Method for producing composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, and crystal of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene

Abstract

The present invention addresses the problem of providing a production method that can be implemented as an industrial production method and that includes a step for efficiently purifying 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene. As a means for solving the problem, provided is a method for producing a composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, the method including a crystallization step for precipitating crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene from a crystallization solution containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene and a C3-6 aliphatic ketone solvent.

Description

Method for producing a composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, and crystal of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene

[0001] The present invention relates to a method for producing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, and more particularly, to a method for isolating and purifying 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene. The present invention also relates to a novel form of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene.

[0002] Fluorene derivatives are excellent in heat resistance and transparency and are promising as raw materials for producing polymers having a high refractive index. In particular, they have been expected in recent years as raw material for optical lenses, films, plastic optical fibers, optical disk substrates, heat-resistant resins, engineering plastics, and the like. Therefore, in order to further enhance the functionality of the materials, the development of novel fluorene derivatives and their production methods is desired.

[0003] Fluorene derivatives having a structure in which phenanthrene is bonded to fluorene, and as a specific example thereof, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene (hereinafter sometimes referred to as Compound A) is known to be suitable as a monomer for forming a resin constituting an optical member, typified by optical lenses and optical films (for example, Patent Document 1). Patent Document 1 lists separation means such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or a metal removal treatment similar thereto, and column chromatography. Specifically, a method of dissolving Compound A in toluene and then adding hexane for recrystallization is described.

[0004] International Publication No. 2022 / 038997

[0005] The present inventors investigated a method for isolating 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene (compound A) based on the method described in Patent Document 1. As described in Comparative Example 1 below, it became clear that compound A has extremely low solubility in toluene, making it difficult to obtain crystals of compound A by crystallization, or that the amount of compound A obtained per unit volume of the crystallization solution is extremely small, making it difficult to implement as an industrial production method. In view of this, the object of the present invention is to provide a production method that can be implemented as an industrial production method and includes a step for efficiently purifying compound A.

[0006] As a result of diligent research to solve the above problems, the inventors of the present invention have found a method for efficiently obtaining a composition containing the target compound in high purity by performing a crystallization step using a specific solvent in the separation and purification of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, and have completed the present invention.

[0007] The present invention is as follows: 1. A method for producing a composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, comprising a crystallization step of precipitating crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene from a crystallization solution containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene and an aliphatic ketone solvent having 3 to 6 carbon atoms. 2. The method according to 1, wherein the crystallization step is a crystallization step of precipitating the crystals by a method comprising at least one of the methods of cooling crystallization, evaporation crystallization, and poor solvent addition crystallization. 3. The method according to 2, wherein the crystallization step is a crystallization step of precipitating the crystals by a method comprising at least poor solvent addition crystallization using an aromatic hydrocarbon solvent having 7 to 9 carbon atoms or an aliphatic hydrocarbon solvent having 5 to 8 carbon atoms in the crystallization solution. 4. The method for producing the composition according to 1, wherein the composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene is in powder form. 5. The method for producing the composition according to 1, wherein the composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene has a peak area of ​​9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene that is 95.0% or more of the peak area of ​​all components detected at a wavelength of 280 nm in high-performance liquid chromatography (HPLC) analysis. 6. The method for producing the composition according to 1, wherein the composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene has a weight loss rate of 10% by weight or less at 300°C by thermogravimetric analysis. 7. The method for producing the composition according to 1, wherein the composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene has a Hazen unit color number (APHA) of 200 or less when the composition is dissolved in a 10% by weight acetone solution. 8. Crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, characterized in that the peak top temperature of the endothermic peak determined by differential scanning calorimetry is in the range of 144 to 163°C.9. The crystal according to 8, further having diffraction peaks at diffraction angles 2θ of 6.3±0.2°, 11.3±0.2°, and 22.5±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays. 10. A method for producing the crystal according to 8, characterized by comprising a crystallization step of precipitating crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene from a crystallization solution containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene and an aliphatic ketone solvent having 3 to 6 carbon atoms.

[0008] The manufacturing method of the present invention makes it possible to produce a composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene with high purity and efficiency. The 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene crystals of the present invention melt at a relatively low temperature of less than 200°C. For example, the melting temperature when used as a resin monomer can be kept low, thus reducing the amount of heat required to melt the monomer and contributing to energy saving, as well as suppressing discoloration and degradation at high temperatures. The manufacturing method of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene crystals of the present invention can be carried out under conditions and operations that are easy to implement industrially.

[0009] The composition (crystals) of compound A obtained in Example 1 １ This is a chart of the 1H-NMR analysis. The composition (crystals) of compound A obtained in Example 1 １３This figure shows the 3C-NMR analysis chart. This figure shows the powder X-ray diffraction (PXRD) analysis chart of the compound A composition (crystal) obtained in Example 1. This figure shows the differential scanning calorimetry (DSC) analysis chart of the compound A composition (crystal) obtained in Example 1. This figure shows the differential thermal and thermogravimetric (TG / DTA) simultaneous measurement thermal analysis chart of the compound A composition (crystal) obtained in Example 1. This figure shows the powder X-ray diffraction (PXRD) analysis chart of the compound A composition (crystal) obtained in Example 2. This figure shows the differential scanning calorimetry (DSC) analysis chart of the compound A composition (crystal) obtained in Example 2. This figure shows the differential thermal and thermogravimetric (TG / DTA) simultaneous measurement thermal analysis chart of the compound A composition (crystal) obtained in Example 2. This figure shows the powder X-ray diffraction (PXRD) analysis chart of the compound A composition (crystal) obtained in Example 3. This figure shows the differential scanning calorimetry (DSC) analysis chart of the composition (crystal) of compound A obtained in Example 3. This figure shows the differential thermal and thermogravimetric (TG / DTA) simultaneous measurement thermal analysis chart of the composition (crystal) of compound A obtained in Example 3. This figure shows the powder X-ray diffraction (PXRD) analysis chart of the composition (crystal) of compound A obtained in Example 4. This figure shows the differential scanning calorimetry (DSC) analysis chart of the composition (crystal) of compound A obtained in Example 4. This figure shows the differential thermal and thermogravimetric (TG / DTA) simultaneous measurement thermal analysis chart of the composition (crystal) of compound A obtained in Example 4. This figure shows the powder X-ray diffraction (PXRD) analysis chart of the composition (crystal) of compound A obtained in Example 5. This figure shows the differential scanning calorimetry (DSC) analysis chart of the composition (crystal) of compound A obtained in Example 5. This figure shows the differential thermal and thermogravimetric (TG / DTA) simultaneous thermal analysis chart of the compound A composition (crystal) obtained in Example 5. This figure shows the powder X-ray diffraction (PXRD) analysis chart of the compound A composition (crystal) obtained in Example 6. This figure shows the differential scanning calorimetry (DSC) analysis chart of the compound A composition (crystal) obtained in Example 6.This figure shows the differential thermal and thermogravimetric (TG / DTA) simultaneous thermal analysis of the compound A composition (crystal) obtained in Example 6.

[0010] The present invention will be described in detail below. <Method for producing a composition containing compound A of the present invention> The method for producing a composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene (compound A) of the present invention is characterized by comprising a crystallization step of precipitating crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene from a crystallization solution containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene and an aliphatic ketone solvent having 3 to 6 carbon atoms.

[0011] The 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene (compound A) according to the present invention is a compound having the following chemical structure.

