JP7146345B2 - Resin raw material composition containing alcohol compound having fluorene skeleton - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin raw material composition suitable as a raw material monomer for resins (optical resins) constituting optical members such as optical lenses and optical films, and excellent in workability and productivity.

Resin materials such as polycarbonates, polyesters, polyacrylates, polyurethanes, and epoxies, which use alcohols with a fluorene skeleton as raw material monomers, have excellent optical properties and heat resistance. attention as a material. Among them, the following formula (1):

で表される構造を有するアルコール化合物は、該アルコール化合物及びその誘導体から製造される樹脂が屈折率等の光学特性、耐熱性、耐水性、耐薬品性、電気特性、機械特性、溶解性等の諸特性に優れることから、特に光学樹脂の原材料として着目されている（例えば特許文献１）。

An alcohol compound having a structure represented by is such that the resin produced from the alcohol compound and its derivative has optical properties such as refractive index, heat resistance, water resistance, chemical resistance, electrical properties, mechanical properties, solubility, etc. Due to its excellent properties, it is drawing particular attention as a raw material for optical resins (for example, Patent Document 1).

On the other hand, the alcohol compound represented by the above formula (1) clathrates the aromatic hydrocarbons used in the production process to form a clathrate compound, and clathrates the clathrate when the clathrate compound is dried under reduced pressure. It is known that it is difficult to remove aromatic hydrocarbons containing aromatic hydrocarbons, and several methods for producing alcohol compounds represented by the above formula (1) that do not clathrate aromatic hydrocarbons have been reported (e.g. Patent documents 2-4).

In Patent Document 2, after producing an alcohol compound represented by the above formula (1) under specific conditions, a compound represented by the above formula (1) at a specific temperature from a solution containing aromatic hydrocarbons and methanol describes a method for obtaining a compound represented by the above formula (1) that does not clathrate aromatic hydrocarbons by precipitating crystals of. Further, in Patent Document 3, by crystallizing the alcohol compound represented by the above formula (1) from a mixed solvent of a water-soluble ketone and a water-soluble alcohol, the above formula ( A method for obtaining the compound represented by 1) is described. The melting points of the crystals of the compound represented by the above formula (1) obtained by the methods described in both documents are both 148 to 151 ° C. (maximum melting endothermic temperature by differential scanning calorimetry), and aromatic hydrocarbons are It is described that it exhibits a melting point comparable to that of the compound represented by the formula (1) in which it clathrates.

In Patent Document 4, from a crystallization solution containing chain ketones having 4 or more carbon atoms and having a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight, at a specific temperature, the above formula It describes a method for obtaining a compound represented by the above formula (1) that does not clathrate aromatic hydrocarbons by precipitating crystals of the compound represented by (1). It is described that a plurality of crystal polymorphs can be obtained by the above method, and the melting point of these crystal polymorphs is between 167 and 196 ° C., and the above formula (1) that includes aromatic hydrocarbons. It is described that it exhibits a melting point higher than that of the compound used.

JP-A-07-149881 Japanese Patent Application Laid-Open No. 2017-200900 JP 2017-141182 A Japanese Patent Application Laid-Open No. 2017-200901

When the inventors of the present application repeated the methods of Patent Documents 2 and 3, the crystals produced by the method had a low bulk density (loose bulk density) of 0.25 to 0.29 g / cm ³ , and during use It was found that there were problems such as poor handleability during transportation. On the other hand, the crystals produced by the method of Patent Document 4 are described to have a bulk density of 0.5 to 1.5 g/cm ³ , and compared to the crystals described in Patent Documents 2 and 3, the bulk density is Although it has been improved, since the melting point is high as mentioned above, when the crystal is melted once and used, such as melt polymerization, more energy is required or a reaction that can be made at a higher temperature. Especially in industrial use, such as the need for a container, there is a problem that the usability is inferior to crystals with a low melting point.

The object of the present invention is to provide a ) to provide a resin raw material composition containing an alcohol compound represented by

As a result of intensive studies to solve the above problems, the present inventors have found that the alcohol compound represented by the above formula (1) contains a certain amount of the alcohol compound represented by the following formula (2) to form a resin. The present inventors have found that the above problems can be solved by using a raw material composition. Specifically, the following inventions are included.

