JP7134579B2 - Method for producing bisphenol compound having fluorene skeleton - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel method for producing a bisphenol compound having a fluorene skeleton, which is useful as a starting monomer for resins (optical resins) constituting optical members such as optical lenses and optical films.

Resins such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy, which are made from bisphenol compounds with a fluorene skeleton as raw material monomers, have excellent optical properties and heat resistance. It is attracting attention as a resin (optical resin) that In particular, the following formula (1):

で表される化合物は、該化合物及びその誘導体から製造される樹脂が、光学特性（屈折率等）、耐熱性、耐水性、耐薬品性、電気特性、機械特性、溶解性等の諸特性に優れることから、前記光学樹脂の原料モノマーとして注目されている（例えば特許文献１、２）。

The compound represented by is a resin produced from the compound and its derivatives, optical properties (refractive index, etc.), heat resistance, water resistance, chemical resistance, electrical properties, mechanical properties, various properties such as solubility Because of its excellent properties, it is attracting attention as a raw material monomer for the optical resin (for example, Patent Documents 1 and 2).

JP-A-2002-47227 Japanese Patent Application Laid-Open No. 2003-221352

The compound represented by the above formula (1) can generally be produced by reacting 9-fluorenone and o-phenylphenol in the presence of an inorganic acid or an organic acid. When using the represented compound as a raw material monomer for a resin, it is preferable to remove the acid used in the reaction. In order to remove the acid, the compound represented by the above formula (1) is dissolved in an organic solvent to form a solution, and if necessary, a base is added to neutralize the acid, and then water is added to the acid or neutralization. It is convenient to perform an operation (water washing) to remove the salt produced by from the organic layer. Such operations are also described in Patent Documents 1 and 2 above, but when the inventors of the present application tried to wash with water under the conditions described in the examples of these documents, crystals precipitated and water washing could not be performed. found.

An object of the present invention is to provide a method for washing with water a solution containing the compound represented by the above formula (1).

As a result of intensive studies aimed at solving the above problems, the present inventors have found that the above problems can be solved by dissolving the compound represented by the above formula (1) in a specific solvent. rice field. Specifically, the present invention includes the following inventions.

[1]
Formula (1) below:

で表される化合物を、分岐を有してもよい炭素数５～９の脂肪族ケトン類を含む溶媒に溶解させて上記式（１）で表される化合物を含む溶液を調製し、該溶液に水を添加、混合した後、該溶液から水層を除去する工程を含む、上記式（１）で表される化合物の製造方法。

A compound represented by is dissolved in a solvent containing aliphatic ketones having 5 to 9 carbon atoms which may have a branch to prepare a solution containing the compound represented by the above formula (1), the solution A method for producing a compound represented by the above formula (1), comprising the step of adding water to and mixing, and then removing the aqueous layer from the solution.

[2]
The production method according to [1], wherein the solution and water are mixed at a temperature of 70 to 95°C.

[3]
Aliphatic ketones include 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, methyl isobutyl ketone, The production method according to [1] or [2], which is at least one selected from the group consisting of methyl isoamyl ketone, diisobutyl ketone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone.

[4]
The amount of aliphatic ketones used is represented by the following formula (1):

で表される化合物１重量部に対し４～１０重量部であり、水の使用量が、上記式（１）で表される化合物１重量部に対し１～５重量部である、［１］～［３］のいずれか一つに記載の製造方法。

The amount of water used is 1 to 5 parts by weight per 1 part by weight of the compound represented by the above formula (1), [1] The manufacturing method according to any one of to [3].

[5]
Furthermore, from the solution, the following formula (1):

で表される化合物の結晶を析出させ、該結晶を分離する工程を含む、［１］～［４］のいずれか一つに記載の製造方法。

The production method according to any one of [1] to [4], comprising the step of precipitating crystals of the compound represented by and separating the crystals.

According to the present invention, the solution containing the compound represented by the above formula (1) can be washed with water, and water-soluble impurities such as acids and inorganics can be reduced. Further, after washing with water, the compound represented by the above formula (1) with significantly reduced coloration can be obtained in good yield by crystallization.