[0012] (Method for producing Compound A) The method for producing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene (Compound A) according to the present invention is not particularly limited and can be produced by conventionally known methods. For example, two equivalents of 9-phenantrol and one equivalent of fluorenone undergo a dehydration condensation reaction to produce one equivalent of 9,9-bis[9-hydroxy-3-phenanthryl]fluorene together with one equivalent of water. Furthermore, a method can be described in which 9,9-bis[9-hydroxy-3-phenanthryl]fluorene is reacted with a hydroxyethoxylation agent to produce Compound A. The reaction for producing Compound A when ethylene carbonate is used as the hydroxyethoxylation agent is shown in the following reaction formula. There are no restrictions on the compound A used in the crystallization step in the manufacturing method of the present invention. For example, compound A obtained by the above-described reaction, compound A obtained by separation operations such as concentration, reprecipitation, and column separation from a reaction solution containing compound A, compound A crystals obtained through the crystallization step of the present invention, and compound A crystals obtained by crystallization methods other than the crystallization step of the present invention can be used.

[0013] (Crystallization Solvent) The aliphatic ketone solvent having 3 to 6 carbon atoms used in the crystallization step in the method for producing the composition of the present invention includes a chain-like aliphatic ketone solvent having 3 to 6 carbon atoms and a cyclic aliphatic ketone solvent having 3 to 6 carbon atoms. Among these, from the viewpoint of ease of operation in the industrial crystallization step, a chain-like aliphatic ketone solvent having 3 to 6 carbon atoms or a cyclic aliphatic ketone solvent having 6 carbon atoms is preferred, a chain-like aliphatic ketone solvent having 3 to 6 carbon atoms is more preferred, and a chain-like aliphatic ketone solvent having 3 or 4 carbon atoms is even more preferred to be acetone or methyl ethyl ketone, and acetone is particularly preferred. Specific examples of aliphatic ketone solvents to be used include acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. At least one of these is preferred, at least one selected from acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, methyl isobutyl ketone, and cyclohexanone is more preferred, at least one selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone is even more preferred, and at least one selected from acetone and methyl ethyl ketone is particularly preferred. Two or more types of aliphatic ketone solvents may be used, but it is preferable to use one type alone. In other words, it is preferable to use one solvent selected from acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; it is more preferable to use one solvent selected from acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, methyl isobutyl ketone, and cyclohexanone; it is even more preferable to use one solvent selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and it is particularly preferable to use acetone or methyl ethyl ketone as the solvent.The amount of aliphatic ketone solvent having 3 to 6 carbon atoms used relative to compound A can be appropriately adjusted in view of the crystallization process conditions and the solubility of the aliphatic ketone solvent used, but it is preferably in the range of 1.0 to 35.0 times by weight, more preferably in the range of 1.0 to 15.0 times by weight, even more preferably in the range of 1.2 to 10.0 times by weight, and particularly preferably in the range of 1.2 to 4.0 times by weight.

[0014] (Crystallization Method) There are no restrictions on the method for precipitating crystals in the crystallization step in the method for producing the composition of the present invention, but examples include cooling crystallization, in which crystals are precipitated by cooling the crystallization solution; evaporation crystallization, in which crystals are precipitated by evaporating the solvent from the crystallization solution; and poor solvent addition crystallization, in which crystals are precipitated by adding a poor solvent to the crystallization solution. It is preferable that the method includes at least one of these methods, and it is more preferable that it includes at least poor solvent addition crystallization. It is also possible to carry out the process using only one of these methods, but it is more preferable to carry out the process using a combination of multiple methods. Examples of methods combining multiple methods include poor solvent addition crystallization and cooling crystallization, evaporation crystallization and cooling crystallization, and crystallization methods using poor solvent addition crystallization, cooling crystallization, and evaporation crystallization. Among these methods for precipitating crystals, poor solvent addition crystallization and cooling crystallization, or a combination of poor solvent addition crystallization, evaporation crystallization, and cooling crystallization are even more preferable. In crystallization methods involving poor solvent addition and evaporation crystallization, it is preferable to add a poor solvent and then evaporate the solvent from the crystallization solution. In crystallization methods including evaporation crystallization and cooling crystallization, it is preferable to evaporate the solvent from the crystallization solution and then cool the solution.

[0015] In the production method of the composition of the present invention, the temperature of the crystallization solution in the cooling crystallization step is such that the upper limit of the temperature of the crystallization solution is 1°C lower than the boiling point of the crystallization solvent used, and the lower limit of the temperature depends on the aliphatic ketone solvent with 3 to 6 carbon atoms used. The crystallization solution is heated to 15°C, preferably 20°C, more preferably 30°C, and particularly preferably 45°C, within the range from the upper limit to the lower limit. After that, the crystallization solution is cooled to a range of 0 to 40°C, preferably 10 to 40°C, more preferably 15 to 35°C, and even more preferably 15 to 30°C. Specifically, the temperature 1°C lower than the boiling point of the crystallization solvent used in the present invention means, for example, 55°C when using acetone with a boiling point of 56°C (at 1 atmosphere). When using two or more aliphatic ketone solvents with 3 to 6 carbon atoms, or when a poor solvent is added, it means the temperature based on the boiling point (at 1 atmosphere) of the type and composition of the solvent used. In the method for producing the composition of the present invention, the evaporation crystallization step involves evaporating an aliphatic ketone solvent having 3 to 6 carbon atoms contained in the crystallization solution to precipitate crystals. In the poor solvent addition crystallization step of the method for producing the composition of the present invention, a poor solvent generally refers to a solvent with low solubility of chemical substances, but in the present invention, it refers to a solvent with low solubility of compound A, which is the solute. Specifically, examples of poor solvents include aromatic hydrocarbon solvents having 7 to 9 carbon atoms and chain-like or cyclic aliphatic hydrocarbon solvents having 5 to 8 carbon atoms. Specific examples of aromatic hydrocarbon solvents having 7 to 9 carbon atoms include toluene, orthoxylene, metaxylene, paraxylene, mixed xylene, and mesitylene, of which at least one is preferred, and among these, at least one aromatic hydrocarbon solvent having 7 or 8 carbon atoms is more preferred, at least one of toluene, orthoxylene, metaxylene, and paraxylene is even more preferred, and toluene, which is an aromatic hydrocarbon solvent having 7 carbon atoms, is particularly preferred. The chain-like or cyclic aliphatic hydrocarbon solvent having 5 to 8 carbon atoms is preferably a chain-like or cyclic aliphatic hydrocarbon solvent having 6, 7, or 8 carbon atoms, and more preferably a chain-like or cyclic aliphatic hydrocarbon solvent having 6 or 8 carbon atoms.Specific examples of the chain-like or cyclic aliphatic hydrocarbon solvent having 5 to 8 carbon atoms include n-pentane, n-hexane, n-heptane, n-octane, isooctane, and cyclohexane, of which at least one is preferred, and among these, at least one of n-hexane, n-heptane, n-octane, isooctane, and cyclohexane is more preferred, at least one of n-hexane, n-octane, isooctane, and cyclohexane is even more preferred, and at least one of isooctane and cyclohexane is particularly preferred. The poor solvent used in the crystallization step of the present invention is preferably at least one of toluene, orthoxylene, metaxylene, paraxylene, mixed xylene, mesitylene, n-pentane, n-hexane, n-heptane, n-octane, isooctane, and cyclohexane; more preferably at least one of toluene, orthoxylene, metaxylene, paraxylene, n-hexane, n-heptane, n-octane, isooctane, and cyclohexane; even more preferably at least one of toluene, n-hexane, n-octane, isooctane, and cyclohexane; and particularly preferably at least one of toluene, isooctane, and cyclohexane. The amount of poor solvent used with respect to the aliphatic ketone solvent having 3 to 6 carbon atoms can be appropriately adjusted in view of the conditions of the crystallization step and the solubility of the aliphatic ketone solvent having 3 to 6 carbon atoms and compound A of the poor solvent, but it is preferably in the range of 1.0 to 200 times by weight, more preferably in the range of 1.0 to 150 times by weight, even more preferably in the range of 1.0 to 50.0 times by weight, even more preferably in the range of 1.0 to 15.0 times by weight, and particularly preferably in the range of 1.0 to 5.0 times by weight. In the crystallization step of the manufacturing method of the present invention, a small amount of solvent other than the above-mentioned organic solvent may be included, as long as it does not impair the effects of the present invention. A small amount means, for example, the amount of organic solvent or water used in the steps preceding the crystallization step, such as the reaction step or water washing step, that remains after the step to remove them.