[1]
Formula (1) below:

で表されるアルコール化合物を８５．０～９９．９重量％、以下式（２）：

85.0 to 99.9% by weight of an alcohol compound represented by the following formula (2):

で表されるアルコール化合物を０．０１～０．５重量％含み、
芳香族炭化水素類の含量が１重量％未満であり、示差走査熱量分析による融解吸熱最大温度が１４８～１５１℃である、樹脂原料用組成物。

Contains 0.01 to 0.5% by weight of an alcohol compound represented by
A resin raw material composition containing less than 1% by weight of aromatic hydrocarbons and having a maximum melting endothermic temperature of 148 to 151° C. as determined by differential scanning calorimetry.

[2]
Furthermore, the following formula (3):

で表されるアルコール化合物の含量が０．１重量％以下である、［１］に記載の樹脂原料用組成物。

The resin raw material composition according to [1], wherein the content of the alcohol compound represented by is 0.1% by weight or less.

[3]
The resin raw material composition according to [1] or [2], which has a loose bulk density of 0.4 g/cm ³ or more.

[4]
Formula (2) below:

で表されるアルコール化合物。

Alcohol compound represented by.

According to the present invention, the above formula (1 ), it is possible to provide a resin raw material composition containing the alcohol compound represented by

In addition, the resin raw material composition of the present invention is characterized by excellent filterability when the resin raw material composition is produced, probably because it contains a certain amount of the alcohol compound represented by the above formula (2). .

1 is an LC-MS chart of the alcohol compound represented by the above formula (2) obtained in Production Example 1. FIG.

<Composition for resin raw material of the present invention>
The resin raw material composition of the present invention contains 85.0 to 99.9% by weight of the alcohol compound represented by the above formula (1). If the content is less than 85.0% by weight, it may not be suitable for use as a resin raw material composition.

The resin raw material composition of the present invention must contain 0.01 to 0.5% by weight of the alcohol compound represented by the above formula (2). If the content is less than 0.01% by weight or more than 0.5% by weight, the bulk density may not be improved and the problems of the present invention may not be solved.

The content of the alcohol compound represented by the above formula (3) contained in the resin raw material composition of the present invention is preferably 0.1% by weight or less. By setting the amount to 0.1% by weight or less, it becomes possible to further improve the strength and heat resistance (glass transition temperature) of the resin produced using the composition for resin raw material of the present invention.

When the alcohol compound represented by the above formula (1) clathrates aromatic hydrocarbons, the content thereof is about 1 to 6% by weight (Patent Document 3, [0005]). Therefore, the alcohol compound represented by the above formula (1) contained in the resin raw material composition of the present invention must mainly be a non-clathrate. The alcohol compound represented by the formula (1), which is a non-clathrate, can be produced, for example, by the methods described in Patent Documents 2 and 3. In addition, since the alcohol compound represented by the above formula (1), which is a non-clathrate, is mainly used, the amount of aromatic hydrocarbons contained in the resin raw material composition of the present invention is usually less than 1% by weight. Yes, preferably 0.5% by weight or less, more preferably 0.1% by weight or less.

The maximum melting endothermic temperature of the resin raw material composition of the present invention is 148 to 151° C. according to differential scanning calorimetry. The maximum melting endothermic temperature by differential scanning calorimetry in the present invention means the temperature at which the maximum endothermic peak is observed when differential scanning calorimetry is performed under the conditions described later.

It is preferable that the resin raw material composition of the present invention does not include an endothermic peak in the range of 165 to 200° C. obtained by differential scanning calorimetry. When an endothermic peak is included in the above range, it is suggested that other crystal forms with a high melting point (crystal polymorphs described in Patent Document 4) are included. More energy may be required than a resin raw material composition that does not contain it.

The loose bulk density of the resin raw material composition of the present invention is 0.4 g/cm ³ or more, specifically 0.4 to 0.5 g/cm ³ . In addition, the loose bulk density in the present invention means the bulk density measured by the method described later.

