JP5578710B2 - Highly transparent 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and process for producing the same - Google Patents

Description

The present invention relates to a highly transparent 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene useful as a highly transparent resin material suitable for the optical field and a method for producing the same.

Fluorene derivatives such as 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene are excellent in heat resistance and transparency, and have a high refractive index (for example, epoxy resins, polyesters, polyethers, polycarbonates, etc.) ) Is promising as a raw material for producing. In particular, transparent resin such as polycarbonate is used for parts of optical system equipment used for information and communication equipment, and is expected as a raw material for optical lenses, films, plastic optical fibers, optical disks and the like.

As a method for producing 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, a method of reacting 9,9-bis (4-hydroxyphenyl) fluorene and ethylene carbonate in the presence of a decarboxylation catalyst (patent) Document 1) is disclosed, and a method of reacting fluorenone and phenoxyethanol using sulfuric acid and thiols as catalysts (Patent Document 2) is disclosed.

However, in these methods, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is highly colored, and repetitive purification is required to use it as a highly transparent resin raw material for optical applications. Disadvantageous.

Disclosed is a method of reacting fluorenone and phenoxyethanol in the presence of a heteropolyacid catalyst as 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene having a good hue and usable as an optical resin raw material (Patent Document 3). In addition, a method of reacting fluorenone and phenoxyethanol in the presence of an ion exchange resin catalyst (Patent Document 4) is disclosed.

However, these are all included in 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, such as high purity by high performance liquid chromatography analysis of the target product, low residual sulfur content and low metal content. The relationship between the physical properties of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (for example, pH) and transparency, or the polymerizability when making a resin, It does not teach how to obtain a compound having these physical properties.

  On the other hand, in recent optical discs, since the wavelength of the recording laser is lowered, it is necessary to improve the transparency at the wavelength used, and in the optical film for flat panel display, transparency is required to improve the quality. There is a need for a highly transparent resin that is free of coloring, such as the need for improvement. For this purpose, a highly transparent 9,9-bis (4- (2 There is a need for -hydroxyethoxy) phenyl) fluorene. In addition, in order to produce a material excellent in thermal and optical properties, a resin having a high molecular weight, a narrow molecular weight distribution, and a low unreacted monomer or oligomer content is required. There is a need for 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. The production methods described in the above-mentioned patent documents are insufficient for obtaining a resin raw material having both high transparency and high polymerizability.

JP-A-9-255609

JP-A-7-165657

JP 2007-197368

JP 2009-46416

The present invention is highly transparent 9,9-bis (4- (2-hydroxyethoxy), which is useful as a highly transparent resin raw material suitable for the optical field, has high transparency, little coloration, and excellent polymerization activity. Phenyl) fluorene and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors have found that 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene having a specific pH when dissolved in a solvent is obtained. , Transparency such as transmittance and molten color, and excellent polymerizability in making a resin, and in the presence of a heteropolyacid catalyst, fluorenone reacts with 2-phenoxyethanol to produce 9,9-bis (4- In the method of obtaining (2-hydroxyethoxy) phenyl) fluorene, it is possible to neutralize with a stoichiometrically insufficient amount of an alkali hydroxide aqueous solution with respect to the heteroacid and polyacid constituting the heteropolyacid, and Has a specific pH when dissolved in a solvent by neutralizing the heteropolyacid and the heteroacid with a stoichiometrically insufficient amount of an aqueous alkali hydroxide solution. That 9,9-bis (4- (2-hydroxyethoxy) phenyl) found that fluorene can be easily manufactured, and have completed the present invention.