[0016] The composition containing compound A obtained by the crystallization step can be separated from the crystallized liquid by filtration and recovered. During filtration, the filtered composition containing compound A can be washed with an organic solvent, such as an aliphatic ketone solvent having 3 to 6 carbon atoms, an aromatic hydrocarbon solvent having 7 to 9 carbon atoms, or a linear or cyclic aliphatic hydrocarbon solvent having 5 to 8 carbon atoms. The obtained composition of compound A can be dried to remove the solvent used. The drying operation can preferably be carried out at a temperature in the range of 30 to 100°C, more preferably in the range of 60 to 95°C, and even more preferably in the range of 70 to 90°C. Drying can be carried out under atmospheric pressure or reduced pressure, but in industrial operations, reduced pressure of about 10 kPa is preferred, more preferably about 5 kPa, and even more preferably about 1.5 kPa, as these reduced pressure conditions are preferable because they allow for more efficient removal of the solvent used.

[0017] The composition containing compound A obtained by the method for producing the composition of the present invention is preferably in the form of a powder, and more preferably in the form of a crystalline powder. A powder is defined as a state in which particles are aggregated, and the powder contains substantially spherical or amorphous particles and is fluid. There are no restrictions on the size of the particles contained in the powder; it may be granular, granular, microcrystalline (needle-shaped, cube-shaped, etc., where the shape is somewhat visible), fine particles, powder, or fine powder. Crystallinity can be demonstrated by the appearance of an endothermic peak indicating melting when differential scanning calorimetry is performed, or by the appearance of a diffraction peak in the powder X-ray diffraction peak pattern. This form is extremely useful as a method for producing the composition of the present invention because it allows the manufacturing process to proceed with a powder that is easy to handle, and it is also easy to handle when producing various materials using compound A as a raw material. The purity of the composition containing compound A obtained by the method for producing the composition of the present invention is preferably such that the ratio of the peak area of ​​compound A to the peak area of ​​all components detected at a wavelength of 280 nm in high-performance liquid chromatography (HPLC) analysis is 95.0% or higher, more preferably 97.0% or higher, even more preferably 98.0% or higher, and particularly preferably 99.0% or higher. The method for HPLC analysis of the purity of the composition of the present invention is the same as the HPLC analysis method in the examples described later. The Hazen unit color number (APHA) when the composition obtained by the method for producing the composition of the present invention is dissolved in a 10% by weight acetone solution is preferably 200 or less, more preferably 180 or less, even more preferably 150 or less, and particularly preferably 100 or less. Since a smaller value for the Hazen unit color number (APHA) is preferable, there is no limit to the lower limit of this value range, but it may be 1 or higher. The upper and lower limits of these ranges can be arbitrarily combined.

[0018] There are no restrictions on the peak top temperature of the endothermic peak shown when differential scanning calorimetry is performed on a composition containing compound A obtained by the method for producing the composition of the present invention, but it is preferable that it be one of the following temperature ranges (i), (ii), (iii), and (iv). Temperature range (i): The peak top temperature of the endothermic peak obtained by differential scanning calorimetry is in the range of 203 to 213°C. It is more preferable that the peak top temperature is in the range of 204 to 212°C, and particularly preferable that it is in the range of 205 to 211°C. Furthermore, it is preferable that the onset temperature of the endothermic peak obtained by differential scanning calorimetry in this case is in the range of 195 to 210°C. It is more preferable that the onset temperature is in the range of 197 to 207°C, even more preferable that it is in the range of 198 to 206°C, and particularly preferable that it is in the range of 199 to 205°C. Temperature range (ii): The peak top temperature of the endothermic peak obtained by differential scanning calorimetry is in the range of 144 to 163°C. The peak top temperature is more preferably in the range of 145 to 162°C, and particularly preferably in the range of 146 to 161°C. Furthermore, in this case, the onset temperature of the endothermic peak determined by differential scanning calorimetry analysis is preferably in the range of 135 to 150°C. The onset temperature is more preferably in the range of 136 to 149°C, even more preferably in the range of 137 to 148°C, and particularly preferably in the range of 138 to 147°C. Temperature range (iii): The peak top temperature of the endothermic peak determined by differential scanning calorimetry analysis is in the range of 144 to 151°C. The peak top temperature is more preferably in the range of 145 to 150°C, and particularly preferably in the range of 146 to 148°C. Furthermore, in this case, the onset temperature of the endothermic peak determined by differential scanning calorimetry analysis is preferably in the range of 135 to 145°C. The onset temperature is more preferably in the range of 136 to 144°C, even more preferably in the range of 137 to 143°C, and particularly preferably in the range of 138 to 142°C. Temperature range (iv): The peak top temperature of the endothermic peak determined by differential scanning calorimetry analysis is in the range of 156 to 163°C.The peak top temperature is more preferably in the range of 157 to 162°C, and particularly preferably in the range of 158 to 161°C. Furthermore, it is preferable that the onset temperature of the endothermic peak determined by differential scanning calorimetry analysis in this case is in the range of 140 to 150°C. The onset temperature is more preferably in the range of 141 to 149°C, even more preferably in the range of 142 to 148°C, and particularly preferably in the range of 143 to 147°C. The differential scanning calorimetry (DSC) method in this invention is the same as the differential scanning calorimetry method in the analysis method of the examples described later.

[0019] Regarding a composition containing compound A obtained by the method for producing the composition of the present invention, there are no particular restrictions on the powder X-ray diffraction peak pattern using Cu-Kα rays, but it is preferable that it be pattern (i) or (ii). Pattern (i): In the powder X-ray diffraction peak pattern using Cu-Kα rays, diffraction peaks are present at diffraction angles 2θ of 10.9±0.2°, 15.1±0.2°, and 19.7±0.2°. In the powder X-ray diffraction peak pattern using Cu-Kα rays, it is more preferable that diffraction peaks are present at diffraction angles 2θ of 17.8±0.2°, 20.8±0.2°, and 21.8±0.2° in addition to the above peaks. If the method for producing the composition of the present invention is a method that includes poor solvent addition crystallization using toluene as the poor solvent, this pattern (i) may be obtained. Pattern (ii): In the powder X-ray diffraction peak pattern using Cu-Kα rays, diffraction peaks are present at diffraction angles 2θ of 6.3±0.2°, 11.3±0.2°, and 22.5±0.2°. In the powder X-ray diffraction peak pattern using Cu-Kα rays, it is more preferable that diffraction peaks are present at 19.7±0.2° and 25.1±0.2° in addition to the above peaks, and even more preferable that diffraction peaks are present at 12.2±0.2°, 14.5±0.2°, and 20.5±0.2° in addition to the above peaks. This pattern (ii) may occur when the method for producing the composition of the present invention is a crystallization method using an aliphatic ketone solvent having 3 to 6 carbon atoms alone, most preferably acetone or methyl ethyl ketone alone, to precipitate crystals. In any diffraction peak pattern, the relative intensity of the powder X-ray diffraction peaks using Cu-Kα rays is preferably 10 or higher, more preferably 15 or higher, and even more preferably 25 or higher, with the peak with the highest intensity as the reference (relative intensity of 100). However, the relative intensity may fluctuate depending on the measuring device and conditions, and in the case of mixtures with other crystals. Therefore, the crystalline phase can be identified based on the analysis method of normal powder X-ray diffraction analysis. The method for performing powder X-ray diffraction (PXRD) analysis in the present invention is the same as the method for powder X-ray diffraction (PXRD) analysis in the analysis method of the examples described later.