The optionally branched aliphatic ketones having 5 to 9 carbon atoms that can be used in the present invention include 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, Examples include 4-heptanone, 2-octanone, 3-octanone, 4-octanone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone or 4-methylcyclohexanone, and these fats. Among the group ketones, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, methyl isobutyl ketone, methyl isoamyl ketone, cyclohexanone, 2 -methylcyclohexanone, 3-methylcyclohexanone or 4-methylcyclohexanone are preferred, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, methylisobutylketone or methylisoamyl Ketones are more preferred. These aliphatic ketones may be used alone, or two or more of them may be used in combination, if necessary. In addition, an organic solvent other than aliphatic ketones having 5 to 9 carbon atoms which may have a branch (hereinafter sometimes referred to as another organic solvent) may be used in combination.

The amount of aliphatic ketones having 5 to 9 carbon atoms which may be branched is usually 4 to 10 parts by weight per 1 part by weight of the compound represented by the above formula (1), from the viewpoint of economy. , preferably 4 to 8 parts by weight. When other organic solvents are used in combination, the amount of such organic solvents used is usually 0.01 to 2 parts by weight, preferably 1 part by weight of aliphatic ketones having 5 to 9 carbon atoms which may have a branch. 0.1 to 1 part by weight.

As a specific method of carrying out the present invention, aliphatic ketones having 5 to 9 carbon atoms which may be branched, water and, if necessary, a base are added to crystals of the compound represented by the above formula (1). Then, a solution containing the compound represented by the above formula (1) (hereinafter sometimes referred to as an organic layer) and water (hereinafter sometimes referred to as an aqueous layer) are mixed at the temperature described below, and mixed A method of carrying out by removing the aqueous layer from the organic layer is exemplified. Alternatively, fluorenone and o-phenylphenol are reacted in the presence of an inorganic acid or an organic acid to obtain a reaction solution containing the compound represented by the above formula (1), and carbon, which may have a branch, is added to the reaction solution. Aliphatic ketones of numbers 5 to 9, water and, if necessary, a base are added, the organic layer and the aqueous layer are mixed at the temperature described below, and after mixing, the aqueous layer is removed from the organic layer. (A series of operations may be hereinafter referred to as "rinsing").

The amount of water used in the present invention is usually 1 to 5 parts by weight, preferably 1 to 3 parts by weight, per 1 part by weight of the compound represented by the above formula (1).

The temperature at which the organic layer and the aqueous layer are mixed is generally 70°C to the boiling point of the organic layer (or aqueous layer) or lower, preferably 70 to 95°C.

The amount of the base added as necessary may be an amount that can neutralize part or all of the acid used in the reaction, and is usually 0.9 to 2 equivalents, preferably 0.9 to 2 equivalents, per 1 equivalent of the acid used in the reaction. 1 to 1.2 equivalents. The base to be used may be an inorganic base or an organic base. Specific examples of the inorganic base include carbonates, hydrogen carbonates, hydroxides, organic bases, and the like. potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, etc.; Lithium etc. are illustrated. Specific examples of organic bases include triethylamine and triphenylphosphine. Among these bases, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydroxide, or potassium hydroxide is preferable from the viewpoint of good handleability. Moreover, these bases may be used alone, or two or more of them may be used in combination, if necessary.

Examples of the method of mixing the organic layer and the aqueous layer include a method of stirring using a stirring device, and a method of mixing the organic layer and the aqueous layer by circulating them using a pump or the like.

As a method for removing the aqueous layer from the organic layer, a method of separating the organic layer and the aqueous layer by mixing the organic layer and the aqueous layer and allowing the mixture to stand still to remove the aqueous layer is exemplified. The temperature for removing the aqueous layer from the organic layer is usually the same temperature as the temperature for mixing the organic layer and the aqueous layer.

The obtained organic layer may be washed with water multiple times as necessary, and the organic solvent contained in the organic layer by concentration (aliphatic ketones having 5 to 9 carbon atoms which may have a branch and optionally Other organic solvents used depending on the situation) may be partially or wholly removed, and purification operations such as filtration and adsorption may be performed. Also, these operations may be combined.