<Method for Producing the Resin Raw Material Composition of the Present Invention>
For example, the resin raw material composition of the present invention is produced by producing an alcohol compound represented by the above formula (1) by the method described in Patent Document 2, and performing a refining operation such as recrystallization to obtain the above formula (2). It can be produced by repeating the purification operation until the content of the alcohol compound is within the range described above.

EXAMPLES The present invention will be specifically described below with reference to Examples, etc., but the present invention is not limited in any way. In addition, various measurements were implemented by the following method in an example. In addition, the content of each component described in the examples below is a value obtained by an absolute calibration curve method based on the area value obtained by high performance liquid chromatography (HPLC) measured under the following conditions. The content of group hydrocarbons is a value determined by an internal standard method (internal standard: 1,2-dimethoxyethane) based on area values obtained by gas chromatography (GC) under the following conditions.

(1) HPLC measurement conditions Apparatus: LC-2010A manufactured by Shimadzu Corporation
Column: Waters XBridge Shield RP18 (3.5 μm, 4.6 mmφ×250 mm)
Mobile phase: pure water/acetonitrile (acetonitrile 70% → 100%)
Flow rate: 1.0ml/min
Column temperature: 40°C
Detection wavelength: UV 254nm

(2) GC measurement conditions Device: GC-2014 manufactured by Shimadzu Corporation
Column: DB-1 (0.25 μm, 0.25 mm ID × 30 m)
Temperature rise: 40°C (held for 5 minutes) → 20°C/min → 250°C (held for 10 minutes)
Inj temperature: 250°C
Det temperature: 300°C
Split ratio 1:10
Carrier: Nitrogen 54.4 kPa (constant)

(3) Conditions for measuring maximum melting endothermic temperature by differential scanning calorimetry (DSC) 5 mg of a sample was precisely weighed in an aluminum pan, and aluminum oxide was measured using a differential scanning calorimeter (SII Nanotechnology Co., Ltd.: DSC7020). was measured under the following operating conditions as a control, and the detected maximum melting endothermic temperature was defined as the melting point.
(Operating conditions)
Heating rate: 10°C/min
Measurement range: 30-250℃
Atmosphere: open, nitrogen 40 ml/min

(4) Conditions for Measuring Loose Bulk Density Loose bulk density was measured using a powder tester PT-X manufactured by Hosokawa Micron Corporation.

(5) LC-MS measurement conditions Apparatus: Xevo G2 Q-Tof manufactured by Waters
Column: X SELECT CSH C18 manufactured by Waters (3.5 μm, 4.6 mmφ×150 mm)
Column temperature: 40°C
Detection wavelength: UV 254nm
Mobile phase: A liquid = pure water, B liquid = acetonitrile. In addition, the analysis was performed by changing the concentration of the liquid B as follows.
B liquid concentration: 50% (0 min) → 70% (10 min) → 70% (18 min) →
100% (25 min) → 100% (35 min)
Mobile phase flow rate: 0.8ml/min
Detection method: Q-Tof
Ionization method: APCI (−) method Ion Source: Corona current 20.0 μA, temperature 150° C.
Sampling Cone: voltage 30V, gas flow 50L/h
Desolvation Gas: temperature 600°C, gas flow 1200L/h
Mass range: 100-1300

<Comparative Example 1>
Into a glass reactor equipped with a stirrer, heating cooler, and thermometer, 900 g of 9,9'-bis(4-hydroxy-3-phenylphenyl)fluorene, 20.4 g of potassium carbonate, 361 g of ethylene carbonate, and 1350 g of toluene. , and 90 g of triethylene glycol dimethyl ether were charged, heated to 115° C., and stirred at the same temperature for 8 hours.
After cooling the obtained reaction liquid to 90° C., 1350 g of water was added, and the mixture was stirred at 80 to 85° C. for 30 minutes, allowed to stand, and then the aqueous layer was separated. After repeating the same operation three times, the solvent was removed by concentrating the obtained organic solvent layer to obtain a concentrate. 294 g of toluene and 1128 g of methanol were added to the resulting concentrate to obtain a crystallization solution.
The resulting crystallization solution was heated to 65°C and stirred at the same temperature for 1 hour to completely dissolve the crystals. Stir at temperature for 2 hours. After further cooling to 20° C., it was filtered to obtain crystals.
The obtained crystals were dried at an internal temperature of 68° C. to 73° C. for 5 hours under a reduced internal pressure of 1.3 kPa to obtain 860 g of the alcohol compound represented by the above formula (1). Each analytical value of the obtained alcohol compound represented by the above formula (1) was as follows.