[0020] The composition containing compound A obtained by the method for producing the composition of the present invention preferably has a weight loss rate of 10% by weight or less at 300°C as determined by thermogravimetric analysis. This weight loss rate is more preferably 8% by weight or less, even more preferably 6% by weight or less, and particularly preferably 4% by weight or less. As for the lower limit of this range, there is no limit as a lower content is preferable, but it may be 0.5% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more. The upper and lower limits of these ranges can be arbitrarily combined. The composition containing compound A may contain organic solvents, raw materials, water, etc., used in the manufacturing process. Examples of organic solvents may include aliphatic ketone solvents with 3 to 6 carbon atoms, aromatic hydrocarbon solvents with 7 to 9 carbon atoms, chain-like or cyclic aliphatic hydrocarbon solvents with 5 to 8 carbon atoms, etc., used in the crystallization process, or organic solvents used in previous processes. The method for performing thermogravimetric analysis is the differential thermal and thermogravimetric (TG / DTA) simultaneous measurement thermal analysis method described in the examples below. The composition containing compound A obtained by the method for producing the composition of the present invention preferably has a sodium content of 5.0 ppm or less, more preferably 3.0 ppm or less, even more preferably 1.0 ppm or less, and particularly preferably 0.5 ppm or less. The composition containing compound A obtained by the method for producing the composition of the present invention preferably has a potassium content of 5.0 ppm or less, more preferably 3.0 ppm or less, even more preferably 1.0 ppm or less, and particularly preferably 0.5 ppm or less. The composition containing compound A obtained by the method for producing the composition of the present invention preferably has an iron content of 5.0 ppm or less, more preferably 3.0 ppm or less, even more preferably 1.0 ppm or less, and particularly preferably 0.5 ppm or less.The composition containing compound A obtained by the method for producing the composition of the present invention preferably has a copper content of 5.0 ppm or less, more preferably 3.0 ppm or less, even more preferably 1.0 ppm or less, and particularly preferably 0.5 ppm or less. The analytical method for the content of these metals is the same as the analytical method described in the examples below.

[0021] <Crystals of Compound A of the Present Invention> The crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene (Compound A) of the present invention are characterized in that the peak top temperature of the endothermic peak determined by differential scanning calorimetry is in the range of 144 to 163°C (this temperature range is referred to as "temperature range A"). The peak top temperature is more preferably in the range of 145 to 162°C, and particularly preferably in the range of 146 to 161°C. Furthermore, in the case of "temperature range A", the onset temperature of the endothermic peak determined by differential scanning calorimetry is preferably in the range of 135 to 150°C. The onset temperature is more preferably in the range of 136 to 149°C, even more preferably in the range of 137 to 148°C, and particularly preferably in the range of 138 to 147°C. In the case of the crystal of compound A of the present invention in the aforementioned "temperature range A," the peak top temperature of the endothermic peak determined by differential scanning calorimetry analysis may be in the range of 144 to 151°C, and this case is also preferable (this temperature range is referred to as "temperature range A-1"). In this case, the peak top temperature is more preferably in the range of 145 to 150°C, and particularly preferably in the range of 146 to 148°C. Furthermore, in the case of this "temperature range A-1," it is preferable that the onset temperature of the endothermic peak determined by differential scanning calorimetry analysis is in the range of 135 to 145°C. The onset temperature is more preferably in the range of 136 to 144°C, even more preferably in the range of 137 to 143°C, and particularly preferably in the range of 138 to 142°C. The crystals of compound A of the present invention in the aforementioned "temperature range A" may also have a peak top temperature of the endothermic peak determined by differential scanning calorimetry analysis in the range of 156 to 163°C, and this case is also preferable (this temperature range is referred to as "temperature range A-2"). In this case, the peak top temperature is more preferably in the range of 157 to 162°C, and particularly preferably in the range of 158 to 161°C. Furthermore, in the case of this "temperature range A-2", it is preferable that the onset temperature of the endothermic peak determined by differential scanning calorimetry analysis is in the range of 140 to 150°C.The onset temperature is more preferably in the range of 141 to 149°C, even more preferably in the range of 142 to 148°C, and particularly preferably in the range of 143 to 147°C. That is, the crystal of compound A of the present invention can also be identified as a crystal characterized in that the peak top temperature of the endothermic peak determined by differential scanning calorimetry analysis is within the "temperature range A-1" or "temperature range A-2" described above. In such cases, the preferred embodiments of "temperature range A-1" and "temperature range A-2" are as described above. The differential scanning calorimetry (DSC) method in the present invention is the method according to the differential scanning calorimetry method in the analysis method of the examples described later. Since the crystal of compound A of the present invention melts at a relatively low temperature of less than 200°C, the melting temperature can be kept low, for example, when used as a resin monomer. This is useful because it can reduce the amount of heat required to melt the monomer, contributing to energy saving, and can also suppress discoloration and deterioration due to high temperatures.

[0022] The crystal of compound A of the present invention preferably has diffraction peaks at diffraction angles 2θ of 6.3±0.2°, 11.3±0.2°, and 22.5±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays. More preferably, in the powder X-ray diffraction peak pattern using Cu-Kα rays, diffraction peaks are further present at diffraction angles 2θ of 19.7±0.2° and 25.1±0.2° in addition to the above peaks, and even more preferably, diffraction peaks are further present at diffraction angles 2θ of 12.2±0.2°, 14.5±0.2°, and 20.5±0.2° in addition to the above peaks. In addition, the peak of powder X-ray diffraction using Cu-Kα rays is preferably 10 or higher, more preferably 15 or higher, and even more preferably 25 or higher, with the peak with the highest intensity as the reference (relative intensity of 100). However, the relative intensity may fluctuate depending on the measuring device and conditions, and in the case of a mixture with other crystals. Therefore, the crystalline phase can be identified based on the analysis method of ordinary powder X-ray diffraction analysis. The method for performing powder X-ray diffraction (PXRD) analysis in the present invention is the same as the method for powder X-ray diffraction (PXRD) analysis in the analysis method of the examples described later.

[0023] The crystals of compound A of the present invention preferably have a ratio of 95.0% or more, more preferably 97.0% or more, even more preferably 98.0% or more, and particularly preferably 99.0% or more, when subjected to high-performance liquid chromatography (HPLC) analysis, to the peak area of ​​compound A relative to the peak area of ​​all components detected at a wavelength of 280 nm. With respect to the crystals of compound A of the present invention, the ratio of the peak area of ​​compound A in the said analysis is referred to as the purity of compound A. The HPLC analysis method is the same as the HPLC analysis method described in the examples below. The crystals of compound A of the present invention preferably have a Hazen unit color number (APHA) of 200 or less, more preferably 180 or less, even more preferably 150 or less, and particularly preferably 100 or less, when the crystals of compound A are prepared as a 10% by weight acetone solution. Since a smaller Hazen unit color number (APHA) value is preferable, there is no lower limit within this range, but it may be 1 or greater. The upper and lower limits of these ranges can be arbitrarily combined. The crystals of compound A of the present invention preferably have a weight loss rate of 10% by weight or less at 300°C, determined by thermogravimetric analysis. This weight loss rate is more preferably 8% by weight or less, even more preferably 6% by weight or less, and particularly preferably 4% by weight or less. While there are no restrictions on the lower limit of this range, as a lower content is preferable, it may be 0.5% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more. The upper and lower limits of these ranges can be arbitrarily combined. The crystals of compound A may contain organic solvents, raw materials, and water used in the manufacturing process. Organic solvents may include, for example, aliphatic ketone solvents with 3 to 6 carbon atoms used in the crystallization process, or organic solvents used in earlier processes. The method for thermogravimetric analysis is the differential thermal and thermogravimetric (TG / DTA) simultaneous measurement thermal analysis method described in the examples below.When the sodium content of the crystals of compound A of the present invention is analyzed, it is preferably 5.0 ppm or less, more preferably 3.0 ppm or less, even more preferably 1.0 ppm or less, and particularly preferably 0.5 ppm or less. When the potassium content of the crystals of compound A of the present invention is analyzed, it is preferably 5.0 ppm or less, more preferably 3.0 ppm or less, even more preferably 1.0 ppm or less, and particularly preferably 0.5 ppm or less. When the iron content of the crystals of compound A of the present invention is analyzed, it is preferably 5.0 ppm or less, more preferably 3.0 ppm or less, even more preferably 1.0 ppm or less, and particularly preferably 0.5 ppm or less. The copper content of the crystals of compound A of the present invention is preferably 5.0 ppm or less, more preferably 3.0 ppm or less, even more preferably 1.0 ppm or less, and particularly preferably 0.5 ppm or less, when analyzed. The method for analyzing the content of these metals is the same as the analytical method described in the examples below.