That is, the present invention provides the following (1) to (6).
(1) Fluorenone and 2-phenoxyethanol are reacted in the presence of a heteropolyacid catalyst, and neutralized with a stoichiometrically insufficient amount of an aqueous alkali hydroxide solution to the heteroacid and polyacid constituting the heteropolyacid after the reaction. A process for producing 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, characterized in that:
(2) Fluorenone and 2-phenoxyethanol are reacted in the presence of a heteropolyacid catalyst, and an aqueous alkali hydroxide solution of 0.33 equivalents or more and less than 0.96 equivalents with respect to the heteroacid and polyacid constituting the heteropolyacid after the reaction The method according to item (1), wherein the method is neutralized.
(3) Fluorenone and 2-phenoxyethanol are reacted in the presence of a heteropolyacid catalyst, and an aqueous alkali hydroxide solution having a heteropolyacid content of 0.40 equivalents or more and less than 0.90 equivalents with respect to the heteroacid and polyacid after the reaction. The production method according to item (1), wherein the neutralization is carried out.
(4) 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene was contained in an amount of 95% by weight or more, and dissolved in 17 times distilled water / dioxane (= 2/3 volume ratio) solvent on a mass basis. 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, characterized in that the solution has a pH at 25 ° C. of 6.2 to 7.8.
(5) The hue APHA at the time of melting is 120 or less, and the transmittance at 400 nm of a solution obtained by dissolving the substance in dioxane is 99% or more, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
(6) Fluorenone and 2-phenoxyethanol are reacted in the presence of a heteropolyacid catalyst, and neutralized with a stoichiometrically insufficient amount of an aqueous alkali hydroxide solution to the heteroacid and polyacid constituting the heteropolyacid after the reaction. The 9,9-bis having a pH of 6.2 to 7.8 at 25 ° C. of a solution dissolved in distilled water / dioxane (= 2/3 volume ratio) solvent 17 times by mass based on mass (4- (2-hydroxyethoxy) phenyl) fluorene.

According to the present invention, a highly transparent 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene having a specific pH when dissolved in a solvent and a method for producing the same are provided. Further, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene obtained by the present invention and having a specific pH when dissolved in a solvent is excellent in transparency such as transmittance and molten color. It is excellent as a raw material for highly transparent resins suitable for the optical field.

Hereinafter, the present invention will be described together with embodiments thereof.
The highly transparent 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene of the present invention contains 95% or more of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, and has a mass. The pH at 25 ° C. of a solution dissolved in 17 times distilled water / dioxane (= 2/3 volume ratio) solvent is 6.2 to 7.8. Furthermore, the hue APHA at the time of melting is 120 or less, and the transmittance at 400 nm of a 16.2% by weight dioxane solution is 99% or more.

  In the present invention, it is important for achieving the object of the present invention that the pH of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is 6.2 to 7.8. When the pH is higher than 7.8, the hue of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is deteriorated, which is not preferable as a highly transparent resin material. When the pH is lower than 6.2, the transparency deteriorates, such as white turbidity when 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene melts, which is not preferable as a highly transparent resin raw material. Moreover, resin polymerization performance falls. More preferably, the pH is in the range of 6.5 to 7.5.

Furthermore, the hue APHA at the time of melting is 120 or less, preferably 100 or less, and the transmittance at 400 nm of a 16.2% by weight dioxane solution is 99% or more. When the hue APHA at the time of melting of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is larger than 120, coloring is observed even when the resin is used, which is not preferable. When the transmittance at 400 nm is lower than 99%, transparency is lowered even when a resin is used, which is not preferable.

In the present invention, a highly transparent 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene production method comprises reacting fluorenone with 2-phenoxyethanol in the presence of a heteropolyacid catalyst, and reacting the heteropolyacid after the reaction. It is carried out by neutralizing with a stoichiometrically deficient amount of an aqueous alkali hydroxide solution with respect to the heteroacid and polyacid that constitute the compound. Usually, the highly transparent 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene obtained by these methods is dissolved in 17 times distilled water / dioxane (= 2/3 volume ratio) solvent on a mass basis. The pH of the solution at 25 ° C. is 6.2 to 7.8.

  The method for carrying out the reaction between fluorenone and 2-phenoxyethanol is not particularly limited. Usually, fluorenone, 2-phenoxyethanol and a heteropolyacid are charged into a reaction apparatus, and in the air or an inert gas such as nitrogen or helium. The reaction can be carried out by heating and stirring at 50 to 300 ° C., preferably 80 to 250 ° C., more preferably 120 to 180 ° C. in the presence or absence of an inert solvent such as toluene and xylene. The dehydration method is not particularly limited, and examples thereof include dehydration by adding a dehydrating agent, dehydration by reduced pressure, dehydration by azeotropy with a solvent under normal pressure or reduced pressure, and the like.

