JP5572430B2 - Process for producing 9,9-bis (4-hydroxyphenyl) fluorenes - Google Patents

Description

The present invention relates to a production method for obtaining 9,9-bis (4-hydroxyphenyl) fluorenes useful as a resin raw material or the like with high purity. Specifically, the present invention relates to a method for producing 9,9-bis (4-hydroxyphenyl) fluorenes using a single aliphatic ketone solvent or a mixed solvent of a single aliphatic ketone and water.

9,9-bis (9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc.
4-Hydroxyphenyl) fluorenes are useful compounds as production raw materials such as epoxy resins, polycarbonate resins, and polyesters, thermal paper storage stabilizers, developers, antioxidants, rubber deterioration inhibitors, and the like. For example, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene has a configuration called a cardo structure, and due to its numerous aromatic rings,
Useful as a monomer for optical applications because it exhibits high refractive index and high heat resistance, and each aromatic ring faces in a different direction, so it has the property of canceling optical anisotropy and low birefringence. Compound.

9,9-bis (4-hydroxyphenyl) fluorenes are usually obtained by dehydrating condensation of two corresponding phenols and the corresponding 9-fluorenone in the presence of an acid catalyst. It is manufactured by refining by a method such as recrystallization. At that time, in the separation of the crude 9,9-bis (4-hydroxyphenyl) fluorene from the reaction mixture, or in the purification of the separated crude 9,9-bis (4-hydroxyphenyl) fluorene, the purity is high. In order to separate and purify the target product by yield, a method is known in which 9,9-bis (4-hydroxyphenyl) fluorenes and a compound that forms an adduct are added and the adduct is separated as crystals. .

For example, as a method for purifying 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, unreacted phenol is distilled off after completion of the reaction, and the resulting 9,9-bis (4-hydroxyphenyl) fluorene is obtained. There is known a method in which diethyl ether, acetone or the like is added to a reaction solution containing, and the precipitated crystals are separated, and then toluene is added thereto for recrystallization, separation and drying (Patent Document 1). However, this purification method has a problem that one or more organic solvents are used, the operation is complicated, and the yield is low.

Further, as a method for purifying 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, a lower aliphatic alcohol and a lower aliphatic are added to the reaction mixture containing 9,9-bis (4-hydroxyphenyl) fluorene. A method of crystallization by adding a mixed solvent containing a ketone (Patent Document 2), or a host guest complex containing bisphenolfluorenes as a host compound and acetonitrile, acetone or the like as a guest compound is decomposed or dissolved in a hydrocarbon solvent. And then purifying bisphenolfluorenes by distilling off the guest compound (Patent Document 3) and the like. However, in these purification methods, one or more or mixed organic solvents are used, and there is a problem that it is difficult to recover and use the solvent for industrial mass production.

Furthermore, a method of performing crystallization by adding nitrile after distilling off generated water together with hydrochloric acid from a reaction mixture containing 9,9-bis (4-hydroxyphenyl) fluorene is also known (Patent Document 4). . This purification method uses a single organic solvent, but the solvent nitriles are expensive,
In order to obtain a high-purity product, it is necessary to perform washing at a low temperature or to perform crystallization multiple times, which is problematic as an industrial method.

Japanese Patent Laid-Open No. 62-230741 Japanese Patent Laid-Open No. 10-245352 JP 2004-91414 A Japanese Patent Laid-Open No. 06-145088

The present invention is intended to solve the problems associated with the prior art as described above, and is high in purity without coloration to such an extent that it can be used in applications requiring excellent optical characteristics. Industrially, 9,9-bis (4
An object of the present invention is to provide a method for producing -hydroxyphenyl) fluorene.