[0024] <Method for producing crystals of compound A of the present invention> The method for producing crystals of compound A of the present invention is characterized by comprising a crystallization step of precipitating crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene (compound A) from a crystallization solution containing an aliphatic ketone solvent having 3 to 6 carbon atoms. Compound A used in the crystallization step can be obtained based on the above-mentioned section (Method for producing compound A).

[0025] (Crystallization Solvent) The aliphatic ketone solvent having 3 to 6 carbon atoms used in the crystallization step in the crystal production method of the present invention includes a linear aliphatic ketone solvent having 3 to 6 carbon atoms and a cyclic aliphatic ketone solvent having 3 to 6 carbon atoms. Among these, from the viewpoint of ease of operation of the industrial crystallization step, a linear aliphatic ketone solvent having 3 to 6 carbon atoms or a cyclic aliphatic ketone solvent having 6 carbon atoms is preferred, a linear aliphatic ketone solvent having 3 to 6 carbon atoms is more preferred, a linear aliphatic ketone solvent having 3 or 4 carbon atoms is even more preferred, and acetone, a linear aliphatic ketone having 3 carbon atoms, is particularly preferred. Specific examples of aliphatic ketone solvents to be used include acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. At least one of these is preferred, at least one selected from acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, methyl isobutyl ketone, and cyclohexanone is more preferred, at least one selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone is even more preferred, and at least one selected from acetone and methyl ethyl ketone is particularly preferred. Two or more types of aliphatic ketone solvents may be used, but it is preferable to use one type alone. In other words, it is preferable to use one solvent selected from acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; it is more preferable to use one solvent selected from acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, methyl isobutyl ketone, and cyclohexanone; it is even more preferable to use one solvent selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and it is particularly preferable to use acetone or methyl ethyl ketone as the solvent.The amount of aliphatic ketone solvent having 3 to 6 carbon atoms used relative to compound A can be appropriately adjusted in view of the conditions of the crystallization step and the solubility of the aliphatic ketone solvent used, but it is preferably in the range of 1.0 to 35.0 times by weight, more preferably in the range of 1.0 to 10.0 times by weight, even more preferably in the range of 1.2 to 6.0 times by weight, and particularly preferably in the range of 1.5 to 3.0 times by weight. In the crystallization step of the method for producing crystals of compound A of the present invention, a small amount of a solvent other than the aliphatic ketone solvent having 3 to 6 carbon atoms may be included as long as it does not impair the effects of the present invention, but it is preferable to precipitate crystals using the aliphatic ketone solvent having 3 to 6 carbon atoms alone. A small amount means, for example, the amount of organic solvent or water used in the steps preceding the crystallization step, such as the reaction step, water washing treatment, and crystallization, that remains after the step to remove them, or the amount included by adding a poor solvent to an extent that does not impair the effects of the present invention.

[0026] (Crystallization Method) There are no restrictions on the method for precipitating crystals in the crystallization step of the crystal manufacturing method of the present invention. Examples include cooling crystallization, in which crystals are precipitated by cooling the crystallization solution; evaporation crystallization, in which crystals are precipitated by evaporating the solvent from the crystallization solution; and poor solvent addition crystallization, in which crystals are precipitated by adding a poor solvent to the crystallization solution in an amount that does not impair the effect of the crystals of the present invention. One of these methods may be used alone, or a combination of multiple methods may be used. A method including at least one of cooling crystallization, evaporation crystallization, and poor solvent addition crystallization is preferred, a method including at least cooling crystallization from among cooling crystallization, evaporation crystallization, and poor solvent addition crystallization is more preferred, and a method including at least cooling crystallization from among cooling crystallization and evaporation crystallization is even more preferred. In a method combining evaporation crystallization and cooling crystallization, it is preferable that the solvent is evaporated from the crystallization solution before cooling.

[0027] In the crystal manufacturing method of the present invention, the temperature of the crystallization solution in the cooling crystallization step is such that the upper limit of the temperature of the crystallization solution is 1°C lower than the boiling point of the crystallization solvent used, and the lower limit of the temperature depends on the aliphatic ketone solvent with 3 to 6 carbon atoms used. The crystallization solution is heated to 15°C, preferably 20°C, more preferably 30°C, and particularly preferably 45°C, within the range from the upper limit to the lower limit. After that, the crystallization solution is cooled to a range of 0 to 40°C, preferably 10 to 40°C, more preferably 15 to 35°C, and even more preferably 15 to 30°C. Specifically, in the crystal manufacturing method of the present invention, the temperature 1°C lower than the boiling point of the crystallization solvent used means, for example, 55°C when using acetone with a boiling point of 56°C (at 1 atmosphere). When two or more aliphatic ketone solvents with 3 to 6 carbon atoms are used, or when a small amount of a solvent other than an aliphatic ketone solvent with 3 to 6 carbon atoms is included, it means the temperature based on the boiling point of the type and composition of the solvent used. In the crystallization method of the present invention, the evaporation crystallization step is a method of precipitating crystals by evaporating the aliphatic ketone solvent having 3 to 6 carbon atoms contained in the crystallization solution.

[0028] The crystals of compound A obtained by the crystallization step can be separated from the crystallization solution by filtration and recovered. During filtration, an organic solvent, such as an aromatic hydrocarbon solvent having 7 to 9 carbon atoms or a chain or cyclic aliphatic hydrocarbon solvent having 5 to 8 carbon atoms, can be used to wash the filtered-off compound A crystals. The obtained compound A crystals can be dried to remove the solvent used. The drying operation can preferably be carried out at a temperature in the range of 30 to 100°C, more preferably in the range of 60 to 95°C, and even more preferably in the range of 70 to 90°C. Drying can be carried out under atmospheric pressure or reduced pressure, but in industrial operations, reduced pressure of about 10 kPa is preferred, more preferably about 5 kPa, and even more preferably about 1.5 kPa, as these reduced pressure conditions are preferable because they allow for more efficient removal of the solvent used.

[0029] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples. <Analysis Method> 1. High-performance liquid chromatography (HPLC) analysis (Apparatus and conditions) High-performance liquid chromatography analyzer: Prominence UFLC / manufactured by Shimadzu Corporation Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Column: HALO C18 column 3.0 × 75 mm Oven temperature: 50℃ Flow rate: 0.7 mL / min. Mobile phase: (A) 0.2 vol% aqueous acetic acid solution, (B) methanol gradient Conditions: (B) vol% (time from start of analysis) 0-7 min.: 50 → 70%, 7-13 min.: 70%, 13-20 min.: 70 → 100%, 20-23 min. : 100% Sample injection volume: 5 μL Analytical sample: Composition of compound A (crystals) 50 mg / 50 mL (solvent: methanol) Detection wavelength: 280 nm

[0030] 2. Differential Scanning Calorimetry (DSC) (Analysis Method) 2-3 mg of crystals were collected in an aluminum sample container, the lid was attached, and the container was pressed to prepare a sample. The obtained sample was analyzed using the following equipment and conditions. (Equipment and Conditions) Equipment: DSC7020 / Hitachi High-Tech Science Co., Ltd. Heating rate: 10°C / min. Measurement temperature range: 30-300°C Measurement atmosphere: 50 mL / min. nitrogen

[0031] 3. Nuclear Magnetic Resonance (NMR) Analysis (Instrument and Conditions) Instrument: Fourier Transform Nuclear Magnetic Resonance AVANCE III HD 400 / BRUKER Solvent: Deuterated Chloroform (CDCl ３ ) measurement: １ H-NMR and １３ Measure the C-NMR spectrum.