The obtained organic layer may be used as it is for producing a resin or reacting with another compound, but once crystals of the compound represented by the above formula (1) are precipitated from the organic layer, and the crystals are Isolation of the compound represented by the above formula (1) as crystals by filtration (hereinafter sometimes referred to as crystallization) improves the purity of the compound and reduces coloration. preferred from

In carrying out crystallization, the content of aliphatic ketones having 5 to 9 carbon atoms which may have a branch contained in the organic layer is 1 weight of the compound represented by the above formula (1) contained in the organic layer. 4 to 10 parts by weight, preferably 4 to 8 parts by weight from the viewpoint of economy. If it is different from the above range, it can be adjusted to the above range by concentrating before crystallization or by newly adding an aliphatic ketone having 5 to 9 carbon atoms which may have a branch. Other organic solvents may also be contained, in which case the content of the other organic solvents is usually 0.00 per 1 part by weight of the optionally branched aliphatic ketones having 5 to 9 carbon atoms. 01 to 2 parts by weight, preferably 0.1 to 1 part by weight.

The temperature at which the crystals of the compound represented by the formula (1) are separated by filtration is usually 5°C or more lower than the temperature at which the crystals of the compound represented by the formula (1) precipitate, preferably 10°C or more. temperature. By setting the temperature to such a temperature, the compound represented by the above formula (1) can be obtained in a higher yield.

The filtered crystals may be further washed with an optionally branched aliphatic ketone having 5 to 9 carbon atoms or the like, and may be dried if necessary. Further, ordinary purification operations such as adsorption, steam distillation and recrystallization may be performed.

EXAMPLES The present invention will be specifically described below with reference to examples, etc., but the present invention is not limited to these. In addition, various measurements were implemented by the following method in an example. In addition, the conversion rate and purity of each component described in Examples and Comparative Examples below are area percentage values of HPLC measured under the following conditions.

(1) HPLC analysis device: LC-2010A manufactured by Shimadzu Corporation,
Column: SUMIPAX ODS A-211 (5 μm, 4.6 mmφ×250 mm),
Mobile phase: pure water/acetonitrile (acetonitrile 30% → 100%),
Flow rate: 1.0 ml/min, column temperature: 40°C, detection wavelength: UV 254 nm.

(2) YI value 1 g of crystals of the alcohol compound represented by the above formula (1) is weighed into a 10 ml volumetric flask, dissolved in diglyme with a purity of 99% by weight or more, and dissolved under the following conditions to obtain a diglyme solution. YI value (yellowness) was measured.
Apparatus: color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., SE6000),
Cell used: Quartz cell with an optical path length of 10 mm.
In addition, the hue of the diglyme was measured and corrected in advance so that the coloring of the diglyme itself used for the measurement did not affect the measured value. (blank measurement). The YI value in the present invention is the value obtained by measuring the sample after performing the blank measurement.

<Production Example 1>
160 g (0.89 mol) of 9-fluorenone, 262 g of 98% sulfuric acid, 8.8 g of dodecanethiol, and 907 g of o-phenylphenol were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, and the mixture was heated to 80°C. After the mixture was stirred at the same temperature for 5 hours, it was confirmed by HPLC that the conversion of 9-fluorenone was 99%. The obtained reaction liquid containing the compound represented by the above formula (1) was 1325 g.

<Example 1>
192 g of water and 26 g of sodium hydroxide were added to 167 g of the reaction solution obtained in Production Example 1, and the mixture was stirred at room temperature for 1 hour. After stirring for an hour and allowing to stand, the aqueous layer was separated. 96 g of water was added to the obtained organic layer, and the mixture was stirred at 80 to 85° C. for 30 minutes, allowed to stand, and then the aqueous layer was separated. After repeating the same operation three times, the obtained organic layer was concentrated to remove methyl isobutyl ketone and o-phenylphenol to obtain a concentrate. 400 g of methyl isobutyl ketone was added to the resulting concentrate, the temperature was raised to 115°C, the mixture was stirred at the same temperature for 1 hour, and then cooled to 25°C at a rate of 0.2°C/min. The crystals were separated by filtration at 25° C., and the obtained crystals were dried at an internal temperature of 90° C. for 8 hours under reduced pressure of 2 kPa to obtain crystals of the compound represented by the above formula (1). The weight of the obtained crystals was 45 g (80% yield), the purity was 99.6%, and the YI value was 0.5.