As a result of intensive studies to solve the above problems, the present inventors have the property that 9,9-bis (4-hydroxyphenyl) fluorenes and aliphatic ketones form an adduct, but the fat In the aromatic ketone solvent, the difference between the solubility of the adduct above the decomposition temperature and the solubility at a temperature at which the adduct is stable is found to be remarkably large. For example, acetone adduct is acetone in acetone at normal pressure. Even if it is below the boiling point of the solution, it is below the decomposition temperature and does not dissolve at all, or it does not dissolve at all, so there is no purification effect. It turns out that when you take advantage of its properties,
It is possible to purify with high purity using a single inexpensive organic solvent, and the recovery of the solvent becomes extremely simple. Therefore, 9,9-bis (4-hydroxyphenyl) with high purity and good hue is obtained.
The present inventors have found that fluorenes can be easily obtained with high yield and good economic efficiency.

That is, according to the present invention, an aliphatic ketone adduct of 9,9-bis (4-hydroxyphenyl) fluorene is added in the presence of the aliphatic ketone solvent or a mixed solvent of the aliphatic ketone and water.
The adduct is decomposed and dissolved at a temperature higher than the decomposition temperature of the adduct, and then cooled, and the precipitated aliphatic ketone adduct is separated to obtain a purified aliphatic ketone adduct. A method for producing 9,9-bis (4-hydroxyphenyl) fluorenes is provided.
Moreover, the manufacturing method of 9,9-bis (4-hydroxyphenyl) fluorene characterized by drying-removing this aliphatic ketone from the obtained refined aliphatic ketone adduct is provided.

In the production method of the present invention, since a single aliphatic ketone solvent or a mixed solvent of a single aliphatic ketone and water is used, there is no need to separate the organic solvent, and the solvent can be easily reused. This is an advantageous manufacturing method. In addition, when a mixed solvent of an aliphatic ketone and water is used, a refined product with a low metal can be obtained, and the decomposition temperature or dissolution temperature of the adduct can be kept low.

Further, by using such a single aliphatic ketone solvent or a mixed solvent of a single aliphatic ketone and water, 9,9-bis (4-hydroxyphenyl) fluorenes having a purity of 99.0% or more can be obtained. A purified aliphatic ketone adduct can be obtained, and then the aliphatic ketone is dried and removed from the purified aliphatic ketone adduct to obtain a high purity 9,9-bis (4-hydroxy) having a purity of 99.0% or more. Phenyl) fluorenes can be produced with good yield. Moreover, the hue of the obtained 9,9-bis (4-hydroxyphenyl) fluorenes is not colored and has high transparency or light transmittance.

（式中、Ｒ_１〜Ｒ_３はそれぞれ独立して水素原子又は炭素原子数４以下のアルキル基であ
り、ｎは０または１〜３の整数であり、但しｎが２以上の場合、Ｒ_３は同一であっても異
なっていてもよい。） In the method for producing 9,9-bis (4-hydroxyphenyl) fluorenes according to the present invention, the 9,9-bis (4-hydroxyphenyl) fluorenes may be represented by the following general formula (1):
It is represented by

(Wherein R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group having 4 or less carbon atoms, n is an integer of 0 or 1 to 3, provided that when n is 2 or more, R ₃ May be the same or different.)

In the formula (1), when R _{1 to} R ₃ are alkyl groups having 4 or less carbon atoms, examples of the alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -A butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, etc. can be mentioned.

In the formula (1), a case where R ₁ and R ₂ are hydrogen atoms is preferable, and a case where R ₁ and R ₂ are hydrogen atoms and n is 1 is more preferable. Most preferred is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene represented by the following formula.

