Crystal polymorph of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene and its manufacturing method

Abstract

To provide a novel amorphous polymorph of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) with high purity and low coloration and a method for producing the same.SOLUTION: Prepared is an amorphous polymorph B, produced through the melting and cooling of crystalline polymorph A of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, having diffraction peaks at diffraction angles 2θ=12.5±0.2°, 20.4±0.2°, 22.2±0.2°, 23.1±0.2°, and 25.9±0.2° in a powder X-ray diffraction pattern.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to 9,9-bis[6-(2-hydroxybenzoyl)methyl]-2,3-dihydro-2,4 ... New Polymorphs (Crystalline and Amorphous Polymorphs) of [(2-naphthyloxyethoxy)-2-fluorene] ) and its manufacturing method. [Background technology]

[0002] Compounds with a fluorene skeleton, such as 9,9-bis(hydroxyaryl)fluorenes It is known that the material has excellent properties such as a high refractive index and high heat resistance. Japanese Patent Application Laid-Open No. 2011-68624 (Patent Document 1) describes 3-mercaptopropionic acid and 9-Fluorenone and ethylene glycol mono(2-naphthyl) ether in the presence of sulfuric acid The reaction mixture was neutralized with an aqueous solution of sodium hydroxide, and then xylene was added to The crystals were washed with distilled water, cooled, filtered, dried, and 9,9-bis[ 6-(2-hydroxyethoxy)-2-naphthyl]fluorene (hereinafter referred to as BNEF) The purity was 98.3% by HPLC. It is stated that the color (APHA) of the solution in which the crystals were dissolved at a concentration of 100% by weight was 30. In addition, when toluene was used instead of xylene, the purity was 99.1% and the color of the solution was It is described that the crystal structure of such a fluorene compound (APHA) was 41. has a high glass transition temperature and a high refractive index, and is useful for obtaining resins such as optical materials. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-68624 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the purity, coloration, and residual solvent content of the BNEF crystals obtained by the above method are not consistent. For example, the BNEF crystals obtained by the above method are Coloring tends to progress under heating conditions such as melting, and polyester is produced using the BNEF crystals. When preparing terephthalate resins, the degree of coloring of the resin increases due to heating or melting during preparation. Furthermore, the solvent remaining in the crystals limits the use of the crystals from the viewpoint of safety. This can be a factor that causes the following.

[0005] In addition, the bulk density of the BNEF crystals is low, requiring large spaces for transportation and storage. Furthermore, the introduction of a naphthalene ring results in a decrease in the ease of measurement and handling. The benzene ring was introduced into 9,9-bis[4-(2-hydroxyethoxy)phenyl]propanol. Compared to [phenyl]fluorene, the BNEF crystals have low solubility in organic solvents.

[0006] Therefore, an object of the present invention is to provide a novel polymorph (crystalline polymorph) of BNEF that is highly pure and has little color. The present invention aims to provide a method for producing the same (amorphous polymorph, amorphous polymorph).

[0007] Another object of the present invention is to provide a novel polymorph of BNEF with a low residual amount of solvent and a method for producing the same. The purpose is to provide

[0008] A further object of the present invention is to provide a novel polymorph of BNEF that exhibits little coloration upon heating and its The object is to provide a manufacturing method.

[0009] Another object of the present invention is to provide a BN having a high bulk density and improved solubility in organic solvents. The object of the present invention is to provide a novel polymorph of EF and a method for producing the same. [Means for solving the problem]

[0010] The present inventors have investigated the crystal obtained by the method of Patent Document 1 (hereinafter simply referred to as "crystal C"). In order to increase the purity of the compound, recrystallization was attempted using xylene and toluene. The fluorene compound forms an inclusion compound with a solvent such as xylene, and the resulting mixture is then dried under reduced pressure. Even after drying, about 1 to 5% by mass of solvent remains, which sufficiently reduces the degree of coloration and improves purity. The present inventors further conducted extensive research to achieve the above object, and as a result, As a result, BNEF has crystalline polymorphs, and the fluorene compound is crystallized from a specific crystallization solvent. This resulted in a product with high purity, no coloring, little residual solvent, high thermal stability, and even under heat. If the temperature is higher than the melting point, polymorph A can be obtained, which is a crystalline form that can effectively prevent coloration even at temperatures higher than the melting point. They discovered that when polymorph A was melted and cooled, an amorphous polymorph B was produced. As a result, the present invention was completed.

[0011] That is, the present invention provides 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl ] fluorene (hereinafter sometimes referred to as BNEF) The amorphous polymorph (hereinafter sometimes simply referred to as Polymorph A) and the amorphous polymorph (hereinafter sometimes simply referred to as Polymorph B) The crystalline polymorph A has a diffraction angle of 2θ=12.5 in the powder X-ray diffraction pattern. ±0.2°, 20.4±0.2°, 22.2±0.2°, 23.1±0.2°, 25.9 Polymorph A has a diffraction peak at a diffraction angle 2θ=14. Diffraction peaks at 3±0.2°, 15.5±0.2°, 17.7±0.2°, and 18.6±0.2° Furthermore, the crystalline polymorph A may have a diffraction angle 2θ=19.5±0.2 In addition, the crystalline polymorph A may have diffraction peaks at 22.6±0.2°. The peak intensity at a diffraction angle 2θ=20.4±0.2° may be the largest.

[0012] The purity of crystalline polymorph A is 97% or more, especially 99% or more, and the melting point is 218±3°C. Furthermore, since polymorph A does not form an inclusion compound with the solvent, the content of the solvent (residual The solvent content is extremely low, with the solvent content being 0.2% by mass or less. When held at 280°C for 2 hours under a nitrogen gas atmosphere, the coloring in the molten state was minimal. The hue (APHA) is 50 to 150.

[0013] Such crystalline polymorph A is selected from water-soluble ethers, water-soluble alcohols, and water-soluble ketones. A solvent containing at least one selected from the group consisting of ether and water-soluble alcohol is particularly preferred. It can be produced by crystallizing BNEF from a solvent.

[0014] The amorphous polymorph B exhibits a halo characteristic of amorphous materials in the powder X-ray diffraction pattern. Such amorphous polymorph B is formed by melting and cooling BNEF. The amorphous polymorph B also shows little coloration when heated and can be prepared by heating in a nitrogen gas atmosphere. When kept at 280°C for 2 hours under atmospheric pressure, the color (APHA) in the molten state is 50 to 200. Amorphous polymorph B has a high bulk density of 0.9-1.25 g / ml.

[0015] In addition, amorphous polymorph B, like crystalline polymorph A, has high purity and an extremely low residual solvent content. Such amorphous polymorph B has high solubility and can be easily dissolved in solvent-based reaction systems. This allows for smooth charging and reaction. [Effects of the Invention]

[0016] The crystalline polymorph A of BNEF of the present invention has high purity and little coloring. For example, it has high storage stability at high temperatures, and coloring can be significantly suppressed even when stored under heat. For example, coloring can be effectively suppressed even at temperatures equal to or higher than the melting point. Both the amorphous polymorph B and amorphous polymorph B have a low residual amount of solvent, making them highly safe and suitable for a wide range of applications. Furthermore, amorphous polymorph B has a high bulk density, which improves handling and Furthermore, the amorphous polymorph B has high purity and is easy to dissolve in organic solvents. It contains amorphous polymorphs that have little coloring and can significantly suppress coloring even when stored under heat. Therefore, crystalline polymorph A and amorphous polymorph B are highly safe and suitable for industrial products, organic chemicals, etc. It can be used in a wide range of applications, including as a compound, a raw material for resins, and a curing agent for resins. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is a chart showing the powder X-ray diffraction pattern of Crystal C obtained in Comparative Example 1. [Figure 2] FIG. 2 is a chart showing the powder X-ray diffraction pattern of the crystalline polymorph A1 obtained in Example 1. [Figure 3] FIG. 3 is a chart showing the powder X-ray diffraction pattern of amorphous polymorph B1 obtained in Example 2. [Figure 4] FIG. 4 is a chart showing the powder X-ray diffraction pattern of the crystalline polymorph A2 obtained in Example 4. [Figure 5] FIG. 5 is a chart showing the powder X-ray diffraction pattern of the crystalline polymorph A3 obtained in Example 5. [Figure 6] FIG. 6 is a chart showing the powder X-ray diffraction pattern of the crystalline polymorph A4 obtained in Example 6. [Figure 7] FIG. 7 is a chart showing the powder X-ray diffraction pattern of the crystalline polymorph A5 obtained in Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0018] [Polymorph] The crystalline form of polymorph A of the present invention is 9,9-bis[6-(2-hydroxyethoxy)-2 1. A crystalline polymorph of [BNEF]-naphthylfluorene (BNEF) having a powder X-ray diffraction pattern (X RD), the diffraction angles 2θ=12.5±0.2°, 20.4±0.2°, 22.2± It has characteristic diffraction peaks at 0.2°, 23.1±0.2°, and 25.9±0.2°. Preferably, the diffraction angle 2θ is 14.3±0.2°, 15.5±0.2°, 17.7±0.2°, It has diffraction peaks at diffraction angles of 18.6±0.2° and 18.6±0.2°. There are also diffraction peaks at angles 2θ=19.5±0.2° and 22.6±0.2°.

[0019] Polymorph A further exhibits diffraction angles 2θ=7.7±0.2°, 8.8±0.2°, and 1 1.1±0.2°, 11.4±0.2°, 12.9±0.2°, 13.8±0.2°, 1 6.9±0.2°, 17.4±0.2°, 21.2±0.2°, 24.7±0.2°, 2 At least one diffraction angle 2θ selected from 5.4±0.2° and 26.7±0.2° Of these 12 diffraction angles 2θ, the diffraction peaks Folding angle 2θ=7.7±0.2°, 11.1±0.2°, 11.4±0.2°, 24.7± 0.2°, 25.4±0.2°, 26.7±0.2° More preferably, the diffraction angle 2θ is 24.7±0.2°, 25.4 26.7±0.2°, 26.7±0.2°, and Of these 12 diffraction angles 2θ, preferably, at least and also have diffraction peaks at at least three, at least six, and at least nine diffraction angles 2θ. Preferably, it has at least diffraction peaks at all 12 diffraction angles 2θ.

[0020] Polymorph A may have the above diffraction peak pattern. Generally, in polymorph A, Peak intensity I at diffraction angle 2θ = 20.4 ± 0.2° 15 (integrated intensity I 15s and peak Height I 15h ) is the largest, followed by the integrated intensity at a diffraction angle of 2θ = 12.5 ± 0.2°. I 5s , the integrated intensity I at 22.2±0.2° 17s , the integrated intensity I at 22.6±0.2° 18s , the integrated intensity I at 23.1±0.2° 19s , the integrated intensity I at 25.9±0.2° 22s The integrated intensity at at least one diffraction angle 2θ selected from the above is large. Of the minute intensities, I 15s The second largest integrated intensity after 5s , I 17s and I1 8s is often an integral intensity selected from, preferably I 17s or I1 8s , more preferably I 18sIt is highly pure and has less coloring, so it is suitable for integral strength. The order of degrees is I 15s ≫I 18s ≧I 19s ,I 17s ,I 22s ,I 5s The order is It is preferable that 15s ≫I 18s ≧I 19s ,I 17s ,I 22s ≧ I 5s The order is particularly preferably I 15s ≫I 18s ≧I 19s ≧I 17s ≧I 22 s ≧I 5s In the description of the order, for example, "I 18s ≧I 19s ,I 17s ,I 22s ≧I 5s " is I 19s ,I 17s and I 22s Both are I1 8s is less than or equal to, and I 5s It means that it is equal to or greater than the specified value. 19s ,I 17s ,I 22s The order between them is not particularly limited.

[0021] Polymorph A usually has a diffraction peak at a diffraction angle 2θ=20.4±0.2° and the diffraction peaks shown in Table 1 below. Furthermore, in polymorph A, the diffraction peaks at the diffraction angle Integrated intensity I at 2θ=20.4±0.2° 15s and peak intensity (peak height) I 15 h When the value is set to "100", the integrated intensity and peak intensity (peak height) are shown in Table 1 below. The powder may have an X-ray powder diffraction pattern as shown in FIG.

[0022] [Table 1]

[0023] Polymorph A has a diffraction peak at a diffraction angle 2θ=20.4±0.2° and the diffraction peaks shown in Table 1 above. In many cases, the diffraction peak is at least 2θ=6.5±0. 0.2°, 8.3±0.2°, 9.9±0.2°, 16.3±0.2°, 16.4±0.2 °, 16.7±0.2°, 18.7±0.2°, 19.8±0.2°, 20.3±0.2 °, 22.3±0.2°, 23.0±0.2°, 23.9±0.2°, 24.1±0.2 one or more diffraction angles 2θ selected from the group consisting of 26.4±0.2°, 26.9±0.2°, Among these diffraction peaks, at least one having a diffraction angle of 2 θ=16.3±0.2°, 18.7±0.2°, 20.3±0.2°, 22.3±0.2 Diffraction peaks at at least one selected from 23.9±0.2°, 23.9±0.2°, and 26.9±0.2°. It is preferable to have a line.

[0024] The powder X-ray diffraction pattern can be measured using a conventional powder X-ray diffractometer. The diffraction angle 2θ, which indicates the peak, varies by approximately ±0.2° or ±0.1° depending on the measurement conditions. This may occur.

[0025] The crystalline polymorph A of the present invention has a high purity, for example, 97% or more, preferably 98% or more, The purity of the crystalline polymorph A is preferably in the range of 98 to 100%. The preferred ranges are as follows: 98.5 to 99.95%, 99 The purity of crystalline polymorph A is 99.9%, 99.3% to 99.9%, and 99.5% to 99.9%. The purity is usually 99 to 100%. The purity can be calculated by HPLC analysis.

[0026] The melting point of the crystalline polymorph A is, for example, 21°C when measured by a differential scanning calorimeter (DSC). 8±4°C, preferably 218±3°C, more preferably 218±2°C. Polymorph A has excellent storage stability, especially at high temperatures. It can be measured based on the endothermic peak (or melting point) in differential scanning calorimetry (DSC).

[0027] Such a crystalline polymorph A has a small content (residual amount) of solvent, and the residual amount of solvent is, for example, 0.2% by mass or less, preferably 0.15% by mass or less, and more preferably 0.1% by mass or less The amount of remaining solvent can be measured based on gas chromatography.

[0028] The bulk density of the crystalline polymorph A may be, for example, about 0.3 to 1 g / ml, and is preferably The ranges are as follows: 0.4-0.9g / ml, 0.5-0.8g / ml, 0. The bulk density is preferably 0.53 to 0.7 g / ml, and more preferably 0.55 to 0.65 g / ml. The bulk density can be measured by the method for measuring bulk density specified in the Japanese Pharmacopoeia.

[0029] The crystalline polymorph A of the present invention can effectively suppress coloration even when stored at high temperatures, and As shown above, even when the sample was kept at 280°C for 2 hours under a nitrogen gas atmosphere, the color of the sample in the molten state (A PHA) may be, for example, about 30 to 200, and the preferred range is as follows: The stages are 40-180, 50-150, 75-125, and 80-120.

[0030] The crystal (crystal C) obtained by the method of Patent Document 1 was powder X as shown in FIG. In the X-ray diffraction pattern, the diffraction angles 2θ=13.8±0.2°, 16.4±0.2°, 1 Specially for 9.5±0.2°, 20.5±0.2°, 22.5±0.2°, and 26.2±0.2° The diffraction angles 2θ=12.1±0.2°, 13.0±0.2°, and 14. 6±0.2°, 19.8±0.2°, 20.0±0.2°, 21.8±0.2°, 24. A peak may also be observed at 2θ=13.8±0.2°, 20.5± The peak at 0.2° is often large, and the peak height at 13.8±0.2° is the largest. Such a powder X-ray diffraction pattern is similar to the diffraction pattern of the crystalline polymorph A. This is very different from the previous version.

[0031] The crystalline polymorph A contains at least one selected from the group consisting of ethers, alcohols, and ketones. From a solvent containing 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl] It can be prepared by crystallizing [benzyl]fluorene (BNEF). The crystallization solvent is highly polar. It is preferable that the crystallization solvent is composed of water-soluble solvents. or aqueous solvents). The solubility of water-soluble solvents (or aqueous solvents) such as alcohols and water-soluble ketones in water [or is the solubility of the crystallization solvent in water] is, for example, 1 g / L or more (e.g., 10 g / L or more), preferably 100 g / L or more (for example, 200 g / L or more), and more preferably Preferably, it is 300 g / L or more (for example, 500 g / L or more), and in particular, it is It is preferable that the solubility in water is too low, and the pure There is a risk that the strength may decrease or the glass may become easily discolored.

[0032] Examples of the ether include cyclic ethers such as dioxane and tetrahydrofuran. Examples of dioxane include 1,3-dioxane and 1,4-dioxane. Water-soluble ethers are often used as ethers. Among these ethers, 1, Dioxanes such as 4-dioxane are preferred.

[0033] As the alcohol, a water-soluble alcohol is usually used. Examples of the solvent include methanol, ethanol, propanol, and isopropanol. Preferred water-soluble alcohols are methanol and ethanol, and methanol is usually used. It is often used.

[0034] The ketones include acetone, methyl ethyl ketone (MEK), methyl propyl ketone (MKE), methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl Luketone etc. C 3-8 Examples of ketones include water-soluble ketones. Among these ketones, C 3-6 Ketones are preferred, as they have high purity and little color. From the point of no C 3-5 Ketones are more preferred, acetone or MEK are even more preferred, and acetone is Ton is particularly preferred.

[0035] These solvents can be used alone or as a mixed solvent of two or more. Among these solvents, water-soluble ethers and other ether-based solvents, water-soluble ketones, etc. A single solvent of any ketone or a mixed solvent of ether and alcohol is preferred. A mixed solvent of an ether and a water-soluble alcohol is preferred.

[0036] Mass ratio of ether such as 1,4-dioxane to water-soluble alcohol such as methanol For example, the former / latter ratio is 90 / 10 to 10 / 90, preferably 80 / 20 to 20 / 80. More preferably, it is 70 / 30 to 30 / 70, and particularly preferably 60 / 40 to 40 / 60. By adjusting the ratio of a good solvent, ether, to a poor solvent, such as methanol, a water-soluble alcohol, As a result, high-quality crystalline polymorph A can be obtained in high yield.

[0037] In addition, when the crystallization solvent is a mixed solvent, it is highly polar or highly water-soluble (or highly miscible with water). As long as the above-mentioned ethers, alcohols and ketones are not affected by the solvent, the solvent may contain other solvents. The other solvent may be a conventional polar solvent (or a water-soluble solvent). These other solvents may be used alone or in combination of two or more. It can also be used.

[0038] Examples of the non-polar solvent include hydrocarbons. For example, aliphatic hydrocarbons, specifically, C 2 such as hexane, heptane, and octane 4- 12 Aliphatic hydrocarbons; alicyclic hydrocarbons, specifically, C 5-1 Aliphatic hydrocarbons; aromatic hydrocarbons, specifically, benzene, alkylbenzenes, etc. C 6-10 These non-polar solvents may be used alone or in combination. Two or more of these non-polar solvents can be used in combination. The elements are preferred.

[0039] The alkylbenzenes include toluene, xylene, ethylbenzene, trimethylbenzene, Mono- or tetra-C such as benzene, ethyltoluene, propylbenzene, and cumene 1-4 a Among these aromatic hydrocarbons, alkylbenzenes and alkyl-benzenes are Preferred are mono- and tri-C 1-3 Alkyl-benzenes are more preferred. Or Mono or DiC 1-2 Alkyl-benzenes, especially toluene or xylene Of these, toluene is particularly preferred.

[0040] When other solvents such as aromatic hydrocarbons are contained, the ratio of the other solvents to the total crystallization solvent is as follows: For example, it may be about 0.1 to 49.9 mass %, and the preferred range is as follows: 1-45% by mass, 5-40% by mass, 10-35% by mass, 15-33% by mass, 20-3 0% by mass. From the viewpoint of purity and ease of suppressing coloration, other solvents such as non-polar solvents are preferred. Therefore, the proportion of other solvents such as non-polar solvents should be kept within the total crystallization solvent. It may be, for example, less than 50% by mass, usually about 0 to 40% by mass, based on the total mass, and is preferred. The ranges are as follows: 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less. % by mass or less, more preferably 0% by mass, i.e., substantially no other solvent is contained. It is preferable that:

[0041] The ratio (or amount) of the crystallization solvent is not particularly limited. 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, per 1 part by mass (calculated as a unit mass), The amount is preferably 1 to 10 parts by mass, particularly 3 to 8 parts by mass, and especially 4 to 5 parts by mass.

[0042] The crystalline polymorph A is obtained by supersaturating the fluorene compound (BNEF) in the crystallization solvent. The BNEF can be precipitated by dissolving it in the crystallization solution and cooling it. Polymorph A can be precipitated or crystallized by heating and dissolving it in a solvent and then cooling it. After dissolution, the solvent may be distilled off under reduced pressure as needed to adjust the amount of the crystallization solvent to fall within the above-mentioned ratio range. BNEF may also be prepared by the method described in Patent Document 1. ,9-bis[6-hydroxy-2-naphthyl]fluorene, ethylene oxide added a method of reacting ethylene carbonate and / or 2-chloroethanol, etc. It may be prepared by any conventional method. BNEF may also be prepared by, for example, conventional methods. Isolated fluorene compounds, whether in crystalline form such as crystalline C or amorphous form, The compound may be dissolved in the crystallization solvent and crystallized. After completion of the reaction, the solvent in the reaction mixture may be replaced with the crystallization solvent to crystallize the crystalline polymorph A. For example, in the case of reaction mixtures and liquid separation, solvents are removed from the organic phase containing toluene, xylene, etc. The residue may be dissolved in the crystallization solvent to crystallize the crystalline polymorph A.

[0043] The temperature at which the BNEF is dissolved in the crystallization solvent is below the boiling point of the solvent, for example, 30 The cooling temperature is not particularly limited, and the final cooling temperature is For example, the temperature is from -10°C to 30°C, preferably from 1 to 20°C, and more preferably from 5 to 15°C. Although rapid cooling is possible, it is usually allowed to cool naturally or slowly.

[0044] In the crystallization operation, seed crystals may be added if necessary, and the crystallization operation may be carried out in one go. In particular, in the present invention, the crystallization can be carried out in one operation. , high purity and colorless crystalline polymorph A, i.e., crystalline polymorph A having the above-mentioned APHA, It can be generated.

[0045] The generated crystals are usually separated by filtration, centrifugation or other separation means, and then dried. This makes it possible to obtain crystalline polymorph A with high purity and less coloration and residual solvent.

[0046] The amorphous polymorph B of the present invention has a powder X-ray diffraction pattern as shown in FIG. , exhibits a halo peak characteristic of amorphous materials and does not exhibit a melting point. Such amorphous polymorph B The block may be a powder or granules pulverized to any particle size, and the block may have a bulk density ( The density is high, for example, 0.9 to 1.25 g / ml, preferably 0.95 to 1.22 g / ml. The density is preferably 1 to 1.2 g / ml, more preferably 1 to 1.2 g / ml. The excluded volume of the block is calculated using the mass and volume of the block. In addition, polymorph B is amorphous and has a high bulk density, making it difficult to transport, store, and transport. The tube space can be reduced, and measurement and handling are improved, while the compatibility with organic solvents is improved. Therefore, it can be quickly dissolved in the solution reaction system, and the raw material can be easily charged and reacted. The bulk density of the powder or granule depends on the particle size. The bulk density may be the same as that of the crystalline polymorph A, and may be 0.1 to 0.6 g / ml. The granular amorphous polymorph B has even better solubility in organic solvents.

[0047] Furthermore, polymorph B, like polymorph A, has a low solvent content (residual amount), The amount is, for example, 0.2% by mass or less, preferably 0.15% by mass or less, and more preferably 0. It is less than 0.1% by mass.

[0048] Even if such polymorph B is produced through a melting process as described below, it is possible to obtain the same polymorph B as polymorph A. The purity is high, for example, 97% or more, preferably 98% or more, and more preferably 99% or more. The purity of polymorph B is usually 98-99.99%, preferably 98.5-99. The purity of polymorph B is usually 99 to 100%, more preferably 95% or more, and more preferably 99 to 99.9% or more. 00%.

[0049] The polymorph B of the present invention, like the polymorph A, can effectively suppress coloration even when stored at high temperatures. As mentioned above, even when held at 280°C for 2 hours under a nitrogen gas atmosphere, the color (A PHA) is, for example, in the range of 50 to 200, and the preferred range is as follows: , 70-180, 80-170, 100-150, and 110-140.

[0050] Amorphous polymorph B can be obtained by melting and cooling crystalline or amorphous BNEF. When crystalline BNEF is used, amorphous polymorph B can be prepared by The polymorph B1 may be prepared by melting and cooling the polymorph A, and the crystalline C The polymorph B1 may be prepared by melting and cooling the As mentioned above, it has high purity, little coloring (including coloring at high temperatures), and low solvent content (residual amount) In contrast, polymorph B2 is less pure than polymorph B1 and is stored at high temperatures. When heated, it tends to be more colored than polymorph B1.

[0051] Amorphous polymorph B is formed by heating BNEF crystals above the melting point. For example, crystalline polymorph A is Heat to 220-300℃, especially 230-280℃ to melt, then cool (or rapidly cool, stand, or slowly cool) The resulting mass can be crushed, classified, etc., if necessary. It may be a powder or granule of a predetermined size. [Example]

[0052] The present invention will be described in more detail below based on examples, but the present invention will not be limited to these examples. The evaluation methods used in the examples and reference examples are as follows: It is.

[0053] (X-ray diffraction (XRD)) Powder X-ray diffraction device (“Fully automatic multi-purpose horizontal X-ray diffraction device Smart Lab”, manufactured by Rigaku Co., Ltd.) ) was used, and measurements were taken under the conditions of an output of 3 kW, a radiation source (Cu tube), and a measurement angle of 5 to 70°.

[0054] (Melting Point) A differential scanning calorimeter (EXSTAR DSC6200, manufactured by SII NanoTechnology, Inc.) The measurement was carried out under conditions of a nitrogen atmosphere, a measurement temperature of 30 to 300°C, and a temperature rise rate of 10°C / min.

[0055] (purity) High performance liquid chromatography (HPLC) equipment (Shimadzu Corporation "LC-2010A HT") Measurement was carried out using a ram ("TSKgel ODS-80™" manufactured by Tosoh Corporation) under the following conditions.

[0056] Detection method: UV, detection wavelength 254 nm Column temperature: room temperature Eluent (volume ratio): acetonitrile / 0.1% by mass phosphoric acid aqueous solution = 55 / 45 → 95 / 5(Gradient) Flow rate: 1.0ml / min.

[0057] (Hue APHA) 20g of sample was placed in a test tube, heated to 280℃ in a nitrogen atmosphere and held for 2 hours. (Molten sample) was measured by a color difference turbidity meter ("COH- The hue was measured using a "300A" (manufactured by Nippon Denshoku Co., Ltd.).

[0058] (Bulk density and density) The bulk density was measured according to the bulk density measurement method of the Japanese Pharmacopoeia. The excluded volume of the block was determined using a cylinder, and the weight and volume of the block were used to calculate the volume. .

[0059] (Residual solvent amount) The sample was dried under reduced pressure at 120°C overnight, then dissolved in tetrahydrofuran and analyzed by gas chromatography. GC equipment (Shimadzu Corporation "GC-2014"), column: CBP-1, detector: F The amount of residual solvent was measured using a thermocouple in a temperature range of 50 to 290°C.

[0060] Comparative Example 1: Crystal C of Patent Document 1 Crystal C was obtained in accordance with Example 13 of Patent Document 1. In a flask, 45 g of 9-fluorenone (0.25 mol, manufactured by Osaka Gas Chemicals Co., Ltd.) Ethylene glycol mono(2-naphthyl) ether 235g (1 mole, manufactured by Meisei Chemical Co., Ltd.) ), add 1 g of 3-mercaptopropionic acid, then heat to 60°C until completely dissolved. After that, 54 g of sulfuric acid was gradually added, and the mixture was stirred for 6 hours while maintaining the temperature at 60°C. By HPLC, it was confirmed that the conversion rate of 9-fluorenone was 99.5% or more. The reaction mixture was neutralized by adding 48% by mass of aqueous caustic soda solution, and then 400 g of xylene was added. The organic phase was washed several times with distilled water and then cooled to precipitate crystals. After further filtration and drying at 120°C, 114g (yield 85%) of crystalline C (white ) was obtained. 1 As a result of H-NMR measurement, the target 9,9-biphenyl It was found that the compound was bis[6-hydroxy(2-hydroxyethyl)-2-naphthyl]fluorene. Confirmed.

[0061] The powder X-ray diffraction pattern of the obtained crystalline C is shown in FIG.

[0062] X-ray diffraction peak (relative integrated intensity; relative peak height in parentheses): diffraction angle 2θ = 6 .46°(3.5;4.5), 8.33°(16.2;12.2), 10.14°(16 .6;11.6), 10.98°(27.2;21.9), 12.06°(30.7;4 1.4), 13.00°(24.4;31.4), 13.76°(76.9;100.0 ), 14.59°(29.1;37.1), 16.04°(33.0;12.5), 16 .43°(41.1;41.3), 16.73°(13.7;8.2), 17.92°( 19.5;21.0), 18.26°(16.9;14.0), 19.53°(41.3 ;61.6), 19.78°(58.7;58.1), 20.04°(27.1;36. 8), 20.46°(100.0;75.2), 21.39°(33.3;40.0), 21.82°(67.9;51.3), 22.59°(63.8;32.5), 24.1 5°(63.3;51.7), 24.82°(38.4;36.6), 26.27°(7 1.9;53.1).

[0063] The melting point of the obtained crystal C was 203°C, the purity was 95.5%, and the bulk density was 0.4g / ml. The color (APHA) of the sample in the heated and melted state (yellow) was 500 or more, and the remaining solvent The amount of silene was 2.7% by mass.

[0064] Example 1: Crystalline Polymorph A1 In Comparative Example 1, the organic phase (xylene phase) after adding and mixing xylene was washed with distilled water. After rinsing, the solvent was distilled off under reduced pressure. The residue was dissolved in a 1,4-dioxane-methanol mixed solvent (1,4- Dioxane / methanol (mass ratio) = 50 / 50 (hereinafter referred to as DOX-MeOH)6 The mixture was redissolved in 00g of water by heating to 70°C and then cooled to 10°C to precipitate crystals. The crystals were filtered and dried at 120°C to obtain 94 g (yield 70%) of crystals A1. .

[0065] The powder X-ray diffraction pattern of the obtained crystalline A1 is shown in FIG.

[0066] X-ray diffraction peak (relative integrated intensity; relative peak height in parentheses): diffraction angle 2θ = 7.66°(23.9;27.8), 8.83°(14.0;14.4), 11.12° (20.1;17.2), 11.40°(23.2;25.5), 12.48°(41. 6;43.4), 12.94°(6.9;7.6), 13.79°(13.6;15.5 ), 14.29°(36.8;38.9), 15.54°(33.2;37.4), 16 .30°(8.3;10.0), 16.89°(18.2;20.4), 17.39°( 6.1;12.2), 17.70°(35.7;40.3), 18.55°(29.4; 26.2), 18.70°(14.8;24.2), 19.53°(34.7;36.3 ), 20.28°(22.0;24.3), 20.37°(100.0;100.0), 21.18°(13.4;19.4), 22.17°(48.0;39.7), 22.3 0°(11.4;19.3), 22.62°(63.0;76.6), 23.13°(4 9.9;41.5), 23.93°(13.1;11.5), 24.73°(26.1; 28.7), 25.38° (28.2;33.0), 25.90° (45.0;38.0) ), 26.74°(25.7;36.2), 26.94°(17.3;23.0).

[0067] The melting point of the obtained crystal A1 was 219°C, the purity was 99.8%, and the bulk density was 0.6 g / ml. The color (APHA) of the sample in the molten state (colorless and transparent) was 102, and the remaining solvent The amount was 0.1% by mass or less.

[0068] Example 2: Amorphous Polymorph B1 The crystalline polymorph A obtained in Example 1 was placed in a three-necked flask and heated to 250°C under reduced pressure. When the mixture was melted and then rapidly cooled to room temperature (20 to 25°C), a mass was obtained.

[0069] This block was crushed and the powder X-ray diffraction pattern of the powder sample is shown in FIG.

[0070] As is clear from Figure 3, a halo peak characteristic of amorphous materials is observed, and the sample does not show a melting point. The purity of the obtained solid was 99.8%, the bulk density was 1.2 g / ml, and the melting point of the solid was 1.2 g / ml. The color (APHA) of the sample (colorless and transparent) was 131, and the residual solvent content was 0.1% by mass. It was as follows.

[0071] Example 3: Amorphous Polymorph B2 The crystals C obtained in Comparative Example 1 were placed in a three-necked flask, heated to 250°C under reduced pressure, and melted. When the mixture was rapidly cooled to room temperature (20 to 25°C), a mass was obtained.

[0072] As in Example 2, this block was crushed and the powder X-ray diffraction pattern of the powder sample was measured. As shown in Figure 3, no halo peak was observed. The aggregates also showed no melting point. The purity of the obtained solid was 95.5%, the bulk density was 1.1 g / ml, and the solid was in a molten state. The color (APHA) of the sample (yellow transparent) is 500 or more, and the residual solvent content is 0.1% by mass or less. It was below.

[0073] Example 4: Crystalline Polymorph A2 In Example 1, 600 g of a 1,4-dioxane-methanol mixed solvent (1,4-dioxane) Instead of 1,4-dioxane / methanol (mass ratio = 50 / 50), 420 g of 1,4-dioxane The procedure of Example 1 was repeated except for using methyl methyl ketone, and 81 g of BNEF crystals A2 (yield 60%) was obtained. Ta.

[0074] The powder X-ray diffraction pattern of the obtained crystalline A2 is shown in FIG.

[0075] X-ray diffraction peak (relative integrated intensity; relative peak height in parentheses): diffraction angle 2θ = 7.63°(26.5;35.3), 8.81°(28.0;28.7), 11.06° (13.0;15.5), 11.34°(19.5;22.0), 12.44°(58. 8;58.5), 12.90°(5.8;6.7), 13.73°(21.4;24.3 ), 14.24°(75.1;82.9), 15.47°(29.8;33.4), 16. 24°(11.4;14.6), 16.84°(22.6;19.2), 17.36°( 16.5;14.7), 17.68°(57.2;68.0), 18.60°(32.0) ;28.5), 19.48°(59.4;65.0), 20.30°(100.0;10 0.0), 21.16°(15.4;12.6), 22.09°(99.1;84.4) , 22.59°(73.2;77.6), 23.06°(42.4;37.2), 24. 10°(19.9;16.8), 24.68°(43.5;46.1), 25.33°( 31.8;33.5), 25.86°(42.6;35.7), 26.69°(59.4 ;67.7), 26.89°(20.5;18.8).

[0076] The melting point of the obtained crystal A2 was 221°C, the purity was 99.6%, and the bulk density was 0.8 g / ml. The color (APHA) of the sample in the molten state (colorless and transparent) was 107, and the remaining solvent The amount was 0.1% by mass or less.

[0077] Example 5: Crystalline Polymorph A3 In Example 1, 600 g of a 1,4-dioxane-methanol mixed solvent (1,4-dioxane) Instead of methyl ethyl ketone / methanol (mass ratio = 50 / 50), 800 g of methyl ethyl ketone was used. The same procedure as in Example 1 was repeated except that MEK was used, and 74 g (yield: 55%) was obtained.

[0078] The powder X-ray diffraction pattern of the obtained crystalline A3 is shown in FIG.

[0079] X-ray diffraction peak (relative integrated intensity; relative peak height in parentheses): diffraction angle 2θ = 7.60°(11.6;11.5), 8.79°(18.7;17.4), 11.07° (27.5;23.5), 11.35°(25.2;24.6), 12.44°(59. 1;57.3), 12.90°(8.7;9.0), 13.72°(12.5;13.8) ), 14.24°(45.8;47.7), 15.47°(35.0;37.6), 16 .25°(10.1;12.5), 16.82°(22.1;22.2), 17.35° (22.1;17.6), 17.66°(40.0;43.7), 18.54°(29. 0;25.8), 18.67°(12.5;20.3), 19.47°(41.7;46 .2), 20.29°(100.0;100.0), 21.27°(19.1;11.5 ), 22.09°(62.0;49.2), 22.30°(11.4;18.4), 22 .57°(69.0;80.4), 23.05°(48.8;42.4), 23.89° (10.9;12.4), 24.66°(25.4;28.1), 25.32°(26. 4;28.3), 25.86°(47.8;38.7), 26.69°(32.8;39) .2), 26.88°(16.8;16.1).

[0080] The melting point of the obtained crystal A3 was 220°C, the purity was 99.7%, and the bulk density was 0.7 g / ml. The color (APHA) of the sample in the molten state (slightly pale yellow) was 163, and the remaining molten The amount of the catalyst was 0.1% by mass or less.

[0081] Example 6: Crystalline Polymorph A4 In Example 1, 600 g of a 1,4-dioxane-methanol mixed solvent (1,4-dioxane) Instead of oxane / methanol (mass ratio = 50 / 50), 1000 g of acetone was used. The residue was heated to 55°C and dissolved, and 400 g of acetone was removed from the resulting solution by distillation under reduced pressure. The same procedure as in Example 1 was repeated except that the temperature was cooled to 10°C to obtain 67 g of BNEF crystals A4 (yield 50%) obtained.

[0082] The powder X-ray diffraction pattern of the obtained crystalline A4 is shown in FIG.

[0083] X-ray diffraction peak (relative integrated intensity; relative peak height in parentheses): diffraction angle 2θ = 7.61°(10.7;10.3), 8.80°(17.5;17.2), 11.09° (19.6;17.4), 11.36°(19.4;21.1), 12.45°(61. 1;63.0), 12.90°(6.6;7.5), 13.74°(12.0;14.6 ), 14.25°(51.5;55.7), 15.49°(27.8;31.6), 16 .27°(9.2;12.8), 16.83°(18.0;18.8), 17.37°( 19.3;14.6), 17.67°(41.6;45.5), 18.54°(12.3 ;11.0), 18.64°(25.2;29.0), 19.49°(45.8;50. 4), 20.32°(100.0;100.0), 21.17°(11.6;13.9) , 22.12°(51.4;49.3), 22.27°(25.4;20.5), 22. 59°(57.9;74.2), 23.09°(43.2;34.9), 23.91°( 9.9;11.0), 24.70°(26.8;29.2), 25.35°(23.3; 26.6), 25.87°(40.3;33.3), 26.70°(33.8;42.7 ), 26.91°(12.5;13.4).

[0084] The melting point of the obtained crystal A4 was 220°C, the purity was 99.5%, and the bulk density was 0.4 g / ml. The color (APHA) of the sample in the heated and melted state (light yellow) was 141, and the amount of remaining solvent was was 0.1 mass % or less.

[0085] Example 7: Crystalline Polymorph A5 In Example 1, 600 g of a 1,4-dioxane-methanol mixed solvent (1,4-dioxane) Instead of oxane / methanol (mass ratio = 50 / 50), 600g of methyl isobutyl ether was used. Ketone (MIBK)-toluene mixed solvent (MIBK / toluene (mass ratio) = 75 / 25, The same procedure as in Example 1 was carried out except that B 105 g (78% yield) of NEF crystals A5 was obtained.

[0086] The powder X-ray diffraction pattern of the obtained crystalline A5 is shown in FIG.

[0087] X-ray diffraction peak (relative integrated intensity; relative peak height in parentheses): diffraction angle 2θ = 6.47°(9.9;16.0), 7.61°(33.5;54.8), 8.25°(3 .6;3.5), 8.80°(13.9;14.9), 9.87°(6.5;8.5), 11.10°(20.8;19.3), 11.38°(13.1;16.3), 12.4 5°(45.3;52.3), 12.95°(20.1;22.9), 13.76°(2 8.3;28.0), 14.28°(41.2;54.0), 15.48°(17.5; 24.4), 16.42°(7.7;13.4), 16.85°(14.2;18.0) , 17.38°(6.8;12.6), 17.69°(29.1;38.3), 18.5 5°(26.8;25.7), 19.51°(45.6;51.3), 19.81°(3 4.5;29.4), 20.31°(100.0;100.0), 21.16°(5.9 ;10.8), 22.12°(56.7;56.1), 22.29°(18.5;26. 0), 22.59°(63.1;83.1), 23.01°(17.1;17.3), 2 3.11°(18.0;31.2), 24.14°(30.9;26.6), 24.67 °(28.6;33.5), 25.35°(24.0;28.7), 25.87°(27 .6;27.0), 26.36°(17.0;14.5), 26.72°(45.3;5) 9.1).

[0088] The resulting crystal A5 had a melting point of 216°C, a purity of 99.3%, and a bulk density of 0.4g / ml. The color (APHA) of the sample in the heated and melted state (light yellow) was 182, and the amount of remaining solvent was , was 0.1 mass % or less.

[0089] The properties of the polymorphs obtained in Comparative Example 1 and Examples 1 to 7 are shown in Table 2.

[0090] [Table 2]

[0091] From Table 2, it can be seen that the crystalline polymorphs A1 to A5 have high melting points, high purity, and little residual solvent. Polymorph B1 also has high purity and little residual solvent. It does not discolor when heated and melted at high temperatures, and has a high bulk density. Polymorph B1 has less residual solvent and a higher bulk density than crystalline C. [Industrial Applicability]

[0092] The polymorph of the present invention has little color, high purity, and a small amount of residual solvent. It can be suitably used as a raw material for industrial products, organic synthesis, resin synthesis, etc. The compound has a bis(hydroxynaphthyl)fluorene skeleton, which gives it various properties (optical properties) Excellent heat resistance, water resistance, moisture resistance, chemical resistance, electrical properties, mechanical properties, dimensional stability, etc. Therefore, the polymorph of the present invention can be suitably used as a resin raw material, a resin curing agent, etc. In particular, the polymorphs of the present invention can be used in thermosetting resins such as epoxy resins (or their curing agents) , acrylic resins (multifunctional (meth)acrylates, etc.), thermoplastic resins (polyethylene When applied to resins such as styrene resins and polyurethane resins, it has high heat resistance, high crosslinking properties, a high refractive index, and The epoxy resin can efficiently impart excellent properties such as transparency and a low linear expansion coefficient. It is suitable for applications requiring such properties, such as semiconductor encapsulants and electrical substrates. The acrylic resin is also useful for optical materials, such as optical overcoating agents and hard coating agents. Useful for hard coating agents, anti-reflective films, eyeglass lenses, optical fibers, optical waveguides, holograms, etc. The thermoplastic resin is also useful as a molding material for optical components, heat-resistant components, etc. Can be used.

Claims

1. Amorphous polymorph B is a melt-cooled product of crystalline polymorph A of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, which has diffraction peaks at diffraction angles 2θ=12.5±0.2°, 20.4±0.2°, 22.2±0.2°, 23.1±0.2°, and 25.9±0.2° in a powder X-ray diffraction pattern, and has a bulk density of 0.9 to 1.25 g / ml.

2. 2. The polymorph B of claim 1, wherein the residual solvent content is 0.2% by weight or less.

3. 3. Polymorph B according to claim 1 or 2, having a purity of 97% or more.

4. A method for producing amorphous polymorph B, which is a molten cooled product of crystalline polymorph A of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, which has diffraction peaks at diffraction angles 2θ=12.5±0.2°, 20.4±0.2°, 22.2±0.2°, 23.1±0.2°, and 25.9±0.2° in a powder X-ray diffraction pattern, by melting and cooling said polymorph A.

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