[0032] 4. Powder X-ray diffraction (PXRD) analysis: The crystals were thoroughly ground in a mortar and packed into the measurement cell. The obtained sample was analyzed using the following equipment and conditions. (Equipment and conditions) Equipment: SmartLab / Rigaku Corporation X-ray source: CuKα Scan axis: 2θ / θ Mode: Continuous Measurement range: 2θ = 5° to 90° Step: 0.02° Speed ​​measurement time: 2θ = 10° / min. Output: 40kV, 30mA

[0033] 5. Analysis of Metal Content (Analysis Method) After dry ashing, acid dissolution was performed, and the sodium and potassium content was analyzed by atomic absorption spectrometry, while the iron and copper content was analyzed by inductively coupled plasma mass spectrometry.

[0034] 6. Moisture content measurement (Equipment and conditions) Equipment: Karl Fischer moisture meter. Moisture content was measured based on the standard Karl Fischer titration method.

[0035] 7. Hue Evaluation (Equipment and Conditions) Equipment: TZ 6000 / Manufactured by Nippon Denshoku Industries Co., Ltd. For the compound to be measured, an acetone solution (10% by weight) was prepared and the hue was measured.

[0036] 8. Headspace Gas Chromatography (HS-GC) (1) HS-GC analyzer and conditions Gas chromatography system: GC-2010 Plus / Shimadzu Corporation Column: InertCap-160m x 0.25mmΦ / GL Sciences Inc. Film thickness: 0.25μm Detector: FID Vaporization chamber temperature: 300℃ Detector temperature: 310℃ Column temperature: 40℃ Column heating conditions (holding time): 40℃ (10 min.) → 20℃ / min. → 300℃ (5 min.) Makeup gas (nitrogen) flow rate: 30.0 mL / min. Hydrogen flow rate: 40.0 mL / min. Air flow rate: 400.0 mL / min. Carrier gas: Nitrogen Pressure: 118 kPa Column flow rate: 0.92 mL / min. Linear velocity: 19.9 cm / sec. Total flow rate: 8.5 mL / min. Split ratio: 5 HS sampler apparatus: Turbo Matrix HS40 / PerkinElmer Co., Ltd. HS carrier gas pressure: 154.0 kPa Oven temperature: 100°C Needle temperature: 105°C Transfer temperature: 105°C Holding time: 20 min. Pressurization time: 3 min. Withdrawal time: 0.5 min. Injection time: 0.05 min. (2) Measurement of the solvent content of the crystals of compound A Samples of multiple N-methylpyrrolidone (NMP) solutions with different concentrations were prepared for the solvent to be quantified and analyzed using the apparatus and conditions described in (1) above. A calibration curve was created from the relationship between the sample concentration of the component to be quantified and the peak area detected by HS-GC analysis. 0.5 g of crystals was dissolved in 9.5 g of NMP, and 3.0 g of the resulting sample solution was analyzed using the apparatus and conditions described in (1) above. The amount of solvent contained in the crystal was calculated using a calibration curve.

[0037] 9. Thermal Analysis by Simultaneous Differential Thermal and Thermogravimetric (TG / DTA) Measurement (Analysis Method) 10 mg of crystals was weighed into an aluminum sample container and analyzed using the following apparatus and conditions. (Apparatus and Conditions) Apparatus: DTG-60A / Shimadzu Corporation Heating rate: 10°C / min. Measurement temperature range: 30 to 300°C Measurement atmosphere: Open, 50 mL / min of nitrogen

[0038] <Comparative Example 1: Further testing of the method described in Patent Document 1> 0.2 g of compound A and 20.0 g of toluene were added to a test tube and stirred for 1 hour while heating at 70°C, confirming that compound A was completely dissolved. The concentration of compound A at this time was 0.98% by weight. Subsequently, 0.4 g of compound A was added to the same test tube and stirred for 1 hour while heating under reflux at 130°C, confirming that compound A was completely dissolved. The concentration of compound A at this time was 2.96% by weight.

[0039] From the results of Comparative Example 1, it became clear that when compound A is completely dissolved in toluene alone, even when heated under reflux at a high temperature of 130°C, exceeding the boiling point of toluene (110°C), the solubility of compound A remains low. Since the concentration of compound A in the crystallization solution using toluene as the solvent is dilute, it is considered that crystal precipitation is difficult, or even if crystals do precipitate, the amount of compound A obtainable relative to the weight of the crystallization solution is very small. Patent Document 1 describes the recrystallization operation of compound A by mixing hexane with the toluene solution. Adding hexane to the crystallization solution of compound A and toluene under reflux to increase the solubility of compound A in toluene is considered to be extremely difficult to operate, given the boiling point of hexane (68.7°C), as there is a risk of rapid vaporization of hexane. For this reason, it was considered that these conditions make it difficult to create a difference in solubility necessary for crystal precipitation. Even when hexane is added to the toluene crystallization solution at 70°C, the toluene solution of compound A is dilute, so it can be understood that the amount of compound A obtained per unit volume will be small. From these findings, it has become clear that the method for producing compound A described in Patent Document 1 is difficult or extremely inefficient in obtaining crystals, and is therefore unsuitable for industrial production.

[0040] <Example 1> In a four-neck flask equipped with a thermometer, a stirrer, and a condenser, 99.0 g of acetone was added to 68.6 g of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene (Compound A: the Hazen unit color number (APHA) of a 10 wt% acetone solution was 190). The inside of the flask was purged with nitrogen and the whole was dissolved. Then, 280.0 g of toluene was added and heated to a maximum of 100 °C, and distillation was carried out to distill acetone out of the reaction vessel. Solids precipitated during the process of distilling acetone. The weight of the recovered distillate was 102.2 g. After distillation, the solution in the reaction vessel was cooled from 100 °C at a rate of 10 °C / hour. The precipitated solid was filtered off by centrifugation, washed with 35.2 g of toluene, and dried under reduced pressure at 80 °C and 4.0 kPa for 5 hours to obtain 68.0 g of a pale yellow powder. The ratio of the weight of Compound A in the obtained powder to the weight of Compound A subjected to the crystallization step (yield of the crystallization step) was 91%. The １ H-NMR and １３ the analysis results of C-NMR are shown in FIGS. 1 and 2. As a result of HPLC analysis, the obtained powder contained 98.8% (area percentage) of Compound A and 0.5% (area percentage) of the monohydroxyethoxy compound. The Hazen unit color number (APHA) of the solution hue when the obtained powder of Compound A was made into a 10 wt% acetone solution was 90. Since the Hazen unit color number (APHA) of the 10 wt% acetone solution of Compound A subjected to the crystallization step was 190, it became clear that the hue was greatly improved by the crystallization step. The contents of sodium, potassium, and iron in the obtained powder of Compound A were less than 0.1 ppm, and the copper content was 0.3 ppm. Since diffraction patterns were observed in the PXRD analysis for the obtained powder, it was revealed that it was crystalline. Table 1 shows the diffraction angle 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 25 or more based on the peak with the highest intensity. The PXRD analysis chart is shown in FIG. 3.

[0041]

[0042] The crystals obtained in Example 1 contained 7.4% by weight of toluene and 0.1% by weight of acetone. As a result of the DSC analysis of the obtained crystals, the onset temperature of the endothermic peak was 200.1 °C, and the endothermic peak top temperature was 207.6 °C. The DSC data is shown in FIG. 4. The results of the TG-DTA analysis of the obtained crystals are shown in FIG. 5. In the TG-DTA analysis, almost no weight loss was observed even at temperatures exceeding the boiling point of toluene (110.6 °C: 1 atm), and a sharp weight loss was observed around 208 °C (peak top temperature) where an endothermic peak appeared. The weight loss ratio in the range of 200 to 220 °C was 3.1%. From this weight loss behavior, it was推测 that the crystals of the obtained Compound A included toluene. The weight loss rate at 300 °C was 6.03%.