  The heteropolyacid used in the present invention is a general term for compounds formed by condensation of two or more different inorganic oxygen acids, and is a different kind of condensate around a central oxygen acid (heteroacid). Various heteropolyacids are possible by combining oxygen acids (polyacids). A small number of elements that form a central oxygen acid are called heteroelements, and an element that forms oxygen acid that condenses around them is called a polyelement. A polyelement may be a single type or multiple types May be used.

The hetero element of the oxygen acid constituting the heteropolyacid is not particularly limited, for example, copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, phosphorus, Examples include arsenic, antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, iridium, and platinum. Preferably it is phosphorus or silicon. Moreover, the poly element of the oxygen acid which comprises heteropoly acid is not specifically limited, For example, vanadium, molybdenum, tungsten, niobium, and tantalum are mentioned. Vanadium, molybdenum and tungsten are preferred.

The heteropolyacid anion constituting the heteropolyacid skeleton includes various compositions. In the present invention, a heteropolyacid having a Keggin structure is used. Here, the Keggin structure is a heteropolyacid in which the structural formula of the anion portion is represented by XM ₁₂ O ₄₀ , and MO ₆ having a regular octahedral structure in which an oxygen atom is six-coordinated to an atom corresponding to M has a side This is a structure in which a unit of M ₃ O ₁₃ formed by gathering three together is formed, and further, four vertices are gathered together to form a configuration in which a hetero atom is coordinated at the center. Specific examples of the heteropolyacid having a Keggin structure include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid.

After the reaction, the heteropolyacid is neutralized with a stoichiometrically insufficient amount of an alkali hydroxide aqueous solution with respect to the heteroacid and polyacid.

Usually, in order to deactivate the function of the acid catalyst, it is conceivable to carry out neutralization with a stoichiometrically equivalent amount or more of alkali hydroxide with respect to the acid used. For example, when tungstic acid (polyacid) and phosphoric acid (heteroacid) constituting phosphotungstic acid [H ₃ (PW ₁₂ O ₄ )] are neutralized with sodium hydroxide, sodium tungstate (Na ₂ WO ₄ ) and phosphorus It becomes sodium acid (Na ₃ PO ₄ ). As is apparent from this chemical formula, 27 moles of sodium hydroxide are usually required to completely neutralize 12 moles of tungstic acid and 1 mole of phosphoric acid.

However, when phosphotungstic acid is actually titrated with a sodium hydroxide solution, the pH becomes neutral with 9 moles (0.33 equivalents) of sodium hydroxide per mole of phosphotungstic acid as shown in FIG. . That is, it was found that neutralization is possible with a stoichiometrically insufficient amount of alkali hydroxide. Furthermore, by neutralizing with a stoichiometrically insufficient amount of alkali hydroxide, the pH at 25 ° C. of a solution dissolved in 17 times distilled water / dioxane (= 2/3 volume ratio) solvent on a mass basis is obtained. It has been found that highly transparent 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, which is 6.2 to 7.8, is easily obtained.

The reason for neutralization with a stoichiometrically insufficient amount of alkali hydroxide is not necessarily clear, but tungstophosphate ion ([PW ₁₁ O ₃₉ ] ⁷⁻ ) and tungstic acid in the process of neutralization of phosphotungstic acid Ions ([WO ₄ ] ²⁻ ) are formed, and sodium ions bind to these anions [PW ₁₁ O ₃₉ ] ⁷⁻ and [WO ₄ ] ²⁻ to substantially convert 1 mol of phosphotungstic acid. It is believed to be neutralized with 9 moles of sodium hydroxide.

Although it does not specifically limit as alkali hydroxide used by this invention, For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide etc. are mentioned. Of these, sodium hydroxide or potassium hydroxide is preferred from the viewpoint of cost and the stability of the compound. More preferred is sodium hydroxide.

  The amount of the alkali hydroxide used is not particularly limited as long as it is a stoichiometrically insufficient amount with respect to the heteroacid and polyacid constituting the heteropolyacid, but is preferably not more than about 0.1 mol per 1 mol of the heteropolyacid. It is 33 equivalents or more and less than 0.96 equivalents, more preferably 0.40 equivalents or more and less than 0.90 equivalents, especially 0.50 equivalents or more and less than 0.90 equivalents.