Such 9,9-bis (4-hydroxyphenyl) fluorenes can be obtained by a known method of dehydrating and condensing fluorenones and phenols in the presence of an acid catalyst.
The raw material fluorenones include, for example, 9-fluorenone, 2-methyl-9-fluorenone, corresponding to the fluorene group of 9,9-bis (4-hydroxyphenyl) fluorenes represented by the general formula (1), , 8-dimethyl-9-fluorenone and the like. Further, as the raw material phenols, for example, corresponding to the hydroxyphenyl group of 9,9-bis (4-hydroxyphenyl) fluorenes represented by the general formula (1), for example, phenol, o-
Examples include cresol, 2-isopropylphenol, 2,5-xylenol, 2,6-xylenol, and 2-t-butylphenol.
In the present invention, the 9,9-bis (4-hydroxyphenyl) thus obtained is obtained.
An aliphatic ketone adduct formed by adding an aliphatic ketone to fluorene is heated to a temperature higher than the decomposition temperature of the adduct in the presence of the aliphatic ketone solvent or a mixed solvent of the aliphatic ketone and water. The adduct is decomposed and dissolved by heating and then cooled, and the precipitated aliphatic ketone adduct is separated to obtain a purified aliphatic ketone adduct, and then the fat is obtained from the obtained purified aliphatic ketone adduct. The high-purity 9,9-bis (4-hydroxyphenyl) fluorenes are obtained by removing the aromatic ketone by drying.

In the reaction of dehydrating condensation of fluorenones and phenols in the presence of an acid catalyst, examples of the acid catalyst include hydrochloric acid, hydrogen chloride gas, 60-98% sulfuric acid and other mineral acids, methanesulfonic acid, solid acid, and the like. Although suitable, it is preferably hydrogen chloride gas, and after replacing the air in the reaction system with an inert gas such as nitrogen gas, hydrogen chloride gas may be blown so that the reaction system becomes saturated. At that time, it is preferable to use a thiol such as alkyl mercaptan together with the acid catalyst because the reaction is accelerated. The molar ratio of fluorenones to phenols (phenols / fluorenones) is usually in the range of 2-20, preferably in the range of 4-10, and usually no organic solvent may be used, but the freezing point of the phenols A small amount of water may be added in order to lower the pH and promote the reaction of the acid catalyst. The reaction temperature is usually about 20 to 60 ° C, preferably about 30 to 50 ° C. Under such conditions, the reaction is usually completed in about 1 to 20 hours, preferably about 3 to 10 hours. The reaction-terminated liquid mixture thus obtained is a solution or a slurry liquid,
Usually, for neutralization of the acid catalyst, for example, an alkali such as an aqueous sodium hydroxide solution is added for neutralization to obtain a reaction mixture containing 9,9-bis (4-hydroxyphenyl) fluorenes.

In the present invention, the aliphatic ketone adduct of 9,9-bis (4-hydroxyphenyl) fluorenes is added to the reaction mixture containing 9,9-bis (4-hydroxyphenyl) fluorenes after neutralization. Even when the aliphatic ketone adduct formed by adding an aliphatic ketone capable of forming an adduct with 9,9-bis (4-hydroxyphenyl) fluorene is separated by filtration or the like In addition, the aliphatic ketone adduct formed by adding an aliphatic ketone capable of forming an adduct to the crude crystals of 9,9-bis (4-hydroxyphenyl) fluorenes in the same manner is separated by filtration or the like. It may be obtained. In the production method of the present invention, an aliphatic ketone formed by adding an aliphatic ketone to the reaction mixture containing the 9,9-bis (4-hydroxyphenyl) fluorenes because the purification process is simple. Those obtained by separating the adduct are preferred.

Such an adduct formation and separation method can be performed, for example, by the method described in Patent Document 1. The separated adduct is preferably washed with water or a mixture of an aliphatic ketone and water as necessary in order to remove impurities such as alkali and catalyst. Specifically, for example, after adding an aliphatic ketone or a mixture of an aliphatic ketone and water that can form an adduct to the reaction mixture containing 9,9-bis (4-hydroxyphenyl) fluorene after neutralization Or after adding an aliphatic ketone or a mixture of an aliphatic ketone and water that can form an adduct to the crude crystals of 9,9-bis (4-hydroxyphenyl) fluorenes, at a temperature sufficiently lower than the boiling point of the solvent at room temperature. The temperature at which crystals are sufficiently precipitated, usually about 5 to 40 ° C., preferably 20 to 30
The aliphatic ketone adduct according to the present invention can be obtained by cooling and separating the adduct which has been cooled to about 0 ° C. and washing it with pure water.