[0043] From the results of Example 1, it became clear that the production method of the present invention has a high yield of Compound A, can obtain crystals of Compound A by a crystallization operation, and can improve the hue of the obtained crystals.

[0044] <Solubility Evaluation of Aliphatic Ketone Solvents> Using the crystals of Compound A obtained in Example 1, the solubility of dissolving Compound A in aliphatic ketone solvents was evaluated. For 0.5 g of the crystals of Compound A, an aliphatic ketone solvent was added at room temperature (20 °C), and the added amount required until dissolution was measured, and the solute concentration of the aliphatic ketone solution was calculated. The dissolution of the crystals of Compound A was confirmed visually. The aliphatic ketone solvents used to evaluate the solubility of Compound A were acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone. The solute concentrations of each solvent are shown in Table 2.

[0045]

[0046] In Patent Document 1, the toluene solvent used to dissolve compound A had a solute concentration of 0.98% by weight at 70°C, as shown in Comparative Example 1, and a solute concentration of 2.96% by weight under heating reflux conditions at 130°C. In contrast, the aliphatic ketone solvent according to the present invention has the solubility shown in Table 2 at room temperature (20°C), indicating high solubility for dissolving compound A, and further increasing solubility for dissolving compound A at higher temperatures. Therefore, it has become clear that it is an organic solvent suitable for the industrial production of compound A by crystallization.

[0047] <Crystallization Method Using Only Aliphatic Ketone Solvents> <Example 2> At room temperature, 0.60 g of the crystals of compound A obtained in Example 1 and 1.41 g of acetone were mixed in a screw-top bottle that could be sealed tightly, and a solution was prepared by heating to 50°C until uniformly dissolved. The prepared solution was left to stand overnight at room temperature to precipitate powder. The precipitated powder was filtered by Kiriyama filtration, washed with acetone, and dried under reduced pressure at 70°C and 1.6 kPa for 3 hours to obtain 0.39 g of white powder. The yield of compound A powder obtained by these operations was 65%. The obtained powder was found to be crystalline, as a diffraction pattern was observed by PXRD analysis. Table 3 shows the diffraction angle 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 10 or more relative to the peak with the greatest intensity. The PXRD analysis chart is shown in Figure 6. The obtained crystals were found to have characteristic peaks different from those of compound A crystals obtained in Example 1.

[0048]

[0049] Differential scanning calorimetry (DSC) analysis of the obtained crystals revealed an onset temperature of 145.0°C for the endothermic peak and a peak-top temperature of 159.3°C for the endothermic peak. The DSC analysis chart is shown in Figure 7. The DSC analysis of the obtained crystals showed an endothermic peak, which was considered to correspond to the melting of the crystals. The TG chart obtained from TG-DTA analysis of the obtained crystals is shown in Figure 8. A weight loss of approximately 3% by weight was observed up to 190°C, and it was found that no significant weight loss was observed thereafter, up to temperatures exceeding 300°C. The weight loss rate at 300°C was 3.04%. The amount of solvent contained in the obtained crystals was measured by HS-GC and found to contain 3.4% by weight of acetone.

[0050] <Example 3> At room temperature, 0.60 g of the compound A crystals obtained in Example 1 and 1.40 g of MEK were mixed in a screw-top bottle that could be sealed tightly, and a solution was prepared by heating to 70°C until uniformly dissolved. The prepared solution was left to stand overnight at room temperature to precipitate powder. The precipitated powder was filtered by Kiriyama filtration, washed with MEK, and dried under reduced pressure at 70°C and 1.6 kPa for 3 hours to obtain 0.28 g of white powder. The yield of compound A powder obtained by these operations was 47%. The obtained powder was found to be crystalline, as a diffraction pattern was observed by PXRD analysis. Table 4 shows the diffraction angle 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 10 or more relative to the peak with the greatest intensity. The PXRD analysis chart is shown in Figure 9. The obtained crystals were found to be crystals with characteristic peaks common to the compound A crystals obtained in Example 2.

[0051]

[0052] Differential scanning calorimetry (DSC) analysis of the obtained crystals revealed an onset temperature of 140.0°C for the endothermic peak and a peak top temperature of 147.0°C. The DSC analysis chart is shown in Figure 10. The DSC analysis of the obtained crystals showed an endothermic peak, which was considered to correspond to the melting of the crystals. The TG chart obtained from TG-DTA analysis of the obtained crystals is shown in Figure 11. A weight loss of approximately 5% by weight was observed up to 180°C, and it was found that no significant weight loss was observed thereafter, up to temperatures exceeding 300°C. The weight loss rate at 300°C was 5.97%. The amount of solvent contained in the obtained crystals was measured by HS-GC and found to contain 5.9% by weight of MEK.

[0053] <Crystallization of Compound A using Aliphatic Ketone Solvent and Aliphatic Hydrocarbon Solvent> <Example 4> At room temperature, a solution was prepared by mixing 0.13 g of the Compound A crystals obtained in Example 1 with 3.88 g of MEK in a screw-top bottle that could be sealed tightly. 21.50 g of toluene was added to this solution and mixed. The mixed solution was heated under reduced pressure to remove the solvent, resulting in the precipitation of a powdery Compound A. The precipitated powder was filtered by Kiriyama filtration, washed with toluene, and dried under reduced pressure at 70°C and 1.6 kPa for 5 hours to obtain 0.11 g of white powder. The yield of Compound A powder obtained by these operations was 85%. The obtained powder was found to be crystalline, as a diffraction pattern was observed by PXRD analysis. Table 5 shows the diffraction angle 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 10 or more relative to the peak with the greatest intensity. The PXRD analysis chart is shown in Figure 12. The obtained crystals were found to have characteristic peaks common to those of the compound A crystal obtained in Example 1.

[0054]

[0055] Differential scanning calorimetry (DSC) analysis of the obtained crystals revealed an onset temperature of 199.5°C for the endothermic peak and a peak top temperature of 205.0°C. The DSC analysis chart is shown in Figure 13. The DSC analysis of the obtained crystals showed an endothermic peak, which was considered to correspond to the melting of the crystals. The TG chart obtained from TG-DTA analysis of the obtained crystals is shown in Figure 14. Similar to the crystals obtained in Example 1, almost no weight loss was observed even at temperatures exceeding the boiling point of toluene (110.6°C: 1 atm), and a steep weight loss was observed around 205°C (peak top temperature) where the endothermic peak appeared. The weight loss rate at 300°C was 6.55%.

[0056] <Example 5> At room temperature, a solution was prepared by mixing 0.14 g of the compound A crystals obtained in Example 1 with 1.36 g of MIBK in a tightly sealed screw-top bottle. 27.08 g of toluene was added to this solution and mixed. The tightly sealed screw-top bottle containing the mixed solution was cooled in a refrigerator (4°C). As a result, microcrystalline powder of compound A precipitated. Furthermore, the solution was heated under reduced pressure to remove the solvent and increase the amount of compound A powder. The precipitated powder was then filtered off by Kiriyama filtration, washed with toluene, and dried under reduced pressure at 70°C and 1.6 kPa for 5 hours to obtain 0.11 g of white powder. The yield of compound A powder obtained by these operations was 79%. The obtained powder was found to be crystalline, as a diffraction pattern was observed by PXRD analysis. Table 6 shows the diffraction angle 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 15 or more relative to the peak with the highest intensity. The PXRD analysis chart is shown in Figure 15. It was revealed that the obtained crystals have characteristic peaks common to those of the compound A crystal obtained in Example 1.

