JP2020121964A - 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene powder - Google Patents

Abstract

To suppress blocking during storage.SOLUTION: In the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene powder according to the embodiment, a frequency distribution obtained by a volume-based dry process grain size distribution measurement has a first peak having a peak in a range of a grain diameter of 10 to 100 μm, and a second peak having a peak in a range of a grain diameter of 150 to 500 μm.SELECTED DRAWING: Figure 1

Description

The present invention relates to 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene powder.

The 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene compound is used as a raw material for optical materials. For example, Patent Documents 1 and 2 describe obtaining powder of the compound by crystallization.

JP, 2014-227387, A JP, 2005-187098, A

However, in general, 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder is likely to be a large lump due to particles sticking to each other during storage, that is, blocking is likely to occur. The strainer may become clogged when used as.

An embodiment of the present invention aims to provide a 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene powder capable of suppressing blocking during storage.

In the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder according to the embodiment of the present invention, the frequency distribution obtained by the volume-based dry particle size distribution measurement has a particle diameter of 10 to 100 μm. It has a first peak having a peak in the range and a second peak having a peak in the particle diameter range of 150 to 500 μm.

According to the embodiment of the present invention, blocking during storage can be suppressed.

FIG. 3 is a diagram showing a particle size distribution of crystals obtained in Example 1. FIG. 5 is a view showing a particle size distribution of crystals obtained in Example 2. 5 is a diagram showing a particle size distribution of crystals obtained in Example 3. FIG. FIG. 5 is a diagram showing a particle size distribution of crystals obtained in Comparative Example 1. 6 is a diagram showing a particle size distribution of crystals obtained in Comparative Example 2. FIG.

The 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder according to the embodiment of the present invention is a conventional 2,2′-bis(2-hydroxyethoxy)-1,1′- It has a particle size distribution different from that of the binaphthalene powder, and is characterized by being multimodal with a plurality of peaks in the particle size distribution.

Specifically, the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder according to the present embodiment is measured by a volume-based dry particle size distribution measurement as shown in FIG. The obtained frequency distribution is a powder having a first peak having a peak (that is, apex) in a particle diameter range of 10 to 100 μm and a second peak having a peak (that is, apex) in a particle diameter range of 150 to 500 μm. It is the body. By having such a multi-modal particle size distribution, blocking during storage can be suppressed, and for example, when the powder is used as a raw material of an optical material, the strainer is less likely to be clogged, and the production of the optical material is suppressed. Workability can be improved.

The dry particle size distribution measurement is a dry method, that is, the particle size distribution is measured in air by using a laser diffraction scattering method, and the abundance ratio for each particle size is measured on a volume basis. In this embodiment, a frequency distribution in which the particle size distribution obtained by this measurement is expressed as a frequency is used. The frequency distribution is a histogram or curve with the horizontal axis as the common logarithmic scale of the particle size (μm) and the vertical axis as the frequency (%).

In the present embodiment, the frequency distribution has a first peak having a peak (hereinafter, referred to as a first peak) in a particle diameter range of 10 to 100 μm and a peak in a particle diameter of 150 to 500 μm (hereinafter, a second peak). It is characterized by having a second mountain with. The frequency distribution may have other peaks as long as it has the first peak and the second peak. Preferably, it has a bimodal distribution consisting of only the first mountain and the second mountain.

The first peak is in the range of particle size 10 μm or more and 100 μm or less, more preferably in the range of particle size 15 to 80 μm, further preferably in the range of 30 to 80 μm, and may be in the range of 50 to 70 μm. ..

The second peak is in the range of 150 μm or more and 500 μm or less in particle size, more preferably in the range of 200 to 400 μm, and further preferably in the range of 250 to 350 μm.

The ratio of the particle diameter of the first peak to the particle diameter of the second peak (second peak/first peak) is not particularly limited, but is preferably 2 to 20 from the viewpoint of further enhancing the effect of the present embodiment. , And more preferably 4 to 18.

It is preferable that the frequency distribution has a bottom between the first peak and the second peak in the particle diameter range of 50 to 200 μm from the viewpoint of further enhancing the effect of the present embodiment. That is, there is a bottom having the lowest frequency (%) between the first peak having the first peak and the second peak having the second peak, and the position of the bottom has a particle diameter of 50 μm or more and 200 μm or less. It is preferably in the range. Here, the particle size at the bottom is larger than the particle size at the first peak and smaller than the particle size at the second peak. The bottom preferably has a particle size of 70 to 180 μm, more preferably 100 to 170 μm. The above frequency distribution preferably has a distribution in which the first mountain and the second mountain are not completely separated, that is, the first mountain and the second mountain are connected via the bottom.

In the present embodiment, the volume ratio of the particles having a smaller particle size than the bottom between the first mountain and the second mountain is 50 to 70% from the viewpoint of further enhancing the effect of the present embodiment. preferable. That is, the total frequency of particles having a particle size smaller than the bottom particle size is preferably 50 to 70% with respect to 100% by volume of all particles. When the frequency distribution has a bimodal distribution consisting only of the first mountain and the second mountain, the volume ratio of particles having a smaller particle size than the bottom is the volume ratio of the first mountain, and therefore the first mountain is It corresponds to the ratio of the particles having a small particle diameter to the whole powder. The volume ratio of the particles having a smaller particle size than the bottom is more preferably 55 to 70%.

The 50% volume particle diameter (D50) of the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder according to the embodiment is not particularly limited, but may be, for example, 30 to 150 μm, or 50 to 50 μm. It may be 100 μm.

The 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene compound constituting the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder according to the present embodiment is , Preferably a racemic body, but may contain many optical isomers.

Purity of 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder according to the present embodiment (that is, 2,2′-bis(2-hydroxyethoxy)-based on the total amount of the powder). The content of 1,1′-binaphthalene, the peak area ratio determined by GC measurement described later.) is not particularly limited, but is preferably 90% or more, more preferably 95% or more, and further preferably. It is 98% or more.

The method for producing the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder according to the present embodiment is not particularly limited, and is, for example, 2,2′-bis(2-hydroxyethoxy). A solution containing -1,1'-binaphthalene (hereinafter referred to as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene solution) was prepared, and 2,2'-bis( was prepared from the solution. It can be produced by precipitating crystals of 2-hydroxyethoxy)-1,1′-binaphthalene.

As the organic solvent used for the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene solution, 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene can be dissolved. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane and heptane, halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene, and dichloromethane. And halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane, etc., and any one of these may be used, or two or more thereof may be used in combination. Among these, aromatic hydrocarbon solvents are preferable, and toluene and/or xylene are more preferable.

Examples of the method for preparing the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene solution include a method in which 1,1′-bi-2-naphthol and ethylene carbonate are reacted, 1,1 A method of adding ethylene oxide to'-bi-2-naphthol, and the like.

The target 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene is a compound in which 1 mol of 1,1'-bi-2-naphthol is reacted with 2 mol of ethylene carbonate or ethylene oxide. In addition to these, as a side reaction product, a compound (1 mol adduct) in which 1 mol of 1,1′-bi-2-naphthol is reacted with 1 mol of ethylene carbonate or ethylene oxide, and 1 mol of 1,1′ -Bi-2-naphthol reacted with 3 mol of ethylene carbonate or ethylene oxide (3 mol adduct) 1 mol of 1,1'-bi-2-naphthol reacted with 4 mol or more of ethylene carbonate or ethylene oxide A compound (4 mol or more adduct), a compound (polymer) obtained by polymerizing the target product by 2 mol or more with a carbonic acid ester bond may be produced. Therefore, the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder according to the present embodiment may contain these by-products.

As a method of reacting 1,1′-bi-2-naphthol and ethylene carbonate, for example, 1,1′-bi-2-naphthol, ethylene carbonate, a reaction catalyst, and an organic solvent are mixed, and a reaction temperature of 70 Examples include a method of reacting at ˜130° C. for 1 to 30 hours. From the viewpoint of increasing the yield, the amount of ethylene carbonate used is preferably 1.8 to 10 mol, and more preferably 2 to 5 mol, based on 1 mol of 1,1′-bi-2-naphthol. It is preferably 2.1 to 3 mol, and further preferably.

As a method for adding ethylene oxide to 1,1′-bi-2-naphthol, for example, 1,1′-bi-2-naphthol is dissolved in an organic solvent, and the reaction temperature is 60 to 150° C. in the presence of a reaction catalyst. Then, a method of introducing ethylene oxide so that the internal pressure of the reaction vessel becomes 0.01 to 1 MPa can be mentioned. From the viewpoint of increasing the yield, the amount of ethylene oxide used is preferably 1.8 to 10 mol, more preferably 2 to 5 mol, per 1 mol of 1,1′-bi-2-naphthol. More preferably, it is 2.1 to 3 mol.

In these methods, an alkali catalyst is preferable as the reaction catalyst, and for example, potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate, etc. are used alone or in combination of two or more. May be. Further, as the organic solvent, those capable of dissolving 1,1′-bi-2-naphthol and ethylene carbonate can be used, and the above-mentioned 2,2′-bis(2-hydroxyethoxy)-1,1′ can be used. -The thing used for a binaphthalene solution is mentioned.

After synthesizing 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene, an organic solvent is added to the reaction solution to prepare 2,2′-bis(2-hydroxyethoxy)-1,1′-. A binaphthalene solution may be prepared. Further, the obtained reaction solution may be washed with alkali and washed with water until it becomes neutral.

As a method for precipitating crystals of 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene from a 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene solution, Examples of the method for decreasing the solubility include cooling and addition of a solvent having a low solubility. A cooling method is preferred. A seed crystal may be added when the crystals are precipitated.

As a crystallization method by cooling, for example, a method of cooling a 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene solution at 70 to 130° C. to 60° C. or lower, preferably 30° C. or lower Is mentioned.

The method for allowing the particle size distribution of the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene powder to have the first peak and the second peak is not particularly limited, A method of adjusting the conditions for crystallization can be mentioned.

For example, in the crystallization method by cooling, if the cooling rate is low, the particle size of the particles to be precipitated becomes large, and the particle size tends to be large and unimodal. Further, if the cooling rate is high, the particle size of the particles to be precipitated becomes small, and the particle size tends to be small and unimodal. In such a case, a bimodal particle size distribution having the first peak and the second peak may be obtained by adopting an intermediate cooling rate between them. The cooling rate is not particularly limited, and may be, for example, 0.2 to 0.8° C./minute.

The particle size distribution can also be adjusted by the concentration of the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene solution at the time of precipitation, the stirring speed of the solution during cooling, and the like. Although not particularly limited, the concentration of the 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene solution used for precipitation may be 5 to 40% by mass, or 10 to 30% by mass. Good. The stirring speed during cooling may be 10 to 400 rpm or 40 to 300 rpm.

The precipitated crystals of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene can be taken out by centrifugation, filtration or the like. The crystals taken out can be washed and dried. Thereby, the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene powder according to the present embodiment can be obtained.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. Various measurements in Examples and Comparative Examples were carried out by the following methods.

[yield]
When the theoretical yield calculated from (RS)-1,1′-bi-2-naphthol used as the starting material was 100% by mass, the yield ratio (% by mass) was calculated.

[purity]
A 0.2% by mass toluene solution of the obtained crystals was prepared and subjected to gas chromatography (GC) measurement under the following conditions to obtain the desired product (RS)-2,2'-bis(2-hydroxyethoxy)-. The peak area of (RS)-2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene when the sum of the peak areas of 1,1′-binaphthalene and by-products is 100. Was calculated as the purity (%). Here, the peak of (RS)-2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene is detected at a retention time of about 24.6 minutes.
(GC measurement conditions)
・Measuring device: Agilent Technologies 7820A (manufactured by Agilent Technologies)
・Column: DB-1125-1011 (manufactured by Shimadzu GC)
・Injection volume: 1 μL
・Injection method: split method (split ratio 1:10)
・Inlet temperature: 300℃
・Temperature increase condition: initial temperature 40℃ 5 minutes hold, temperature increase at 10℃/minute, final 300℃ hold 5 minutes ・Carrier gas: Helium (5.8mL/min)
・Detector: Hydrogen flame ionization detector (FID)

[Measurement of particle size distribution]
A frequency distribution (histogram) is obtained by measuring a volume-based dry particle size distribution by a laser diffraction scattering method, and from the frequency distribution, the particle size of the first peak and the particle size of the second peak (the first peak in the case of a single peak) Only), the particle diameter of the bottom between the first peak and the second peak, the sum of the frequencies of the particle diameters smaller than the particle diameter of the bottom (volume ratio of the first peak), and the 50% volume particle diameter. The measurement conditions are as follows.
・Measuring device: Microtrac MT3000II (manufactured by Microtrac Bell)
・Measurement range: 0.243 to 2000 μm
・Light source: Semiconductor laser 780nm x 3 ・Dispersion solvent: Air (refractive index 1.00)
-Particle refractive index: 1.81
・Number of measurement channels: 104

[Blocking test]
After storing 500 g of sample at 40°C for 1 week, 1 month, 3 months, sieving the sample using a sieve with mesh opening of 850 μm, and measuring the mass of blocking substances remaining on the sieve, total sample mass The mass ratio (mass %) of the blocking substance to

[Example 1]
In a glass reactor (diameter 8 cm, height 14 cm, capacity 500 mL) equipped with a stirrer (Three One Motor BLW-1200, manufactured by Shinto Kagaku Co., stirring blade: anchor type stirring rod), a cooler, and a thermometer, (RS)-1,1′-bi-2-naphthol 286 g (1 mol), ethylene carbonate 194 g (2.2 mol), potassium carbonate 15 g and toluene 450 g were charged and reacted at 110° C. for 10 hours. The obtained reaction solution was transferred to a reactor (diameter 12 cm, height 14.5 cm, capacity 1000 mL) equipped with a stirrer (Three One Motor BLW-1200, manufactured by Shinto Kagaku Co., stirring blade: anchor type stirring rod). , 540 g of toluene was added to dilute the mixture, and the temperature was adjusted to 80° C., then, while maintaining 80° C., 290 g of a 10 mass% sodium hydroxide aqueous solution was added to wash the organic solvent layer, and subsequently, 500 g of water was used. Washing with water was repeated until the water after washing became neutral. After washing with water, the organic solvent layer was cooled from 80° C. to 30° C. at a rate of 0.5° C./min while stirring at a rate of 300 rpm, filtered under reduced pressure (50 kPa) and dried (RS)-2, 311 g (yield: 82.9% by mass, purity: 99.6%) of white crystals of 2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene compound were obtained.

[Example 2]
(RS)-2,2'-bis(2-hydroxyethoxy)-1,1'- was performed in the same manner as in Example 1 except that the stirring speed of the organic solvent layer after washing with water was 100 rpm during cooling. 313 g of white crystals of the binaphthalene compound (yield: 83.5% by mass, purity: 99.6%) were obtained.

[Example 3]
The same operation as in Example 1 was repeated except that the amount of toluene added to the reaction solution for dilution was 1000 g, to obtain (RS)-2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene. 292 g (yield: 77.9% by mass, purity: 99.4%) of white crystals of the compound were obtained.

[Example 4]
(RS)-2,2'-bis(2-hydroxyethoxy)-1,1'- was performed in the same manner as in Example 1 except that the stirring speed of the organic solvent layer after washing with water was 75 rpm during cooling. 313 g of white crystals of the binaphthalene compound (yield: 82.7% by mass, purity: 99.4%) were obtained.

[Comparative Example 1]
(RS)-2,2′-Bis(2-hydroxyethoxy)-1 was performed in the same manner as in Example 1 except that the cooling rate of the organic solvent layer after washing with water was changed to 0.1° C./min. As a result, 309 g of white crystals of the 1'-binaphthalene compound (yield: 82.4% by mass, purity: 99.3%) were obtained.

[Comparative example 2]
(RS)-2,2′-Bis(2-hydroxyethoxy)-1 was performed in the same manner as in Example 1 except that the cooling rate of the organic solvent layer after washing with water was changed to 1.0° C./min. As a result, 301 g of white crystals of the 1'-binaphthalene compound (yield: 80.3% by mass, purity: 99.4%) were obtained.

Particle size distribution measurement and blocking test were performed using the obtained crystals of (RS)-2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene compound. The results are shown in FIGS. 1 to 5 and Table 1 below.

The particle size distribution of the crystals obtained in Examples 1 to 4 had a bimodal distribution having a first peak at a particle size of 10 to 100 μm and a second peak at a particle size of 150 to 500 μm (FIG. 1 3). On the other hand, the grain size distribution of the crystals obtained in Comparative Example 1 had a unimodal distribution having a large particle size as a peak, as shown in FIG. In addition, the grain size distribution of the crystals obtained in Comparative Example 2 had a unimodal distribution having a small grain size as a peak, as shown in FIG.

As shown in Table 1, in the crystal of Comparative Example 1 having a unimodal particle size distribution composed of large-sized particles, blocking during storage could not be suppressed, and many blocking substances remained after long-term storage. occured. Even the crystals of Comparative Example 2 having a unimodal particle size distribution composed of particles having a small particle size were unable to suppress blocking during storage, and were more likely to be blocked than Comparative Example 1.

On the other hand, in the crystals of Examples 1 to 4 having the bimodal particle size distribution having the first peak and the second peak, blocking during storage was clearly suppressed. Therefore, for example, it can be understood that the strainer is less likely to be clogged when used as a raw material of an optical material, and the workability of manufacturing the optical material can be improved.

The 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene powder according to the embodiment of the present invention can be preferably used as a raw material of a resin for optical materials, for example.

Claims (3)

The frequency distribution obtained by the volume-based dry particle size distribution measurement has a first peak having a peak in the particle diameter range of 10 to 100 μm and a second peak having a peak in the particle diameter range of 150 to 500 μm. 2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene powder. The 2,2′-bis(2-hydroxyethoxy)-1 according to claim 1, wherein the frequency distribution has a bottom between the first peak and the second peak in a particle diameter range of 50 to 200 μm. , 1'-Binaphthalene powder. The 2,2′-bis(2-hydroxy) according to claim 1 or 2, wherein the volume ratio of the particles having a smaller particle size than the bottom between the first mountain and the second mountain is 50 to 70%. Ethoxy)-1,1′-binaphthalene powder.