Content of the alcohol compound represented by the above formula (1): 98.20% by weight
Content of the alcohol compound represented by the above formula (2): 0.74% by weight
Content of the alcohol compound represented by the above formula (3): 0.00% by weight (not detected)
Toluene content: 0.03% by weight
DSC melting endothermic maximum temperature: 150°C (there is no endothermic peak in the range of 165-200°C)
Loose bulk density: 0.253 g/cm ³

<Comparative Example 2>
Into a glass reactor equipped with a stirrer, heating cooler, and thermometer, 900 g of 9,9′-bis(4-hydroxy-3-phenylphenyl)fluorene), 20.4 g of potassium carbonate, 361 g of ethylene carbonate, and toluene. 1350 g and 900 g of triethylene glycol dimethyl ether were charged, heated to 115° C., and stirred at the same temperature for 13 hours.
After cooling the resulting reaction solution to 85° C., 1350 g of water was added, and the mixture was stirred at 80 to 85° C. for 30 minutes, allowed to stand, and separated into an aqueous layer. After repeating the same operation three times, the obtained organic solvent layer was partially concentrated to obtain a solution containing the alcohol compound represented by the above formula (1), toluene and methyl diglyme. After adding 330 g of toluene and 510 g of methanol to the solution to obtain a crystallization solution, the resulting crystallization solution was heated to 65° C. and stirred at the same temperature for 1 hour to completely dissolve the crystals. When 0.1 g of the crystals obtained in Comparative Example 1 were added as seed crystals when the temperature was lowered to 40° C. by cooling at 15° C./min, crystals precipitated. After that, the mixture was stirred at the same temperature for 1 hour. After stirring, the mixture was further cooled to 25°C and filtered to obtain crystals.
The obtained crystals were dried under a reduced internal pressure of 1.1 kPa at an internal temperature of 68° C. to 73° C. for 5 hours to obtain 801 g of the alcohol compound represented by the above formula (1). Each analytical value of the obtained alcohol compound represented by the above formula (1) was as follows.

Content of the alcohol compound represented by the above formula (1): 98.40% by weight
Content of the alcohol compound represented by the above formula (2): 0.56% by weight
Content of the alcohol compound represented by the above formula (3): 0.00% by weight (not detected)
Toluene content: 0.05% by weight
DSC melting endothermic maximum temperature: 150°C (there is no endothermic peak in the range of 165-200°C)
Loose bulk density: 0.290 g/cm ³

<Comparative Examples 3 to 6>
After the reaction, washing with water, and concentration, the same operation as in Comparative Example 1 was performed except that the amounts of toluene and methanol added to the resulting concentrate were changed to the amounts shown in Table 1 below. compound was prepared. Each analysis value of the obtained alcohol compound represented by the above formula (1) was as shown in Table 1 below.

なお、上記表（１）中、式（３）で表される化合物のピークは検出されなかったため、その含量を０．００％とした。また、融点とはＤＳＣ融解吸熱最大温度を表し、いずれの比較例においても１６５～２００℃の範囲に吸熱ピークは存在しなかった。

Since no peak of the compound represented by formula (3) was detected in Table (1) above, the content was set to 0.00%. The melting point represents the DSC melting endothermic maximum temperature, and no endothermic peak was present in the range of 165 to 200°C in any of the comparative examples.

<Comparative Example 7>
The same operation as in Example 1 of JP-A-2017-141182 was performed to produce a compound represented by the above formula (1). Each analytical value of the obtained alcohol compound represented by the above formula (1) was as follows.