The 9,9-bis (4- (2-hydroxyethoxy) phenyl obtained when an alkali hydroxide of a stoichiometrically larger amount than the heteroacid and polyacid constituting the heteropolyacid is used. ) Hue APHA and transmittance at the time of melting fluorene deteriorate.
When the amount of alkali hydroxide used is small, the catalytic function cannot be completely deactivated, and high-purity 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene may not be obtained. In addition, when a resin such as polycarbonate is produced, sufficient polymerization activity may not be obtained, or the resin may become turbid.
When the heteropolyacid catalyst is not neutralized, impurities increase due to the influence of the remaining catalyst, and high-purity 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene cannot be obtained. In addition, sufficient polymerization activity cannot be obtained when a resin such as polycarbonate is produced.

  According to the present invention, unreacted 2-phenoxyethanol is then distilled off from the neutralized solution by heating and concentration, and the product layer is washed with water.

The heating and concentration conditions for unreacted 2-phenoxyethanol are not particularly limited, but under normal pressure or reduced pressure, preferably under reduced pressure of 0.1 kPa to 4.7 kPa, 80 to 250 ° C., preferably 100 to 170. It concentrates at the temperature of 100 degreeC, More preferably, 100-150 degreeC. When the concentration temperature is high, the yield and purity decrease due to the decomposition reaction. Moreover, although it is preferable to distill off the whole amount of unreacted 2-phenoxyethanol, the following operation can be performed while leaving a part.

After concentration, water and an organic solvent that can be separated from water are added and dissolved in the concentrated residue, and then separated into a product layer and an aqueous layer containing the organic solvent and washed. At this time, the pH of the drainage water layer is usually 6.0 to 8.0.

Although the water used for this invention is not specifically limited, Industrial water, tap water, deionized water, distilled water, etc. can be used. In particular, it is preferable to use deionized water or distilled water because the metal content in 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene decreases.

  The organic solvent that can be separated from water used in the present invention is not particularly limited, but aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, and halogenated aromatics such as chlorobenzene and dichlorobenzene. Hydrocarbons, aliphatic hydrocarbons such as pentane, hexane, heptane, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, di-iso-propyl ether, methyl-tert-butyl ether, Examples include ethers such as diphenyl ether, and esters such as ethyl acetate and n-butyl acetate. Among these, toluene, xylene, chlorobenzene, and dichlorobenzene are preferable. The amount to be used is not particularly limited, but is usually 0.1 times or more, preferably 0.5 to 100 times by weight, more preferably 1 from the weight of fluorenone from the viewpoint of economy. About 20 times by weight. These organic solvents may be used alone or in a mixture of two or more.

The method for isolating 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene from the product layer after washing is not particularly limited, but dehydration, crystallization, washing, filtration, drying, etc. The conventional method can be used. For example, after the dehydration operation, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene crystals are precipitated by cooling crystallization.
The precipitated crystals are collected by filtration or the like. The obtained crystal may be washed using a solvent or the like used for crystallization, or may be dried.

The 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene thus obtained was obtained by dissolving a solution in 17 times distilled water / dioxane (= 2/3 volume ratio) solvent on a mass basis at 25 ° C. It is a highly transparent 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene having a pH of 6.2 to 7.8 and excellent as a highly transparent resin raw material.

(Example)
Examples of the present invention are shown below, but the present invention is not limited thereto. In addition, pH, the transmittance | permeability, and the polymerization evaluation method in an Example and a comparative example are as follows.