In the production method of the present invention, it is preferable not to use an organic solvent in the dehydration condensation reaction of fluorenone and phenols, and a single ketone is used as the aliphatic ketone used for the adduct formation.
The amount of the aliphatic ketone used for adduct formation is usually 2 with respect to 9,9-bis (4-hydroxyphenyl) fluorenes contained in the reaction mixture when used for taking out the adduct from the reaction mixture. ˜20 mol times, preferably 4 to 10 mol times of aliphatic ketone may be added, and the more the amount of phenols and moisture other than the object, the more necessary.
The adduct is usually formed by adding 1 mol or 2 mol of an aliphatic ketone to 1 mol of 9,9-bis (4-hydroxyphenyl) fluorene.

Next, in the production method of the present invention, the aliphatic ketone solvent or a mixed solvent of the aliphatic ketone and water is added to the obtained aliphatic ketone adduct of 9,9-bis (4-hydroxyphenyl) fluorenes. Add As such an aliphatic ketone, the same aliphatic ketone solvent as the aliphatic ketone used for the adduct formation is used.

Accordingly, the aliphatic ketone used in the present invention can form an adduct with 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4- Hydroxyphenyl) fluorene or / and its adduct dissolves,
Below the decomposition temperature of the adduct, it is an aliphatic ketone that is a poor solvent for the adduct. Specifically, for example, 3 to 3 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
6 aliphatic ketones. In particular, acetone is preferred because of its low boiling point and easy recovery.
Moreover, as a mixed solvent of an aliphatic ketone and water, a mixed solvent in which an aliphatic ketone solvent and water are uniformly mixed is preferable, and a mixed solvent of acetone and water is particularly preferable.

The weight ratio of aliphatic ketone to water (aliphatic ketone / water) in the mixed solvent is usually 50/50.
In the range of ~ 99/1, preferably in the range of 60/40 to 95/5, more preferably 70/30.
It is in the range of ~ 90/10.
The addition amount of the aliphatic ketone solvent or the mixed solvent of the aliphatic ketone and water is not particularly limited as long as there is no problem in operation. However, if the amount is too large, the volumetric efficiency is lowered and the economic efficiency is deteriorated.

Therefore, it is usually 0.4 for the pure 9,9-bis (4-hydroxyphenyl) fluorene.
It is in the range of ˜20 times by weight, preferably in the range of 1 to 10 times by weight, more preferably in the range of 1.5 to 5 times by weight.
In the case of the single aliphatic ketone according to the present invention, for example, 9,9-bis (4-hydroxyphenyl) fluorene is used as long as it does not hinder the formation and / or decomposition of the adduct and does not hinder the solvent recovery. A small amount of the other organic solvent may be contained to the extent that the other organic solvent adheres to the aliphatic ketone adduct of the kind.

Next, in the production method of the present invention, the aliphatic ketone adduct of the 9,9-bis (4-hydroxyphenyl) fluorene obtained above is mixed with the aliphatic ketone solvent or a mixed solvent of the aliphatic ketone and water. After the addition, the temperature is raised above the temperature at which the adduct decomposes, and the adduct is decomposed and dissolved. The decomposition and dissolution of an adduct is a state in which the adduct is dissolved after it has been decomposed, or partially dissolved as an adduct, and the rest is dissolved after decomposition to eliminate solids. Depends on the aliphatic ketone forming the aliphatic ketone adduct and the aliphatic ketone solvent to be added. For example, in the case of acetone, it is usually about 70 to 130 ° C, preferably about 75 to 95 ° C. In the case of a mixed solvent of acetone and water, the temperature is usually about 60 to 130 ° C, preferably about 65 to 90 ° C.
In order to maintain the temperature at which the adduct decomposes and dissolves in this way, it is necessary to maintain a pressurized state when the decomposition temperature of the adduct is higher than the boiling point of the solvent to be added. Alternatively, in the case of a mixed solvent of acetone and water, the pressure is 0.05 to 0.65 MPa (gauge pressure).