Content of the alcohol compound represented by the above formula (1): 98.60% by weight
Content of the alcohol compound represented by the above formula (2): 0.00% by weight (not detected)
Content of the alcohol compound represented by the above formula (3): 0.19% by weight
Toluene content: 0.05% by weight
DSC melting endothermic maximum temperature: 150°C (there is no endothermic peak in the range of 165-200°C)
Loose bulk density: 0.260 g/cm ³

<Comparative Example 8>
A compound represented by the above formula (1) was produced in the same manner as in Example 2 of JP-A-2017-141182. Each analytical value of the obtained alcohol compound represented by the above formula (1) was as follows.

Content of the alcohol compound represented by the above formula (1): 98.70% by weight
Content of the alcohol compound represented by the above formula (2): 0.00% by weight (not detected)
Content of the alcohol compound represented by the above formula (3): 0.12% by weight
Toluene content: 0.03% by weight
DSC melting endothermic maximum temperature: 150°C (there is no endothermic peak in the range of 165-200°C)
Loose bulk density: 0.242 g/cm ³

<Production Example 1 Isolation and identification of the alcohol compound represented by the above formula (2)>
A concentrate was obtained by concentrating the filtrate obtained during the filtration operation in Comparative Examples 1 to 6, and after dissolving the concentrate in methyl-tert-butyl ether, fractionation was performed using a PLC plate (Merck silica gel 60PLC plate). By doing so, the alcohol compound represented by the above formula (2) was isolated. The obtained alcohol compound represented by the above formula (2) was confirmed to have the structure represented by the above formula (2) by LC-MS analysis under the above conditions. An LC-MS chart is shown in FIG. 1, and the analysis results are described below.
Analysis value: 545.21 ([MH] ⁻ )

<Example 1>
700 g of the alcohol compound represented by the above formula (1) obtained in Comparative Example 1, 770 g of toluene, and 770 g of methanol were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, and the mixture was heated to 65°C. After the temperature was raised, the alcohol compound represented by the above formula (1) was dissolved by stirring at the same temperature for 2 hours. Thereafter, the mixture was cooled at 0.1°C/min to precipitate crystals at 44°C, and stirred at the same temperature for 2 hours. After further cooling to 20° C., it was filtered to obtain crystals.
The resulting crystals were dried at an internal pressure of 1.1 kPa at an internal temperature of 68° C. to 73° C. for 5 hours to obtain 641 g of the composition for resin raw material of the present invention. Each analysis value of the obtained resin raw material composition was as follows.

Content of the alcohol compound represented by the above formula (1): 98.50% by weight
Content of the alcohol compound represented by the above formula (2): 0.31% by weight
Content of the alcohol compound represented by the above formula (3): 0.00% by weight (not detected)
Toluene content: 0.03% by weight
DSC melting endothermic maximum temperature: 150°C (there is no endothermic peak in the range of 165-200°C)
Loose bulk density: 0.442 g/cm ³

<Example 2>
490 g of the resin raw material composition obtained in Example 1, 539 g of toluene, and 539 g of methanol were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer. The resin raw material composition was dissolved by stirring for 2 hours at . Thereafter, the mixture was cooled at 0.1°C/min to precipitate crystals at 42°C, and stirred at the same temperature for 2 hours. After further cooling to 20° C., it was filtered to obtain crystals.
The resulting crystals were dried at an internal temperature of 68° C. to 73° C. for 5 hours under a reduced internal pressure of 1.1 kPa to obtain 451 g of the resin raw material composition of the present invention. Each analysis value of the obtained resin raw material composition was as follows.