Method for measuring physical properties of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene:
[PH measurement]
After 3 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene was dissolved in 30 ml of dioxane, 20 ml of distilled water was added and the mixture was shaken well to have pH 4.01, pH 6.86 and pH 9.18. Using a pH measuring device (HORIBA D-13, electrode: HORIBA 6378 type) calibrated with a standard solution (manufactured by Kishida Chemical Co., Ltd.), the pH was measured according to JIS K3362-1998.
[Melting hue measurement]
A molten color after 15 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene was placed in a colorimetric tube and heated and melted at 230 ° C. for 2 hours was compared with the APHA standard solution.
[Transmittance measurement]
Weighed 1.67 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene in a 10 ml volumetric flask and made a constant volume with 1,4-dioxane as a sample solution. Using a meter (UV-2450, manufactured by Shimadzu Corporation), the sample solution was put into a square cell having an optical path length of 10 mm, and light transmittance within a wavelength range of 400 to 700 nm was measured at room temperature. The higher the transmittance at the above wavelength, the better the transparency.
[Polymerization test]
A reaction comprising 80.0 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 39.8 g of diphenyl carbonate, and 9.0 × 10 ⁻³ g of cesium carbonate, equipped with a stirrer, a distillation column, and a decompression device After putting in a container and dissolving in a nitrogen atmosphere, the ester exchange reaction was carried out by gradually reducing the pressure and raising the temperature to 230 ° C./1 torr while distilling off the produced phenol. The obtained polycarbonate resin was measured for polystyrene-converted weight average molecular weight (Mw) using GPC (HLC-8220 manufactured by TOSOH) and THF as a developing solvent.

In a glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a reflux condenser, fluorenone 50.0 g (0.28 mol), phosphotungstic acid 1.2 g (3.51 × 10 ⁻⁴ mol), phenoxyethanol 383 0.0 g (2.77 mol) was added, and the temperature was gradually raised to 130 ° C. under a reduced pressure of 2.0 kPa. Thereafter, the reaction was carried out by stirring for 5 hours under the reduced pressure of 2.0 to 3.0 kPa while removing water produced at a temperature of 130 to 135 ° C. from the reaction system.
The resulting reaction mixture was cooled to 80 ° C., and 1.2 g of a 29% aqueous sodium hydroxide solution (8.42 × 10 ⁻³ mol, 0.89 equivalent to phosphotungstic acid) was added and stirred for 1 hour. Thereafter, the solution was concentrated under reduced pressure while gradually raising the temperature to 150 ° C., and phenoxyethanol was distilled off.
The obtained concentrated liquid was cooled, 350 g of toluene and 50 g of ion-exchanged water were added, and the mixture was stirred at 80 ° C. for 30 minutes to distribute the target product to the organic layer. The solution was allowed to stand for 30 minutes, and then the aqueous layer was separated and the organic layer was recovered. Furthermore, the obtained organic layer was washed twice with 50 g of ion-exchanged water.
The obtained organic layer was heated to 110 ° C. and stirred for 1 hour. During this time, water distilled out of the system was separated and removed by an oil-water separator. Next, after confirming that the obtained organic phase was a homogeneous solution, it was cooled to 65 ° C. To this solution, 0.2 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene crystal was added as a seed crystal, and the mixture was kept at 65 ° C. for 2 hours to confirm crystal precipitation. Subsequently, it cooled to 25 degreeC and the precipitated crystal | crystallization was separated by filtration.
The crystals were dried under reduced pressure, and the solvent was removed to obtain 97.5 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene white crystals. The product yield based on the raw material fluorenone was 80.1%, and the LC purity was 98.8%.
The resulting 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene had a pH of 7.0, a melt hue of APHA80, and a transmittance of 99.5%. As a result of the polymerization test, the molecular weight Mw of the obtained resin was 38000.

In a glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a reflux condenser, fluorenone 50.0 g (0.28 mol), phosphotungstic acid 1.2 g (3.51 × 10 ⁻⁴ mol), phenoxyethanol 383 0.0 g (2.77 mol) was added, and the temperature was gradually raised to 130 ° C. under a reduced pressure of 2.0 kPa. Thereafter, the reaction was carried out by stirring for 5 hours under the reduced pressure of 2.0 to 3.0 kPa while removing water produced at a temperature of 130 to 135 ° C. from the reaction system.
The obtained reaction mixture was cooled to 80 ° C., 0.75 g of a 29% aqueous sodium hydroxide solution (5.27 × 10 ⁻³ mol, 0.56 equivalent to phosphotungstic acid) was added, and the mixture was stirred for 1 hour. Thereafter, the solution was concentrated under reduced pressure while gradually raising the temperature to 150 ° C., and phenoxyethanol was distilled off.
The obtained concentrated liquid was cooled, 350 g of toluene and 50 g of ion-exchanged water were added, and the mixture was stirred at 80 ° C. for 30 minutes to distribute the target product to the organic layer. The solution was allowed to stand for 30 minutes, and then the aqueous layer was separated and the organic layer was recovered. Furthermore, the obtained organic layer was washed twice with 50 g of ion-exchanged water.
The obtained organic layer was heated to 110 ° C. and stirred for 1 hour. During this time, water distilled out of the system was separated and removed by an oil-water separator. Next, after confirming that the obtained organic phase was a homogeneous solution, it was cooled to 65 ° C. To this solution, 0.2 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene crystal was added as a seed crystal, and the mixture was kept at 65 ° C. for 2 hours to confirm crystal precipitation. Subsequently, it cooled to 25 degreeC and the precipitated crystal | crystallization was separated by filtration.
The crystals were dried under reduced pressure, and the solvent was removed to obtain 97.9 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene white crystals. The product yield based on the raw material fluorenone was 80.5%, and the LC purity was 98.3%.
The resulting 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene had a pH of 6.5, a melt hue of APHA 60, and a transmittance of 99.5%. As a result of the polymerization test, the molecular weight Mw of the obtained resin was 34,000.