Next, the mixed solution in which the adduct is decomposed and dissolved is cooled to form an adduct and precipitate.
The cooling temperature is not particularly limited as long as the temperature is lower than the decomposition temperature of the adduct, sufficiently lower than the boiling point of the solvent at normal pressure, and the adduct crystals are sufficiently precipitated, but is usually in the range of about 0 to 40 ° C. Preferably, it is the range of about 15-30 degreeC. The adduct thus precipitated is separated by a method such as filtration, and the adduct obtained by separation is preferably washed with a solvent. The solvent used for washing is not particularly limited as long as it is a poor solvent and can be evaporated at the time of drying, but in the present invention, the same aliphatic ketone and / or the same aliphatic ketone as the adduct is formed. It is preferable to use water because the solvent can be easily recovered. The purified aliphatic ketone adduct thus obtained is an aliphatic ketone adduct of high-purity 9,9-bis (4-hydroxyphenyl) fluorenes having a purity of 99.0% or more, and the aliphatic ketone adduct Can be used as an aliphatic ketone adduct in applications where it is not necessary to dry remove the.

In addition, if necessary, the separated purified aliphatic ketone adduct is dried and removed if there is an added aliphatic ketone and residual solvent. For example, it is heated and dried under normal pressure or reduced pressure. Do.
The resulting purified aliphatic ketone adduct has a large amount of aliphatic ketone added, but when the aliphatic ketone is excluded, high-purity 9,9-bis (4-hydroxyphenyl) having a purity of 99.0% or more is obtained. Since it is a fluorene, it can be used for applications other than those in which mixing of aliphatic ketones is not preferable, but it is preferable to heat the adduct under normal pressure or reduced pressure and dry it.
Usually, the adduct decomposes during drying to remove the aliphatic ketone.
In order to improve the hue of the target product, it is preferable that the interior of the dryer system is replaced with an inert gas such as nitrogen during drying.
The drying temperature (final temperature) and pressure vary depending on the solvent used. For example, in the case of acetone, the temperature is usually in the range of 90 to 130 ° C, preferably in the range of 90 to 105 ° C.
Absolute pressure) is usually in the range of 24.0-101.3 kPa, preferably 53.3-80.0 kPa.
It is the range of a.
Thus, in the production method of the present invention, a high purity 9,9-bis having a purity of 99.0% or more is obtained using only a single aliphatic ketone solvent or a mixed solvent of a single aliphatic ketone and water as the organic solvent. (4-Hydroxyphenyl) fluorenes can be produced with good yield.

(Acetone single solvent)
In a 1000 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 148.9 g (1.38 mol) of o-cresol, n-dodecyl mercaptan;
After charging 6 g and 2.9 g of water and replacing the inside of the system with nitrogen gas, hydrogen chloride gas was blown into the system until the inside was saturated while maintaining the internal temperature of 40 to 45 ° C.
While maintaining the temperature in the flask at 40 to 45 ° C., 106.5 g (0.99 m) of o-cresol.
ol) and 71.0 g (0.39 mol) of 9-fluorenone were added dropwise over 1.5 hours with stirring. After completion of the dropping, the reaction was allowed to proceed for 5 hours while maintaining the same temperature to obtain a reaction solution of a red and white cloudy slurry.
After completion of the reaction, the solution was neutralized by adding 83.6 g of a 12% aqueous sodium hydroxide solution, and then 142.2 g of acetone was added to dissolve the crystals. Then, it cooled to 26 degreeC, the precipitated crystal | crystallization was separated by filtration, and it wash | cleaned by adding distilled water.
187.1 g of the obtained crude crystals and 374.2 g of acetone were charged into a 1000 ml pressure-resistant glass container and replaced with nitrogen gas, and then heated to 100 ° C. with stirring. At this time, it was initially in a white slurry state, but started to dissolve when the internal temperature reached 80 ° C., and completely dissolved at 90 ° C. When the internal temperature reached 100 ° C. and then cooled, a large amount of crystals precipitated at around 68 ° C. After further cooling, the crystals were filtered off at 26 ° C. and then washed with acetone to obtain purified adduct crystals. The obtained crystals were dried under reduced pressure at 105 to 107 ° C. to obtain 129.0 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene as the target product.