[0057]

[0058] Differential scanning calorimetry (DSC) analysis of the obtained crystals revealed an onset temperature of 204.5°C for the endothermic peak and a peak top temperature of 209.0°C. The DSC analysis chart is shown in Figure 16. The DSC analysis of the obtained crystals showed an endothermic peak, which was considered to correspond to the melting of the crystals. The TG chart obtained from TG-DTA analysis of the obtained crystals is shown in Figure 17. Similar to the crystals obtained in Example 1, almost no weight loss was observed even at temperatures exceeding the boiling point of toluene (110.6°C: 1 atm), and a steep weight loss was observed around 209°C (peak top temperature) where the endothermic peak appeared. The weight loss rate at 300°C was 6.59%.

[0059] <Example 6> At room temperature, a solution was prepared by mixing 0.16 g of the crystalline compound A obtained in Example 1 with 0.45 g of cyclohexanone in a screw-top bottle that could be sealed tightly. 31.01 g of toluene was added to this solution and mixed. The sealed screw-top bottle containing the mixed solution was cooled in a refrigerator (4°C). As a result, microcrystalline powder of compound A precipitated. When the screw-top bottle was left to stand at room temperature, granular powder that had grown from the microcrystalline state was obtained. The precipitated powder was filtered by Kiriyama filtration, washed with toluene, and dried under reduced pressure at 70°C and 1.6 kPa for 5 hours to obtain 0.11 g of white powder. The yield of compound A powder obtained by these operations was 69%. The obtained powder was found to be crystalline from the diffraction pattern observed by PXRD analysis. Table 7 shows the diffraction angle 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 10 or more relative to the peak with the greatest intensity. The PXRD analysis chart is shown in Figure 18. It was revealed that the obtained crystals have characteristic peaks common to those of the compound A crystal obtained in Example 1.

[0060]

[0061] Differential scanning calorimetry (DSC) analysis of the obtained crystals revealed an onset temperature of 204.1°C for the endothermic peak and a peak top temperature of 210.4°C. The DSC analysis chart is shown in Figure 19. The DSC analysis of the obtained crystals showed an endothermic peak, which was considered to correspond to the melting of the crystals. The TG chart obtained by TG-DTA analysis of the obtained crystals is shown in Figure 20. Similar to the crystals obtained in Example 1, almost no weight loss was observed even at temperatures exceeding the boiling point of toluene (110.6°C: 1 atm), and a steep weight loss was observed around 210°C (peak top temperature) where the endothermic peak appeared. The weight loss rate at 300°C was 6.58%.

[0062] <Example 7> At room temperature, a solution was prepared by mixing 0.14 g of the crystals of compound A obtained in Example 1 with 1.87 g of acetone in a screw-top bottle that could be sealed tightly. 1.89 g of isooctane was added to this solution and mixed. As a result, turbidity occurred in the solution, and the precipitation of compound A was confirmed. The tightly sealed screw-top bottle containing the mixed solution was cooled in a refrigerator (4°C). As a result, it was confirmed that crystals of the powdered compound A composition had precipitated.

[0063] <Example 8> At room temperature, a solution was prepared by mixing 0.14 g of the crystals of compound A obtained in Example 1 with 1.86 g of acetone in a screw-top bottle that could be sealed tightly. 5.77 g of cyclohexane was added to this solution and mixed. As a result, turbidity occurred in the solution, and the precipitation of compound A was confirmed. The tightly sealed screw-top bottle containing the mixed solution was cooled in a refrigerator (4°C). As a result, it was confirmed that crystals of the powdered compound A composition had precipitated.

[0064] <Example 9> At room temperature, a solution was prepared by mixing 0.13 g of the crystals of compound A obtained in Example 1 with 3.88 g of MEK in a screw-top bottle that could be sealed tightly. 5.67 g of isooctane was added to this solution and mixed. As a result, turbidity occurred in the solution, and the precipitation of compound A was confirmed. The tightly sealed screw-top bottle containing the mixed solution was cooled in a refrigerator (4°C). As a result, it was confirmed that crystals of the composition of compound A in microcrystalline form had precipitated.

[0065] <Example 10> At room temperature, a solution was prepared by mixing 0.13 g of the crystals of compound A obtained in Example 1 with 3.88 g of MEK in a screw-top bottle that could be sealed tightly. 16.82 g of cyclohexane was added to this solution and mixed. As a result, turbidity occurred in the solution, and the precipitation of compound A was confirmed. The sealed screw-top bottle containing the mixed solution was cooled in a refrigerator (4°C). As a result, it was confirmed that crystals of the powdered compound A composition had precipitated.

[0066] <Example 11> At room temperature, a solution was prepared by mixing 0.14 g of the crystalline form of compound A obtained in Example 1 with 1.36 g of MIBK in a screw-top bottle that could be sealed tightly. 0.61 g of isooctane was added to this solution and mixed. As a result, turbidity occurred in the solution, and the precipitation of compound A was confirmed. The tightly sealed screw-top bottle containing the mixed solution was cooled in a refrigerator (4°C). As a result, it was confirmed that crystals of the compound A composition in microcrystalline and powdery forms had precipitated.

[0067] <Example 12> At room temperature, a solution was prepared by mixing 0.14 g of the compound A crystals obtained in Example 1 with 1.36 g of MIBK in a screw-top bottle that could be sealed tightly. 1.79 g of cyclohexane was added to this solution and mixed. As a result, turbidity occurred in the solution, and the precipitation of compound A was confirmed. The sealed screw-top bottle containing the mixed solution was cooled in a refrigerator (4°C). As a result, a solid of powdered compound A was found at the bottom of the screw-top bottle, confirming that crystals of the powdered compound A composition had precipitated.

[0068] From the above, it has become clear that by using the aliphatic ketone solvent having 3 to 6 carbon atoms according to the present invention, a composition and crystals containing compound A can be precipitated from a crystallization solution containing the solvent and compound A. Furthermore, it has become clear that the manufacturing method of the present invention is extremely useful because it can efficiently produce a composition and crystals containing compound A under conditions and operations that are easy to implement industrially. In addition, it has become clear that the resulting compound A crystals are easy to handle during manufacturing and use.

Claims

1. A method for producing a composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, comprising a crystallization step of precipitating crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene from a crystallization solution containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene and an aliphatic ketone solvent having 3 to 6 carbon atoms.

2. The manufacturing method according to claim 1, wherein the crystallization step is a crystallization step that precipitates the crystals by a method comprising at least one of the methods of cooling crystallization, evaporation crystallization, and poor solvent addition crystallization.

3. The manufacturing method according to claim 2, wherein the crystallization step comprises a method for precipitating the crystals by adding a poor solvent to the crystallization solution, using an aromatic hydrocarbon solvent having 7 to 9 carbon atoms or an aliphatic hydrocarbon solvent having 5 to 8 carbon atoms.

4. The manufacturing method according to claim 1, wherein the composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene is in powder form.

5. The manufacturing method according to claim 1, wherein the composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene is such that the ratio of the peak area of ​​9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene to the peak area of ​​all components detected at a wavelength of 280 nm in high-performance liquid chromatography (HPLC) analysis is 95.0% or more.

6. The manufacturing method according to claim 1, wherein the composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene has a weight loss rate of 10% by weight or less at 300°C determined by thermogravimetric analysis.

7. The manufacturing method according to claim 1, wherein the composition containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene has a Hazen unit color number (APHA) of 200 or less when the composition is prepared as a 10% by weight acetone solution.

8. A crystal of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, characterized in that the peak top temperature of the endothermic peak determined by differential scanning calorimetry is in the range of 144 to 163°C.

9. The crystal according to claim 8, further comprising diffraction peaks at diffraction angles 2θ of 6.3±0.2°, 11.3±0.2°, and 22.5±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

10. A method for producing crystals according to claim 8, characterized by comprising a crystallization step of precipitating crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene from a crystallization solution containing 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene and an aliphatic ketone solvent having 3 to 6 carbon atoms.

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