In a glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a reflux condenser, fluorenone 80.0 g (0.44 mol), silicotungstic acid 1.8 g (5.44 × 10 ⁻⁴ mol), phenoxyethanol 610 0.0 g (4.42 mol) was added, and the temperature was gradually raised to 130 ° C. under a reduced pressure of 2.0 kPa. Thereafter, the reaction was carried out by stirring for 5 hours under the reduced pressure of 2.0 to 3.0 kPa while removing water produced at a temperature of 130 to 135 ° C. from the reaction system.
The obtained reaction mixture was cooled to 80 ° C., and 1.7 g (1.19 × 10 ⁻² mol, 0.84 equivalent to silicotungstic acid) of 40% aqueous potassium hydroxide solution was added and stirred for 1 hour. Thereafter, the solution was concentrated under reduced pressure while gradually raising the temperature to 150 ° C., and phenoxyethanol was distilled off.
The obtained concentrated liquid was cooled, 560 g of toluene and 80 g of ion-exchanged water were added, and the mixture was stirred at 80 ° C. for 30 minutes to distribute the target product to the organic layer. The solution was allowed to stand for 30 minutes, and then the aqueous layer was separated and the organic layer was recovered. Furthermore, the obtained organic layer was washed twice with 80 g of ion exchange water.
The obtained organic layer was heated to 110 ° C. and stirred for 1 hour. During this time, water distilled out of the system was separated and removed by an oil-water separator. Next, after confirming that the obtained organic phase was a homogeneous solution, it was cooled to 65 ° C. To this solution, 0.3 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene crystals was added as a seed crystal, and the mixture was kept at 65 ° C. for 2 hours to confirm crystal precipitation. Subsequently, it cooled to 25 degreeC and the precipitated crystal | crystallization was separated by filtration.
The crystals were dried under reduced pressure, and the solvent was removed to obtain 155.4 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene white crystals. The product yield based on the raw material fluorenone was 79.8%, and the LC purity was 98.5%.
The obtained 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene had a pH of 7.1, a melt hue of APHA60, and a transmittance of 99.5%. As a result of the polymerization test, the obtained resin had a molecular weight Mw of 38000.