<Example 2>
Crystals of the compound represented by the above formula (1) were obtained in the same manner as in Example 1 except that methyl isobutyl ketone was changed to 2-heptanone. The weight of the obtained crystals was 42 g (75% yield), the purity was 99.5%, and the YI value was 0.6.

<Comparative Example 1>
370 g of toluene, 192 g of water, and 26 g of sodium hydroxide were added to 167 g of the reaction solution obtained in Production Example 1, and the mixture was stirred at 85° C. for 10 hours. rice field.

<Production Example 2>
160 g (0.89 mol) of 9-fluorenone, 902 g of 35% hydrochloric acid, 8.8 g of dodecanethiol, and 907 g of o-phenylphenol were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, and the mixture was heated to 80°C. After the mixture was stirred at the same temperature for 26 hours, it was confirmed by HPLC that the conversion of 9-fluorenone was 99%. The obtained reaction liquid containing the compound represented by the above formula (1) was 1950 g.

<Example 4>
317 g of water and 43 g of sodium hydroxide were added to 247 g of the reaction solution obtained in Production Example 2, and the mixture was stirred at room temperature for 1 hour. After stirring and standing, the aqueous layer was separated. 96 g of water was added to the obtained organic layer, and the mixture was stirred at 80 to 85° C. for 30 minutes, allowed to stand, and then the aqueous layer was separated. After repeating the same operation three times, the obtained organic layer was concentrated to remove methyl isobutyl ketone and o-phenylphenol to obtain a concentrate. 400 g of methyl isobutyl ketone was added to the resulting concentrate, the temperature was raised to 115°C, the mixture was stirred at the same temperature for 1 hour, and then cooled to 24°C at a rate of 0.2°C/min. The crystals were separated by filtration at 24° C., and the obtained crystals were dried at an internal temperature of 90° C. for 8 hours under reduced pressure of 2 kPa to obtain crystals of the compound represented by the above formula (1). The weight of the obtained crystals was 41 g (74% yield), the purity was 99.1%, and the YI value was 0.7.

<Comparative Example 2>
370 g of toluene, 317 g of water, and 43 g of sodium hydroxide were added to 247 g of the reaction solution obtained in Production Example 2, and the mixture was stirred at 85° C. for 10 hours. I couldn't do it.

<Reference example 1>
9-Fluorenone and o-phenylphenol are reacted in the same manner as described in Example 3 of JP-A-2003-221352, except that the scale is 1/3.5. A reaction solution containing the compound obtained was obtained. 86 g of toluene and 23 g of water were added to the resulting reaction solution, but the crystals did not dissolve. Therefore, the liquid separation operation could not be performed.

Claims (5)

Formula (1) below:

A compound represented by is dissolved in a solvent containing aliphatic ketones having 5 to 9 carbon atoms which may have a branch to prepare a solution containing the compound represented by the above formula (1), the solution A method for producing a compound represented by the above formula (1), comprising the step of adding water to and mixing, and then removing the aqueous layer from the solution. The production method according to claim 1, wherein the temperature at which the solution and water are mixed is 70 to 95°C. Aliphatic ketones include 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, methyl isobutyl ketone, The production method according to claim 1 or 2, wherein at least one selected from the group consisting of methyl isoamyl ketone, diisobutyl ketone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone. The amount of aliphatic ketones used is represented by the following formula (1):

4 to 10 parts by weight per 1 part by weight of the compound represented by the formula (1), and the amount of water used is 1 to 5 parts by weight per 1 part by weight of the compound represented by the above formula (1). 4. The production method according to any one of -3. Furthermore, from the solution, the following formula (1):

The production method according to any one of claims 1 to 4, comprising a step of precipitating crystals of the compound represented by and separating the crystals.