, polyarylate resin, polycarbonate resin, polyurethane resin, which is used for various purposes such as optical materials, recording materials, insulating materials, transparent materials, electronic materials, adhesive materials, and heat resistant materials.
• Components, curing agents, additives or precursors thereof such as various thermoplastic resins such as acrylic resin, various thermocurable resins such as epoxy resin, unsaturated polyester resin, phenol resin, polybenzoxazine resin and cyanate resin. It can be used as such.
• the bisphenol of the present invention is also useful as an additive such as a color developer such as a heat-sensitive recording material, a fading inhibitor, a bactericide, and an antibacterial and antifungal agent.
• the bisphenol of the present invention is preferably used as a raw material (monomer) for a thermoplastic resin or a thermosetting resin, and more preferably as a raw material for a polycarbonate resin or an epoxy resin, because it can impart good mechanical properties.
• the bisphenol of the present invention is also preferably used as a color developer, and more preferably used in combination with a leuco dye and a discoloration temperature adjuster.
• 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 bisphenol of the present invention is a production in which a bisphenol produced by the above method and diphenyl carbonate or the like are subjected to a transesterification reaction in the presence of an alkali metal compound and / or an alkaline earth metal compound. The method.
• the bisphenol of the present invention only one kind may be used, or two or more kinds may be used to produce a copolymerized polycarbonate resin.
• Dihydroxy compounds other than the bisphenol of the present invention can also be used in combination for the reaction.
• the transesterification reaction can be carried out by appropriately selecting a known method.
• An example of using the bisphenol and diphenyl carbonate of the present invention as raw materials will be described below.
• the amount of diphenyl carbonate used for bisphenol is preferably large in that the produced polycarbonate resin has few terminal hydroxyl groups and is excellent in thermal stability of the polymer.
• the amount of diphenyl carbonate used for bisphenol is preferably small in that the transesterification reaction rate is high and a polycarbonate resin having a desired molecular weight can be easily produced. From these facts, the amount of diphenyl carbonate used with respect to 1 mol of bisphenol is usually 1.001 mol or more, preferably 1.002 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less.
• the bisphenol and diphenyl carbonate of the present invention can be supplied in solid form, but it is preferable to supply one or both of them in a liquid state by melting them.
• a transesterification catalyst When producing a polycarbonate resin by transesterification reaction between diphenyl carbonate and bisphenol, a transesterification catalyst is usually used.
• a transesterification catalyst In the above method for producing a polycarbonate resin, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound as the transesterification catalyst. These may be used alone or in combination of two or more in any combination and ratio. Practically, it is desirable to use an alkali metal compound.
• the amount of the catalyst used is usually 0.05 ⁇ mol or more, preferably 0.08 ⁇ mol or more, more preferably 0.10 ⁇ mol or more, and usually 100 ⁇ mol or less, preferably 50 ⁇ mol, based on 1 mol of bisphenol or diphenyl carbonate. Below, it is more preferably 20 ⁇ mol or less.
• the amount of the catalyst used is within the above range, the polymerization activity required for producing a polycarbonate resin having a desired molecular weight can be easily obtained, the polymer hue is excellent, and excessive polymer branching does not proceed. It is easy to obtain a polycarbonate resin with excellent fluidity during molding.
• both of the above raw materials are continuously supplied to the raw material mixing tank, and the obtained mixture and the transesterification catalyst are continuously supplied to the polymerization tank.
• both raw materials supplied to the raw material mixing tank are usually stirred uniformly and then supplied to a polymerization tank to which a transesterification catalyst is added to produce a polymer.
• the polymerization reaction temperature is preferably 80 to 400 ° C, particularly 150 to 350 ° C.
• the polymerization time is appropriately adjusted depending on the ratio of raw materials, the desired molecular weight of the polycarbonate resin, and the like. If the polymerization time is long, quality deterioration such as color tone deterioration becomes apparent. Therefore, it is preferably 10 hours or less, and more preferably 8 hours or less.
• the lower limit of the polymerization time is usually 0.1 hours or more, or 0.3 hours or more.
• a polycarbonate resin having excellent hue and transparency can be produced.
• a polycarbonate resin having a viscosity average molecular weight (Mv) of 10,000 or more, preferably 15,000 or more, 100,000 or less, preferably 35,000 or less, and a pellet YI of 10 or less and excellent hue and transparency can be produced in a short time.
• metal coordination refers to a compound that can be bonded to a metal ion by a coordination bond to form a complex, and the organic compound (I) has a partial structure (I) to form a metal ion. Functions as a ligand for.
• X and Y are the same or different elements, and are elements selected from the group consisting of trivalent nitrogen, divalent oxygen, trivalent phosphorus, and divalent sulfur.
• the line connecting X and Y is a carbon chain.
• Each of X and Y in the formula (I) may further have a substituent containing an element selected from the group consisting of trivalent nitrogen, divalent oxygen, trivalent phosphorus, and divalent sulfur. ..
• the "carbon chain” refers to a link in which carbon atoms are connected by a single bond, a double bond, or a triple bond, and is not limited to a chain such as a linear or branched bond, but includes a cyclic structure. It may be a combination of these.
• the organic compound (I) is a metal-coordinating compound in which the partial structure (I) functions as a ligand for a metal ion. Therefore, the organic compound (I) may be present in the reaction product as a metal compound used as a catalyst in the production process or as a complex compound coordinated to the metal due to impurities mixed in the production process. There are many. In the use of the organic compound (I), the product incorporating the metal causes problems such as coloring, decomposition, and alteration due to the contained metal.
• the metal is efficiently removed from the organic compound (I) to obtain a high-purity and high-quality organic compound ( I) can be manufactured.
• the organic phase 1'of the mixed solution 1'of the aqueous phase 1'and the organic phase 1'containing the organic compound (I) and the chelating agent are mixed and pH 6
• the step of removing the aqueous phase having a pH of 8 or more from the obtained mixed solution 3'to obtain the organic phase 3A', and the solubility of the mixed solution 3'of the organic compound (I) in the organic phase of the mixed solution 3 is included.
• an amide group, a hydrazide group, an imide group, an amidin group in which X and / or Y are nitrogen elements examples thereof include those having a nitrile group, an alcohol group which is an oxygen element, a phenol group, an ether group, a thiol group which is a sulfur element, and a sulfide group.
• the chelating agent different from the organic compound (I) is selected.
• the organic compound (I) is the carboxylic acid
• the ⁇ -diketones or the dioxime are selected as the chelating agent.
• the organic compound (I) is the ⁇ -diketones
• the carboxylic acids or the dioximes are selected as the chelating agent.
• the organic compound (I) is the dioxime
• the carboxylic acid or ⁇ -diketone is selected as the chelating agent.
• organic compound (I) examples include the following, but the organic compound (I) to which the method for producing an organic compound of the present invention is applied is not limited to any of the following.
• Organic compound (I) with the same X and Y> Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.
• Oxamide, malonic acid diamide, succinate diamide, glutaru Diamides such as acid diamide, adiponic acid diamide, pimelliate diamide, suberic acid diamide, azelaic acid diamide, sebacic acid diamide, phthalic acid diamide, isophthalic acid diamide, and terephthalic acid diamide.
• Biphenols such as biphenol, dimethylbiphenol, tetramethylbiphenol
• Diamines such as ethylenediamine, propylenediamine, butenediamine, pentendiamine, hexenediamine, heptenediamine, octenediamine, nonenediamine, decenediamine, benzenediamine, etc.
• Diamines such as pentanediamine, hexanediamine, heptanediamine, octanediamine, nonandidiimin, decanediamine
• Dihydrazines such as ethylenedihydrazine, propylene dihydrazine, butenedihydrazine, pentendihydrazine, hexenedihydrazine, heptendihydrazine, octendihydrazine, nonanedihydrazine, decenedihydrazine, benzenedihydrazine, dimethoxymethane, dimethoxyethane, Dimethoxypropane, dimethoxybutane, dimethoxypentane, dimethoxyhexane, dimethoxyheptane, dimethoxyoctane, dimethoxynonane, dimethoxydecane, dimethoxybenzene, diethoxymethane, diethoxyethane, diethoxypropane, diethoxybutane, diethoxypentane, diethoxyhexane , Diethoxyheptane, diethoxyoct
• Nitrile isocyanates such as methine nitrile isocyanate, ethylene nitrile isocyanate, propylene nitrile isocyanate, butene nitrile isocyanate, penten nitrile isocyanate, hexene nitrile isocyanate, heptene nitrile isocyanate, octene nitrile isocyanate, nonen nitrile isocyanate, decene nitrile isocyanate, and benzene nitrile isocyanate.
• Nitrile isocyanates such as methine nitrile isocyanate, ethylene nitrile isocyanate, propylene nitrile isocyanate, butene nitrile isocyanate, penten nitrile isocyanate, hexene nitrile isocyanate, heptene nitrile isocyanate, octene nitrile is
• Hydroxynitriles such as hydroxymethylnitrile, hydroxyethylnitrile, hydroxypropylnitrile, hydroxybutylnitrile, hydroxypentylnitrile, hydroxyhexylnitrile, hydroxyheptylnitrile, hydroxyoctylnitrile, hydroxynonylnitrile, hydroxydecylnitrile, and hydroxyphenylnitrile
• Hydroxyphenylmethylnitrile hydroxyphenylethylnitrile, hydroxyphenylpropylnitrile, hydroxyphenylbutylnitrile, hydroxyphenylpentylnitrile, hydroxyphenylhexylnitrile, hydroxyphenylheptylnitrile, hydroxyphenyloctylnitrile, hydroxyphenylnonylnitrile, hydroxyphenyldecylnitrile , Hydroxyphenylnitriles such as hydroxyphenylphenylnitriles
• Aminonitriles such as aminomethylnitrile, aminoethylnitrile, aminopropylnitrile, aminobutylnitrile, aminopentylnitrile, aminohexylnitrile, aminoheptylnitrile, aminooctylnitrile, aminononylnitrile, aminodecylnitrile, aminophenylnitrile
• Iminonitriles such as iminomethylnitrile, iminoethylnitrile, iminopropylnitrile, iminobutylnitrile, iminopentylnitrile, iminohexylnitrile, iminoheptylnitrile, iminooctylnitrile, iminononylnitrile, iminodecylnitrile, iminophenylnitrile
• Nitrile hydrazines such as methinenitrile hydrazine, ethylenenitrile hydrazine, propylenenitrile hydrazine, butenenitrile hydrazine, pentennitrile hydrazine, hexenenitrile hydrazine, heptenenitrile hydrazine, octenenitrile hydrazine, nonennitrile hydrazine, decenenitrile hydrazine, benzenenitrile hydrazine.
• Nitrile sulfides such as methine nitrile sulfide, ethylene nitrile sulfide, propylene nitrile sulfide, butene nitrile sulfide, penten nitrile sulfide, hexene nitrile sulfide, heptene nitrile sulfide, octene nitrile sulfide, nonen nitrile sulfide, decene nitrile sulfide, and benzene nitrile sulfide.
• Hydroxy isocyanates such as hydroxymethyl isocyanate, hydroxyethyl isocyanate, hydroxypropyl isocyanate, hydroxybutyl isocyanate, hydroxypentyl isocyanate, hydroxyhexyl isocyanate, hydroxyheptyl isocyanate, hydroxyoctyl isocyanate, hydroxynonyl isocyanate, hydroxydecyl isocyanate, hydroxyphenyl isocyanate, etc.
• Hydroxyphenylmethyl isocyanate hydroxyphenylethyl isocyanate, hydroxyphenylpropyl isocyanate, hydroxyphenylbutyl isocyanate, hydroxyphenylpentyl isocyanate, hydroxyphenylhexyl isocyanate, hydroxyphenyl heptyl isocyanate, hydroxyphenyloctyl isocyanate, hydroxyphenylnonyl isocyanate, hydroxyphenyldecyl isocyanate , Hydroxyphenyl isocyanates such as 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, aminophenylisocyanate, etc.
• Iminomethyl isocyanate iminoethyl isocyanate, iminopropyl isocyanate, iminobutyl isocyanate, iminopentyl isocyanate, iminohexyl isocyanate, iminoheptyl isocyanate, iminooctyl isocyanate, iminononyl isocyanate, iminodecyl isocyanate, iminophenyl isocyanate and other iminoisocyanates
• Silica sulfides such as methine isocyanate sulfide, ethylene isocyanate sulfide, propylene isocyanate sulfide, butene isocyanate sulfide, penten isocyanate sulfide, hexene isocyanate sulfide, heptene isocyanate sulfide, octene isocyanate sulfide, nonene isocyanate sulfide, decene isocyanate sulfide, and benzene isocyanate sulfide.