(Comparative Example 1)
In a glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a reflux condenser, fluorenone 50.0 g (0.28 mol), phosphotungstic acid 1.2 g (3.51 × 10 ⁻⁴ mol), phenoxyethanol 383 0.0 g (2.77 mol) was added, and the temperature was gradually raised to 130 ° C. under a reduced pressure of 2.0 kPa. Thereafter, the reaction was carried out by stirring for 5 hours under the reduced pressure of 2.0 to 3.0 kPa while removing water produced at a temperature of 130 to 135 ° C. from the reaction system.
The obtained reaction mixture was cooled to 80 ° C., 1.7 g of a 29% sodium hydroxide aqueous solution (1.23 × 10 ⁻² mol, 1.30 equivalents relative to phosphotungstic acid) was added, and the mixture was stirred for 1 hour. Thereafter, the solution was concentrated under reduced pressure while gradually raising the temperature to 150 ° C., and phenoxyethanol was distilled off.
The obtained concentrated liquid was cooled, 350 g of toluene and 50 g of ion-exchanged water were added, and the mixture was stirred at 80 ° C. for 30 minutes to distribute the target product to the organic layer. The solution was allowed to stand for 30 minutes, and then the aqueous layer was separated and the organic layer was recovered. Furthermore, the obtained organic layer was washed twice with 50 g of ion-exchanged water.
The obtained organic layer was heated to 110 ° C. and stirred for 1 hour. During this time, water distilled out of the system was separated and removed by an oil-water separator. Next, after confirming that the obtained organic phase was a homogeneous solution, it was cooled to 65 ° C. To this solution, 0.2 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene crystal was added as a seed crystal, and the mixture was kept at 65 ° C. for 2 hours to confirm crystal precipitation. Subsequently, it cooled to 25 degreeC and the precipitated crystal | crystallization was separated by filtration.
The crystals were dried under reduced pressure, and the solvent was removed to obtain 96.5 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene white crystals. The product yield based on the raw material fluorenone was 79.3%, and the LC purity was 98.1%.
The resulting 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene had a pH of 7.9, a molten hue of APHA 250, and a transmittance of 97.1%.

(Comparative Example 2)
In a glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a reflux condenser, fluorenone 50.0 g (0.28 mol), phosphotungstic acid 1.2 g (3.51 × 10 ⁻⁴ mol), phenoxyethanol 383 0.0 g (2.77 mol) was added, and the temperature was gradually raised to 130 ° C. under a reduced pressure of 2.0 kPa. Thereafter, the reaction was carried out by stirring for 5 hours under the reduced pressure of 2.0 to 3.0 kPa while removing water produced at a temperature of 130 to 135 ° C. from the reaction system.
The obtained reaction mixture was cooled to 80 ° C., 0.2 g of a 29% aqueous sodium hydroxide solution (1.31 × 10 ⁻³ mol, 0.14 equivalent to phosphotungstic acid) was added, and the mixture was stirred for 1 hour. Thereafter, the solution was concentrated under reduced pressure while gradually raising the temperature to 150 ° C., and phenoxyethanol was distilled off.
The obtained concentrated liquid was cooled, 350 g of toluene and 50 g of ion-exchanged water were added, and the mixture was stirred at 80 ° C. for 30 minutes to distribute the target product to the organic layer. The solution was allowed to stand for 30 minutes, and then the aqueous layer was separated and the organic layer was recovered. Furthermore, the obtained organic layer was washed twice with 50 g of ion-exchanged water.
The obtained organic layer was heated to 110 ° C. and stirred for 1 hour. During this time, water distilled out of the system was separated and removed by an oil-water separator. Next, after confirming that the obtained organic phase was a homogeneous solution, it was cooled to 65 ° C. To this solution, 0.2 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene crystal was added as a seed crystal, and the mixture was kept at 65 ° C. for 2 hours to confirm crystal precipitation. Subsequently, it cooled to 25 degreeC and the precipitated crystal | crystallization was separated by filtration.
The crystals were dried under reduced pressure, and the solvent was removed to obtain 97.3 g of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene white crystals. The product yield based on the raw material fluorenone was 80.0%, and the LC purity was 98.0%.
The resulting 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene had a pH of 5.0, a melt hue of APHA90, and a transmittance of 99.0%. Further, as a result of the polymerization test, the polymerization reaction hardly proceeded, and a polycarbonate resin could not be obtained.

Claims (2)

Fluorenone is reacted with 2-phenoxyethanol in the presence of a heteropolyacid catalyst, and neutralized with an aqueous alkali hydroxide solution of 0.33 equivalents or more and less than 0.96 equivalents to the heteroacid and polyacid constituting the heteropolyacid after the reaction. 9 you, characterized in that, 9- bis (4- (2-hydroxyethoxy) phenyl) mETHOD fluorene. Fluorenone and 2-phenoxyethanol are reacted in the presence of a heteropolyacid catalyst, and neutralized with an aqueous alkali hydroxide solution in an amount of 0.40 equivalents or more and less than 0.90 equivalents based on the heteroacid and polyacid constituting the heteropolyacid after the reaction. The manufacturing method according to claim 1, wherein: