TW202030172A - 2, 2'-bis(2-hydroxyethoxy)-1, 1'-binaphthalene compound and method for producing same - Google Patents

Abstract

The present invention suppresses coloring during storage. A 2, 2'-bis(2-hydroxyethyoxy)-1, 1'-binaphthalene compound according to one embodiment of the present invention has an elemental silicon content of 0.1-150 ppm by mass as determined by ICP emission spectrometry. A method for producing a 2, 2'-bis(2-hydroxyethyoxy)-1, 1'-binaphthalene compound according to one embodiment of the present invention comprises a step for having a 2, 2'-bis(2-hydroxyethyoxy)-1, 1'-binaphthalene compound precipitate from a 2, 2'-bis(2-hydroxyethyoxy)-1, 1'-binaphthalene solution that contains a silicon-containing compound.

Description

2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound and manufacturing method thereof

The present invention relates to a 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound and its manufacturing method.

The 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound is used as a raw material (for example, a monomer) of an optical material represented by an optical lens or an optical film. For example, Patent Document 1 and Patent Document 2 describe that the powder of the compound is obtained by crystallization. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-227387 [Patent Document 2] Japanese Patent Laid-Open No. 2015-187098

[The problem to be solved by the invention] However, the conventional 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound has a problem that it is easy to color when it becomes high temperature during storage or transportation, for example. The coloration of the raw materials will cause the coloration of subsequent reaction products, ie, polymers. Therefore, it is required to improve heat resistance, that is, to suppress coloration during storage at high temperatures.

The object of the embodiment of the present invention is to provide a 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound that can suppress coloration during storage. [Means to solve the problem]

Among the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compounds according to the embodiment of the present invention, the content of silicon is based on inductively coupled plasma (ICP) emission spectroscopy analysis The content is 0.1 mass ppm to 150 mass ppm.

The manufacturing method of one embodiment is a method of manufacturing the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound, which includes 2,2'-bis(2) containing a silicon-containing compound The step of depositing 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound in the solution of -hydroxyethoxy)-1,1'-binaphthyl. [Effects of the invention]

If it is the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound of the embodiment of the present invention, the coloration during storage can be suppressed.

The 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound according to the embodiment of the present invention is characterized in that the content of silicon based on ICP emission spectroscopic analysis is 0.1 mass ppm to 150 mass ppm ppm. By containing a small amount of silicon in this way, the heat resistance during storage is excellent, that is, coloring is suppressed even when the temperature becomes high during storage or transportation. Therefore, when the compound is used as, for example, a raw material of an optical material, the coloration of the reaction product (polymer, etc.) can be suppressed.

Here, ICP (Inductively Coupled Plasma) emission spectroscopy analysis is to excite the constituent elements (atoms) contained in the sample by applying energy of argon plasma to the sample from the outside, and measure that the excited atoms return to low The method of emitting luminescence lines (spectral lines) at the energy level of the luminescence line can determine the type of component elements from the position (wavelength) of the luminescence line, and obtain the content of each element from its intensity.

The content of the silicon element is the mass ratio of silicon element relative to the total amount of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound. In this embodiment, it is 0.1 mass ppm or more and 150 mass ppm or less. The content of the silicon element is preferably 1 mass ppm or more, more preferably 5 mass ppm or more, may be 10 mass ppm or more, or may be 15 mass ppm or more. Furthermore, the content of silicon element is preferably 140 ppm by mass or less, and may be 100 ppm by mass or less.

The form of silicon contained in the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound is not particularly limited. It can be contained in the form of a silicon monomer or a silicon compound Form to contain. Examples of the silicon-containing compound include silicon oxides such as silicon dioxide; silicic acids such as orthosilicic acid and metasilicic acid; silicates such as sodium silicate, potassium silicate, aluminum silicate, and calcium silicate. These can be used in any one type or in combination of two or more types. As an embodiment, an alkali metal salt of silicic acid may be used, or silicon dioxide may be used.

The 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound of one embodiment is 2,2'-bis(2-hydroxyethoxy) obtained by the crystallization described later )-1,1'-binaphthyl crystals are crystallization products. The crystallization products contain silicon-containing compounds, so they can be said to contain 2,2'-bis(2-hydroxyethoxy)-1,1' -A crystalline complex of binaphthyl and silicon-containing compounds. Moreover, this crystallization product is a powder, so it can also be called 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl powder.

In addition, the silicon element is preferably contained in the crystallization at the stage of crystallization, and it may be added or mixed in the steps of washing and drying after crystallization.

The 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound of this embodiment is preferably a racemate, and may contain a large amount of any optical isomer.

The purity of the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound of this embodiment (that is, the target 2,2'-bis The content of (2-hydroxyethoxy)-1,1'-binaphthyl is the peak area ratio obtained by gas chromatography (GC) measurement described later). It is not particularly limited, but is preferably It is 90% or more, more preferably 95% or more, and still more preferably 98% or more.

The production method of the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound of this embodiment is not particularly limited, but it is preferable to prepare the compound containing 2,2'-bis(2 -Hydroxyethoxy)-1,1'-binaphthyl solution (hereinafter, referred to as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution), and from this solution 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl crystals are precipitated in it.

As an organic solvent used in the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution, a soluble 2,2'-bis(2-hydroxyethoxy)- Examples of 1,1'-binaphthyl include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, and heptane, and halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene. Halogenated aliphatic hydrocarbon solvents, such as dichloromethane, 1,2-dichloroethane, etc., can be used either alone or in combination of two or more. Among these, an aromatic hydrocarbon solvent is preferred, and toluene and/or xylene are more preferred.

As a preparation method of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution, for example, a method of reacting 1,1'-bin-2-naphthol with ethylene carbonate Method, adding ethylene oxide to 1,1'-bin-2-naphthol, etc.

The targeted 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene is 1 mol of 1,1'-bin-2-naphthol and 2 mol of ethylene carbonate Or a compound formed by the reaction of ethylene oxide. In addition, as a side reaction product, 1 mol of 1,1'-bin-2-naphthol and 1 mol of ethylene carbonate or cyclic A compound formed by the reaction of ethylene oxide (1 mol adduct), 1 mol of 1,1'-bi-2-naphthol and 3 mol of ethylene carbonate or ethylene oxide Compound (3 mol adduct), 1 mol of 1,1'-bi-2-naphthol and 4 mol or more of ethylene carbonate or ethylene oxide reacted compound (4 mol or more Adducts), target compounds (polymers) formed by polymerizing 2 mol or more of carbonate bonds, etc. Therefore, the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound of this embodiment may contain these side reaction products.

As a method of reacting 1,1'-bin-2-naphthol and ethylene carbonate, for example, 1,1'-bin-2-naphthol, ethylene carbonate, reaction catalyst, and organic solvent A method of mixing and reacting at a reaction temperature of 70°C to 130°C for 1 hour to 30 hours. From the viewpoint of increasing the yield, the amount of ethylene carbonate used is 1 mol of 1,1'-bin-2-naphthol, preferably 1.8 mol to 10 mol, more preferably 2 mol ~5 mol, more preferably 2.1 mol to 3 mol.

As a method of adding ethylene oxide to 1,1'-bin-2-naphthol, for example, dissolving 1,1'-bin-2-naphthol in an organic solvent, in the presence of a reaction catalyst , A method of introducing ethylene oxide so that the internal pressure of the reaction vessel becomes 0.01 MPa to 1 MPa at a reaction temperature of 60°C to 150°C. From the viewpoint of increasing the yield, the amount of ethylene oxide used is preferably 1.8 mol to 10 mol, more preferably 2 mol relative to 1 mol of 1,1'-bin-2-naphthol ~5 mol, more preferably 2.1 mol to 3 mol.

In these methods, the reaction catalyst is preferably an alkali catalyst. For example, any one or a combination of potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate, etc. can be used Use the above. Furthermore, as the organic solvent, those used in the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene solution can be cited.

After the synthesis of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, an organic solvent can be added to the reaction solution to prepare 2,2'-bis(2-hydroxyethoxy)- 1,1'-Binaphthalene solution. Furthermore, the obtained reaction solution may be washed with an alkali and washed with water until it becomes neutral.

As a 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl crystal from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution As a method of reducing its solubility, for example, cooling and the addition of a solvent with low solubility can be cited. Preferably, it is a method of cooling. In addition, when crystals are precipitated, seed crystals can also be added.

In the crystallization step of the precipitated crystals, a 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution containing a silicon-containing compound can also be used to precipitate 2,2'-binaphthyl from the solution. 2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl crystal. By performing precipitation in the presence of a silicon-containing compound in this way, a 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl crystallization product containing silicon element can be obtained.

In addition, the solution containing the silicon-containing compound may be prepared by adding a silicon-containing compound to the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution prepared by the method, or It can also be used in the preparation of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution (during reaction, washing, washing, etc.) For example, a silicon-containing compound is included as an impurity, and the silicon-containing compound is mixed into the solution.

The amount of the silicon-containing compound in the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution is not particularly limited, for example, relative to 2,2'-bis(2-hydroxyethoxy (Base) 100 parts by mass of the -1,1'-binaphthyl compound may contain 0.001 parts by mass to 5 parts by mass of the silicon-containing compound, 0.01 parts by mass to 2 parts by mass, or 0.05 parts by mass to 1.5 parts by mass.

The concentration of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound in 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution It is not specifically limited, For example, it may be 5 mass%-50 mass %, and it may be 10 mass%-40 mass %.

As a crystallization method based on cooling, for example, cooling the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution at 70°C to 130°C to 60°C or less is preferred. Method below 30°C. The cooling rate is not particularly limited, and, for example, it may be 0.1°C/min to 10°C/min, or 0.2°C/min to 1.0°C/min.

The precipitated crystals of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl can be taken out by centrifugation, filtration, etc. The crystals taken out can be washed, dried, etc. Thereby, the powder of the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound of the embodiment can be obtained.

The 50% volume particle diameter (D50) of the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound of this embodiment is not particularly limited, and may be, for example, 30 μm to 150 μm. It can also be 50 μm to 100 μm. [Example]

Hereinafter, a more specific description will be given with examples, but the present invention is not limited to these. In addition, various measurements in the examples and comparative examples were carried out by the following methods.

[Yield] The theoretical yield calculated from (RS)-1,1'-bin-2-naphthol used as a starting material was set to 100% by mass, and the ratio (mass%) of the yield in this case was calculated.

[purity] A 0.2% by mass toluene solution of the obtained crystals was prepared and subjected to gas chromatography (GC) measurement based on the following conditions. The target substance (RS)-2,2'-bis(2-hydroxyethoxy ) The sum of the peak areas of -1,1'-binaphthalene and the side reaction product is set to 100. In this case, (RS)-2,2'-bis(2-hydroxyethoxy)-1,1'- The ratio of the peak area of binaphthyl was calculated as purity (%). Here, the peak of (RS)-2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl was detected around the holding time of 24.6 minutes. (GC measurement conditions) ･Measurement device: Agilent Technologies 7820A (manufactured by Agilent Technologies) ･Pipe string: DB-1 125-1011 (manufactured by Shimadzu JLC) ･Injection volume: 1 μL ･Injection method: Diversion method (Diversion ratio 1:10) ･Inlet temperature: 300℃ ･Conditions for heating up: initial temperature 40°C for 5 minutes, temperature rise at 10°C/min, and finally 300°C for 5 minutes ･Carrier gas: helium (5.8 mL/min) ･Detector: Hydrogen flame ionization type detector (FID)

[Silicon content] The content of silicon in the sample was measured using an ICP emission spectrometer (Agilent 5100) manufactured by Agilent Technologies. After the sample was ashed using sulfuric acid, sodium carbonate as a flux was used for alkali fusion, and the obtained was used as a test solution, and quantification was performed based on a calibration curve prepared using a standard sample with a known concentration.

[D50] The frequency distribution (histogram) is obtained by dry particle size distribution measurement based on the volume standard of the laser diffraction scattering method, and the 50% volume particle diameter (D50) is obtained from the frequency distribution. The measurement conditions are as follows. ･Measuring device: Microtrac MT3000II (manufactured by MicrotracBEL) ･Measuring range: 0.243 μm～2000 μm ･Light source: Semiconductor laser 780 nm×3 ･Dispersing solvent: air (refractive index 1.00) ･Particle refractive index: 1.81 ･Measurement channels (Channel): 104

[Heat resistance: heat test] 10 g of the obtained crystals were placed in a thermostat at 80°C and 100°C, respectively, and the YI value (yellowness) was measured for the crystals after 1 week (after the heat resistance test). The YI value was also measured for the crystals before the heat resistance test. The YI value is measured using a 10 w/w% methanol solution in accordance with Japanese Industrial Standards (JIS) K2580. ･Measuring device: OME-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) ･Cell: Glass cell ･Light path length: 33 mm

[Example 1] Put 286 g (1 mol) of (RS)-1,1'-bi-2-naphthol and 194 g (2.2 mol) of ethylene carbonate into a glass reactor equipped with a stirrer, a cooler and a thermometer , 15 g of potassium carbonate and 450 g of toluene, react at 110°C for 10 hours. After adding 540 g of toluene to the reaction solution for dilution, 290 g of a 10% by mass aqueous sodium hydroxide solution was added to wash the organic solvent layer. Then, it was washed repeatedly with 500 g of water until the water after washing became neutral. After washing with water, 1.0 g of sodium silicate aqueous solution (trade name: sodium silicate solution, manufactured by FUJI FILM and Wako Pure Chemical Industries, Ltd.) was added to the organic solvent layer, and stirred for 30 minutes. Thereafter, it was cooled from 80°C to 30°C at a rate of 0.5°C/min, and filtered under reduced pressure (50 kPa) and dried to obtain (RS)-2,2'-bis(2-hydroxyethoxy) 313 g (yield: 83.5% by mass, purity: 99.6%, D50: 55 μm) of white crystals of -1,1'-binaphthyl compound. The silicon element content in the obtained crystal was 73 mass ppm.

[Example 2] Except that the amount of the sodium silicate solution added to the organic solvent layer after washing with water was 500 mg, the same operation as in Example 1 was performed to obtain (RS)-2,2'-bis(2-hydroxyethoxy) 309 g of white crystals of -1,1'-binaphthyl compound (yield: 82.4% by mass, purity: 99.5%, D50: 64 μm). The silicon element content in the obtained crystal was 16 mass ppm.

[Example 3] Except that the amount of the sodium silicate solution added to the organic solvent layer after washing with water was set to 2 g, the same operation as in Example 1 was performed to obtain (RS)-2,2'-bis(2-hydroxyethoxy) 303 g of white crystals of -1,1'-binaphthyl compound (yield: 80.8% by mass, purity: 99.4%, D50: 53 μm). The silicon element content in the obtained crystal was 130 mass ppm.

[Example 4] After washing with water, 30 mg of vapor phase silicon dioxide was added to the organic solvent layer instead of the sodium silicate solution, except that the same operation as in Example 1 was performed to obtain (RS)-2,2'-bis(2-hydroxyethoxy) (Base) 311 g of white crystals of the -1,1'-binaphthyl compound (yield: 82.9% by mass, purity: 99.4%, D50: 59 μm). The silicon element content in the obtained crystal was 25 mass ppm.

[Comparative Example 1] Except that the sodium silicate solution was not added to the organic solvent layer after washing with water, the same operation as in Example 1 was performed to obtain (RS)-2,2'-bis(2-hydroxyethoxy)-1,1'- 311 g of white crystals of the binaphthyl compound (yield: 82.9% by mass, purity: 99.6%, D50: 52 μm). The silicon element content in the obtained crystal was 0 mass ppm.

[Comparative Example 2] Except that the amount of sodium silicate solution added to the organic solvent layer after washing with water was set to 4 g, the same operation as in Example 1 was performed to obtain (RS)-2,2'-bis(2-hydroxyethoxy) 304 g of white crystals of -1,1'-binaphthyl compound (yield: 81.1% by mass, purity: 99.4%, D50: 54 μm). The silicon content in the obtained crystal was 287 ppm by mass.

Using the obtained crystals of (RS)-2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound, an evaluation test of heat resistance was performed. The results are shown in Table 1 below.

[Table 1] Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Silicon content (mass ppm) 73 16 130 25 0 287 YI value before heat resistance test 0.8 1.0 0.9 1.0 1.1 0.8 YI value after heat resistance test (80℃, 1 week) 1.3 1.2 1.3 1.4 4.1 3.4 YI value after heat resistance test (100℃, 1 week) 3.4 3.2 3.8 3.2 7.2 6.7

As shown in Table 1, in Comparative Example 1 containing no silicon and Comparative Example 2 containing too much silicon, the YI value after the heat resistance test increased, and yellowing occurred. In contrast, in Examples 1 to 4, by including a small amount of silicon in the crystals, the change in YI value after the heat resistance test is small, yellowing is suppressed, and the heat resistance during storage is excellent. [Industrial availability]

The 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound of the embodiment of the present invention can be preferably used as a raw material for resins for optical materials, for example.

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Claims (2)

A 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound, wherein the content of silicon element based on inductively coupled plasma emission spectroscopy analysis is 0.1 mass ppm to 150 mass ppm. A manufacturing method, which is a method for manufacturing the 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound as described in claim 1, comprising a silicon-containing compound containing 2,2 The step of depositing 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl compound in the'-bis(2-hydroxyethoxy)-1,1'-binaphthyl solution.