• Hydroxyalkylphenols such as hydroxymethylphenol, hydroxyethylphenol, hydroxypropylphenol, hydroxybutylphenol, hydroxypentylphenol, hydroxyhexylphenol, hydroxyheptylphenol, hydroxyoctylphenol, hydroxynonylphenol, hydroxydecylphenol
• Hydroxyalkylamines such as hydroxymethylamine, hydroxyethylamine, hydroxypropylamine, hydroxybutylamine, hydroxypentylamine, hydroxyhexylamine, hydroxyheptylamine, hydroxyoctylamine, hydroxynonylamine, hydroxydecylamine, etc.
• Hydroxyalkylimines such as hydroxymethylimine, hydroxyethylimine, hydroxypropylimine, hydroxybutylimine, hydroxypentylimine, hydroxyhexyluimine, hydroxyheptylimine, hydroxyoctylimine, hydroxynonylimine, hydroxydecylimine, etc.
• Hydroxyalkyl hydrazines such as hydroxymethyl hydrazine, hydroxyethyl hydrazine, hydroxypropyl hydrazine, hydroxybutyl hydrazine, hydroxypentyl hydrazine, hydroxyhexyl hydrazine, hydroxyheptyl hydrazine, hydroxyoctyl hydrazine, hydroxynonyl hydrazine, hydroxydecyl hydrazine
• 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.
• Hydroxyphenylmethylimine hydroxyphenylethylimine, hydroxyphenylpropylimine, hydroxyphenylbutylimine, hydroxyphenylpentylimine, hydroxyphenylhexyluimine, hydroxyphenylheptylimine, hydroxyphenyloctylimine, hydroxyphenylnonylimine, hydroxyphenyldecylimine, Hydroxyphenylimines such as hydroxyphenylphenylimines
• Hydroxyphenylmethylhydrazine hydroxyphenylethylhydrazine, hydroxyphenylpropylhydrazine, hydroxyphenylbutylhydrazine, hydroxyphenylpentylhydrazine, hydroxyphenylhexylhydrazine, hydroxyphenylheptylhydrazine, hydroxyphenyloctylhydrazine, hydroxyphenylnonylhydrazine, hydroxyphenyldecylhydrazine , Hydroxyphenylhydrazines such as hydroxyphenylphenylhydrazine
• Hydroxyphenyl methyl sulfide hydroxyphenyl ethyl sulfide, hydroxyphenyl propyl sulfide, hydroxyphenyl butyl sulfide, hydroxyphenyl pentyl sulfide, hydroxyphenyl hexyl sulfide, hydroxyphenyl heptyl sulfide, hydroxyphenyl octyl sulfide, hydroxyphenyl nonyl sulfide, hydroxyphenyl decyl sulfide.
• Hydroxyphenyl sulfides such as hydroxyphenyl phenyl sulfide
• ⁇ Methanol-dissolved color of bisphenol C For the methanol-dissolved color of bisphenol C, put 10 g of bisphenol C and 10 g of methanol in a test tube "P-24" (24 mm ⁇ x 200 mm) manufactured by Niommen Rika Glass Co., Ltd. to make a uniform solution, and then at room temperature (about 20 ° C), Japan. The number of Hazen colors was measured and evaluated using "SE6000" manufactured by Denshoku Kogyo Co., Ltd.
• ⁇ Pyrolysis stability of bisphenol C For the thermal decomposition stability of bisphenol C, 20 g of bisphenol C was placed in a test tube "P-24" (24 mm ⁇ x 200 mm) manufactured by Niommen Rika Glass Co., Ltd. and melted at 190 ° C. for 2 hours to analyze the composition of the bisphenol C production reaction solution. The same procedure as above was carried out, and the amount of isopropenyl cresol produced was measured and evaluated.
• CM-A212 for petri dish measurement was fitted into the measuring section, and the zero calibration box “CM-A124" was placed over it to perform zero calibration, and then white calibration was performed using the built-in white calibration plate. ..
• CM-A210 white calibration plate
• L * was 99.40 ⁇ 0.05
• a * was 0.03 ⁇ 0.01
• b * was -0.43 ⁇ 0.01.
• YI was confirmed to be ⁇ 0.58 ⁇ 0.01.
• YI was measured by packing pellets to a depth of about 40 mm in a cylindrical glass container having an inner diameter of 30 mm and a height of 50 mm. The operation of taking out the pellets from the glass container and then performing the measurement again was repeated twice, and the average value of the measured values of a total of three times was used.
• the obtained third organic phase is cooled from 80 ° C. to 10 ° C., and after reaching 10 ° C., solid-liquid separation is performed using centrifugation (2,500 rpm for 10 minutes), and the first I got a wet cake.
• the obtained first wet cake was transferred to a beaker, 500 g of toluene was added thereto, and suspension washing was performed.
• the obtained slurry liquid was subjected to solid-liquid separation again using centrifugation (2,500 rpm for 10 minutes) to obtain 415 g of a second wet cake.
• the iron concentration of bisphenol C contained in the obtained second wet cake was 4.7 mass ppm.
• Example 1 A part of 300 g of the second wet cake of Reference Example 2 and 420 g of toluene were placed in a full-jacket type separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ° C. After confirming that the solution was uniform, a fourth organic phase was obtained. To 700 g of the obtained fourth organic phase, 200 g of 5% by mass hydrochloric acid was added and mixed for 30 minutes to remove the third aqueous phase of the lower phase to obtain a fifth organic phase. 200 g of desalinated water was added to the obtained fifth organic phase and mixed for 30 minutes to remove the fourth aqueous phase of the lower phase to obtain a sixth organic phase. When the pH of the fourth aqueous phase (the pH of the aqueous phase before supplying disodium ethylenediaminetetraacetate) was confirmed, it was pH 2.
• the obtained eighth organic phase was cooled from 80 ° C. to 10 ° C. Then, filtration was performed using a centrifuge (3000 rpm for 10 minutes) to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, a light boiling point was distilled off at an oil bath temperature of 80 ° C. under reduced pressure to obtain 210 g of white bisphenol C.
• the iron concentration of the obtained bisphenol C was 16 mass ppb.
• the number of Hazen colors was 0.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 36.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 100 mass ppm.
• Example 2 In Example 1, the same procedure as in Example 1 was carried out except that 10 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added instead of 1 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution.
• the aqueous phase before supplying disodium ethylenediaminetetraacetate was pH 2
• the aqueous phase from which disodium ethylenediaminetetraacetate was extracted was pH 9.
• the iron concentration of the obtained bisphenol C was 20 mass ppb.
• the number of Hazen colors was 0.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 34.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 95 mass ppm.
• Example 3 In Example 1, the same procedure as in Example 1 was carried out except that 100 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added instead of 1 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution.
• the aqueous phase before supplying disodium ethylenediaminetetraacetate was pH 2, and the aqueous phase from which disodium ethylenediaminetetraacetate was extracted was pH 9.
• the iron concentration of the obtained bisphenol C was 18 mass ppb.
• the number of Hazen colors was 0.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 33.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 91 parts by mass ppm.
• Example 4 A part of 300 g of the second wet cake of Reference Example 2 and 420 g of toluene were placed in a full-jacket type separable flask equipped with a thermometer and a stirrer, and the temperature was raised to 80 ° C. After confirming that the solution was uniform, a fourth organic phase was obtained. To 700 g of the obtained fourth organic phase, 300 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution was added, mixed for 30 minutes, and the liquid property was confirmed with pH test paper, and it was confirmed that the aqueous phase was pH 5. did.
• a saturated aqueous solution of sodium carbonate (18% by mass) was added thereto until the aqueous phase showed basicity, and the mixture was mixed for 30 minutes to extract the fourth aqueous phase to obtain a fifth organic phase.
• the pH of the fourth aqueous phase (the pH of the aqueous phase from which disodium ethylenediaminetetraacetate was extracted) was confirmed, it was pH 9.
• the obtained fifth organic phase was repeatedly washed with desalinated water until the electrical conductivity of the lower aqueous phase became 3.0 ⁇ S / cm or less to obtain a sixth organic phase.
• the obtained sixth organic phase was cooled from 80 ° C. to 10 ° C. Then, filtration was performed using a centrifuge (3000 rpm for 10 minutes) to obtain wet purified bisphenol C. 209 g of white bisphenol C was obtained by distilling off a light boiling point at an oil bath temperature of 80 ° C. under reduced pressure using an evaporator equipped with an oil bath.
• the iron concentration of the obtained bisphenol C was 54 mass ppb.
• the number of Hazen colors was 0.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 19.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 38.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 127 mass ppm.
• the obtained fifth organic phase 10 g of a 5% by mass aqueous solution of disodium ethylenediaminetetraacetate was added and mixed for 30 minutes, and the fourth aqueous phase was extracted to obtain a sixth organic phase.
• the fourth aqueous phase pH 9.
• the obtained sixth organic phase was repeatedly washed with desalinated water until the electrical conductivity of the lower aqueous phase became 3.0 ⁇ S / cm or less to obtain a seventh organic phase.
• the obtained seventh organic phase was cooled from 80 ° C. to 10 ° C. Then, filtration was performed using a centrifuge (3000 rpm for 10 minutes) to obtain wet purified bisphenol C. Using an evaporator equipped with an oil bath, a light boiling point was distilled off at an oil bath temperature of 80 ° C. under reduced pressure to obtain 212 g of white bisphenol C.
• the iron concentration of the obtained bisphenol C was 102 mass ppb.
• the number of Hazen colors was 12.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 42.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 65.
• the amount of isopropenyl cresol produced was 250 mass ppm.
• the fourth aqueous phase (pH of the aqueous phase before supplying disodium ethylenediaminetetraacetate) was pH 2.
• 10 g of a 5% by mass aqueous solution of disodium ethylenediaminetetraacetate was added and mixed for 30 minutes to remove the fifth aqueous phase to obtain a seventh organic phase.
• the fifth aqueous phase had a pH of 2.
• a saturated aqueous sodium carbonate solution was added to the obtained seventh organic phase until the aqueous phase showed basicity, and the mixture was mixed for 30 minutes to extract the sixth aqueous phase to obtain an eighth organic phase.
• the obtained eighth organic phase was repeatedly washed with desalinated water until the electrical conductivity of the lower aqueous phase became 3.0 ⁇ S / cm or less to obtain a ninth organic phase.
• the obtained ninth organic phase was cooled from 80 ° C. to 10 ° C. Then, filtration was performed using a centrifuge (3000 rpm for 10 minutes) to obtain wet purified bisphenol C. 209 g of white bisphenol C was obtained by distilling off a light boiling point at an oil bath temperature of 80 ° C. under reduced pressure using an evaporator equipped with an oil bath.
• the iron concentration of the obtained bisphenol C was 89 mass ppb.
• the number of Hazen colors was 5.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 41.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 80.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 210 mass ppm.
• the iron of bisphenol C obtained is obtained when the liquidity of the aqueous phase before supplying disodium ethylenediaminetetraacetic acid is acidic and the liquidity of the aqueous phase extracted from disodium ethylenediaminetetraacetic acid is basic. It can be seen that the concentration, methanol-dissolved color, melt color difference, thermal color stability, and thermal decomposition stability are improved. In Comparative Example 2, since the saturated aqueous sodium carbonate solution was added to the organic phase from which the aqueous phase had been removed after the addition of disodium ethylenediaminetetraacetate, the effect of removing iron by the chelating agent was not obtained.
• Example 5 In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5 mass% aqueous citric acid solution was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate.
• the iron concentration of the obtained bisphenol C was 22 mass ppb.
• the number of Hazen colors was 0.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 32.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 99 mass ppm.
• Example 6 In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5 mass% aqueous solution of oxalic acid was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate.
• the iron concentration of the obtained bisphenol C was 32 mass ppb.
• the number of Hazen colors was 0.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 35.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 98 mass ppm.
• Example 7 In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5% by mass aqueous solution of malonic acid was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate.
• the iron concentration of the obtained bisphenol C was 35 mass ppb.
• the number of Hazen colors was 0.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 33.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 95 mass ppm.
• Example 8 In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5 mass% aqueous solution of succinic acid was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate.
• the iron concentration of the obtained bisphenol C was 23 mass ppb.
• the number of Hazen colors was 0.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 32.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 90 mass ppm.
• Example 9 In Example 2, the same procedure as in Example 2 was carried out except that 10 g of a 5 mass% aqueous solution of tartaric acid was added instead of 10 g of a 5 mass% aqueous solution of disodium ethylenediaminetetraacetate. The iron concentration of the obtained bisphenol C was 21 mass ppb.
• the number of Hazen colors was 0.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 10.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 31.
• the thermal decomposition stability of the obtained bisphenol C was measured, the amount of isopropenyl cresol produced was 85 mass ppm.
• Comparative Example 3 In Comparative Example 2, the same procedure as in Comparative Example 2 was carried out except that 10 g of a 5 mass% aqueous citric acid solution was added instead of 10 g of a 5 mass% disodium ethylenediaminetetraacetate aqueous solution.
• the iron concentration of the obtained bisphenol C was 102 mass ppb.
• the number of Hazen colors was 10.
• the melt color difference of the obtained bisphenol C was measured, the number of Hazen colors was 39.
• the thermal color stability of the obtained bisphenol C was measured, the number of Hazen colors was 77.
• the amount of isopropenyl cresol produced was 310 mass ppm.
• Table 2 summarizes the chelating agent used, the iron concentration of the obtained bisphenol C, the methanol-dissolved color, the melt color difference, the thermal color tone stability, and the thermal decomposition stability in Examples 5 to 9 and Comparative Example 3.
• Example 10 100.00 g (0.39 mol) of bisphenol C, 86.49 g (0.4 mol) and 400 of diphenyl carbonate obtained in Example 2 in a glass reaction tank having an internal volume of 150 mL equipped with a stirrer and a distillate. 479 ⁇ L of a mass ppm cesium carbonate aqueous solution was added. The operation of reducing the pressure of the glass reaction vessel to about 100 Pa and then restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reaction vessel with nitrogen. Then, the reaction vessel was immersed in an oil bath at 200 ° C. to dissolve the contents.
• the rotation speed of the stirrer is set to 100 times per minute, and the pressure in the reaction vessel is adjusted to absolute pressure over 40 minutes while distilling off the phenol produced by the oligomerization reaction of bisphenol C and diphenyl carbonate in the reaction vessel.
• the pressure was reduced from 101.3 kPa to 13.3 kPa.
• the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the reaction vessel at 13.3 kPa and further distilling off phenol.
• the temperature outside the reaction vessel was raised to 250 ° C., and the pressure inside the reaction vessel was reduced from 13.3 kPa to 399 Pa in absolute pressure over 40 minutes to remove the distilled phenol from the system.
• the temperature outside the reaction vessel was raised to 280 ° C.
• the absolute pressure in the reaction vessel was reduced to 30 Pa, and the polycondensation reaction was carried out.
• the polycondensation reaction was terminated when the stirrer in the reaction tank became a predetermined stirring power.
• the time from the temperature rise to 280 ° C. to the end of the polymerization was 210 minutes.
• the reaction vessel was repressurized to 101.3 kPa with nitrogen at an absolute pressure, and then the pressure was increased to 0.2 MPa with a gauge pressure, and the polycarbonate resin was extracted from the bottom of the reaction vessel in a strand shape to obtain a strand-shaped polycarbonate resin. .. Then, the strands were pelletized using a rotary cutter to obtain a pellet-shaped polycarbonate resin.
• the viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24700, and the pellet YI was 7.7, so that a polycarbonate resin having a good hue could be obtained.
• Example 11 10 g of 1,1-bis (4-hydroxyphenyl) dodecane and 14 g of toluene obtained in Reference Example 3 were placed in an eggplant-shaped flask equipped with a magnetic rotor and dissolved at 80 ° C. to obtain a toluene solution. 7 g of 5% by mass hydrochloric acid was added thereto, and the mixture was stirred. After allowing the obtained mixed solution to stand for 30 minutes, the aqueous phase was removed to obtain a first organic phase. The pH of the removed aqueous phase was less than 1.
• the obtained third organic phase was washed repeatedly with 7 g of desalinated water three times to obtain a fourth organic phase.
• the obtained fourth organic phase was cooled to 10 ° C. to obtain a slurry liquid.
• the obtained slurry liquid was filtered, and the obtained cake was dried at 70 ° C. under reduced pressure to obtain 7.5 g of 1,1-bis (4-hydroxyphenyl) dodecane.
• the iron concentration of the obtained 1,1-bis (4-hydroxyphenyl) dodecane was 100 mass ppb.
• the obtained second organic phase was cooled to 10 ° C. to obtain a slurry liquid.
• the obtained slurry liquid was filtered, and the obtained cake was dried at 70 ° C. under reduced pressure to obtain 7.5 g of 1,1-bis (4-hydroxyphenyl) dodecane.
• the iron concentration of the obtained 1,1-bis (4-hydroxyphenyl) dodecane was 400 mass ppb.
• Table 3 shows the presence or absence of a pH change before and after the addition of a 5% by mass aqueous solution of disodium ethylenediaminetetraacetate and the iron concentration of the obtained 1,1-bis (4-hydroxyphenyl) dodecane in Example 11 and Comparative Example 4. I summarized it in.

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