Appearance; white crystal purity; 99.6% (high performance liquid chromatography method)
Melting point: 219.0 ° C. (Differential scanning calorimetry)

(Mixed solvent of acetone and water)
A 1000 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 148.9 g (1.38 mol) of o-cresol and the system was replaced with nitrogen gas. While maintaining 45 ° C., hydrogen chloride gas was blown in until the system was saturated. Next, 5.2 g of a 15% methyl mercaptan sodium aqueous solution was added, and hydrogen chloride gas was further blown so as to keep the pressure in the system at normal pressure.
Next, while maintaining the temperature in the flask at 40 to 45 ° C., 106.5 g (0.99) of o-cresol.
mol) and 71.0 g (0.39 mol) of 9-fluorenone was added dropwise over 3 hours with stirring. After completion of the dropwise addition, the reaction was continued for 4 hours while maintaining the same temperature to obtain a light red slurry reaction solution.
After completion of the reaction, 68.7 g of a 16% aqueous sodium hydroxide solution was added for neutralization. Distilled water 75.
After adding 3 g, acetone 142.0 g was added to dissolve the crystals. Thereafter, the mixture was cooled to 25 ° C., and the precipitated crystals were separated by filtration and washed with distilled water.
The obtained crude crystal 188.4g, acetone 320.3g and distilled water 56.5g 1000m
1 was charged in a pressure-resistant glass container and replaced with nitrogen gas, and then heated to 90 to 95 ° C. with stirring. At this time, it was initially in a white slurry state, but when the internal temperature reached 73 ° C., it started to dissolve and completely dissolved at 78 ° C.
After the internal temperature reached 90 ° C., the mixture was kept under stirring for 30 minutes and then cooled. When a small amount of seed crystal was added at around 70 ° C., a large amount of crystal was precipitated. Thereafter, the mixture was further cooled and the crystals were filtered off at 27 ° C. The filtered crystals were washed with acetone and distilled water to obtain purified adduct crystals.
The obtained crystals were dried under reduced pressure at 95 to 100 ° C. to obtain 126.2 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene which was the target product.

Appearance; white crystal purity; 99.5% (high performance liquid chromatography method)
Melting point: 219.1 ° C. (Differential scanning calorimetry)

Claims (3)

The addition of 9,9-bis (4-hydroxy -3- methylphenyl) fluorene with an acetone adduct is carried out in the presence of acetone or a mixed solvent of acetone and water at a temperature higher than the decomposition temperature of the adduct. The method for producing 9,9-bis (4-hydroxy -3- methylphenyl) fluorene is characterized in that after the product is decomposed and dissolved, it is cooled, and the precipitated acetone adduct is separated to obtain a purified acetone adduct. . An 9,9-bis (4-hydroxy -3- methylphenyl) fluorene acetone adduct was obtained by dehydrating condensation of 9- fluorenone and o-cresol in the presence of an acid catalyst. - hydroxy-3-methylphenyl) fluorene formed by adding acetone to the reaction mixture containing the acetone adduct is obtained by separating claim 1, wherein the 9,9-bis (4-hydroxy A process for producing -3- methylphenyl) fluorene. Claim 1 or 2 Ri by the method described in 9, with the 9-bis (4-hydroxy-3-methylphenyl) purified acetone adducts of fluorene, and then characterized by drying to remove the acetone 9, A method for producing 9-bis (4-hydroxy -3- methylphenyl) fluorene.