Content of the alcohol compound represented by the above formula (1): 98.70% by weight
Content of the alcohol compound represented by the above formula (2): 0.11% by weight
Content of the alcohol compound represented by the above formula (3): 0.00% by weight (not detected)
Toluene content: 0.04% by weight
DSC melting endothermic maximum temperature: 149°C (no endothermic peak in the range of 165 to 200°C)
Loose bulk density: 0.433 g/cm ³

<Example 3>
300 g of the resin raw material composition obtained in Example 2, 330 g of toluene, and 330 g of methanol were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer. The resin raw material composition was dissolved by stirring for 2 hours at . Thereafter, the mixture was cooled at 0.1°C/min to precipitate crystals at 43°C, and stirred at the same temperature for 2 hours. After further cooling to 20° C., it was filtered to obtain crystals.
The obtained crystals were dried at an internal temperature of 68° C. to 73° C. for 5 hours under a reduced internal pressure of 1.1 kPa to obtain 272 g of the resin raw material composition of the present invention. Each analysis value of the obtained composition for upper resin raw material was as follows.

Content of the alcohol compound represented by the above formula (1): 99.10% by weight
Content of the alcohol compound represented by the above formula (2): 0.01% by weight
Content of the alcohol compound represented by the above formula (3): 0.00% by weight (not detected)
Toluene content: 0.02% by weight
DSC melting endothermic maximum temperature: 150°C (there is no endothermic peak in the range of 165-200°C)
Loose bulk density: 0.490 g/cm ³

<Example 4>
Example except that the alcohol compound represented by the above formula (1) was changed to that obtained in Comparative Example 2, the amount used was 600 g, the amount of toluene used was 660 g, and the amount of methanol used was 660 g. Purification was carried out in the same manner as in 1 to obtain 546 g of the resin raw material composition of the present invention. Each analysis value of the obtained resin raw material composition was as follows.

Content of the alcohol compound represented by the above formula (1): 98.60% by weight
Content of the alcohol compound represented by the above formula (2): 0.19% by weight
Content of the alcohol compound represented by the above formula (3): 0.00% by weight (not detected)
Toluene content: 0.03% by weight
DSC melting endothermic maximum temperature: 150°C (there is no endothermic peak in the range of 165-200°C)
Loose bulk density: 0.463 g/cm ³

<Example 5>
The purification operation was carried out in the same manner as in Example 1 except that the alcohol compound represented by the above formula (1) was changed to that obtained in Comparative Example 3, the amount of toluene used was 850 g, and the amount of methanol used was 470 g. 617 g of the resin raw material composition of the present invention was obtained. Each analysis value of the obtained resin raw material composition was as follows.

Content of the alcohol compound represented by the above formula (1): 98.50% by weight
Content of the alcohol compound represented by the above formula (2): 0.37% by weight
Content of the alcohol compound represented by the above formula (3): 0.00% by weight (not detected)
Toluene content: 0.04% by weight
DSC melting endothermic maximum temperature: 149°C (no endothermic peak in the range of 165 to 200°C)
Loose bulk density: 0.424 g/cm ³

<Example 6>
Except for changing the alcohol compound represented by the above formula (1) to the one obtained in Comparative Example 6, the purification operation was carried out in the same manner as in Example 5 to obtain 613 g of the resin raw material composition of the present invention. Each analysis value of the obtained resin raw material composition was as follows.

Content of the alcohol compound represented by the above formula (1): 98.50% by weight
Content of the alcohol compound represented by the above formula (2): 0.41% by weight
Content of the alcohol compound represented by the above formula (3): 0.00% by weight (not detected)
Toluene content: 0.04% by weight
DSC melting endothermic maximum temperature: 150°C (there is no endothermic peak in the range of 165-200°C)
Loose bulk density: 0.401 g/cm ³

Claims (4)

Formula (1) below:

85.0 to 99.9% by weight of an alcohol compound represented by the following formula (2):

Contains 0.01 to 0.5% by weight of an alcohol compound represented by
A resin raw material composition containing less than 1% by weight of aromatic hydrocarbons and having a maximum melting endothermic temperature of 148 to 151° C. as determined by differential scanning calorimetry. Furthermore, the following formula (3):

2. The resin raw material composition according to claim 1, wherein the content of the alcohol compound represented by is 0.1% by weight or less. The resin raw material composition according to claim 1 or 2, having a loose bulk density of 0.4 g/cm ³ or more. Formula (2) below:

Bulk density improving agent represented by.

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