JP2022072597A - 9,9-bis(3-methyl-5-ethyl-4-aminophenyl) fluorene compound and method for producing the same - Google Patents

Abstract

To provide a diamine monomer that achieves higher glass transition temperature and higher mechanical properties of 9,9-bis(4-aminophenyl) fluorene compound-based polyimide resin and cured epoxy resin.SOLUTION: A novel 9,9-bis(4-aminophenyl) fluorene compound, 9,9-bis(3-methyl-5-ethyl-4-aminophenyl) fluorene, is produced by reacting 9-fluorenone and 2-methyl-6-ethylaniline in an aprotic polar solvent having an amide bond and with a boiling point of 170°C or higher, in coexistence with an acid catalyst.SELECTED DRAWING: Figure 1

Description

The present invention relates to a novel 9,9-bis (4-aminophenyl) fluorene compound, 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene, and a method for producing the same. The present invention relates to industrially useful 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene and a method for producing the same.

The 9,9-bis (4-aminophenyl) fluorene compound is a compound used in the field of polymer chemistry, and is particularly useful as a raw material for polyimide, polyamide, and epoxy resin. Polyimides, polyamides, and epoxy resins containing this compound are used in a wide range of industrial applications such as electronic information materials, optical materials, and composite materials.

In Non-Patent Document 1, 9,9-bis (4-aminophenyl) fluorene (BAFL), 9,9-bis (3-methyl-4-aminophenyl) fluorene, 9,9-bis (3,5-dimethyl) A polyimide is made using -4-aminophenyl) fluorene, 9,9-bis (3-ethyl-4-aminophenyl) fluorene, and 9,9-bis (3,5-diethyl-4-aminophenyl) fluorene. Has been done.

However, when the conventional 9,9-bis (4-aminophenyl) fluorene compound is used, for example, as a monomer of a polyimide resin, the glass transition temperature and mechanical properties of the obtained polyimide resin are not always sufficient. Since the optical characteristics were not sufficient, the applicable range of the polyimide resin was limited. That is, it has been desired to increase the glass shift temperature, high mechanical characteristics, and high optical characteristics of the 9,9-bis (4-aminophenyl) fluorene compound-based polyimide resin.

Polymer 46 (2005) 5278-5283

In various fields, high strength, high elastic modulus, high adhesiveness, high toughness, heat resistance, high optical properties, and the like of the polyimide resin have been desired.
Therefore, an object of the present invention is to provide a novel diamine and a method for producing the same, which improve the performance of the polyimide resin.

In view of the current state of the prior art, the present inventors have diligently studied a novel polyimide resin, and as a result, 9,9-bis (3-methyl-5), which is a novel diamine capable of obtaining a high-performance polyimide resin, can be obtained. -Ethyl-4-aminophenyl) fluorene was found. The method for producing 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene of the present invention is carried out in an aprotonic polar solvent having an amide bond and having a boiling point of 170 ° C. or higher in the coexistence of an acid catalyst. It is characterized in that 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene is produced by reacting 9-fluorenone with 2-methyl-6-ethylaniline.

The novel diamine 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene of the present invention has high strength, high elastic modulus, high adhesiveness, and high adhesiveness when used as a diamine component of a polyimide resin. It is possible to obtain a highly functional polyimide resin having toughness, heat resistance, high optical properties and the like. 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene is useful in a wide range of industrial applications such as fine chemicals, medical and agricultural chemical raw materials, resin raw materials, electronic information materials, and optical materials. be.

The method for producing 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene of the present invention contains 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene. It can be manufactured efficiently. According to the production method of the present invention, 9-fluorenone and 2-methyl-6-ethyl-4-aniline are subjected to a condensation reaction to obtain a high yield of 9,9-bis (3-methyl-5-ethyl-4-aniline). Aminophenyl) Fluorenone can be produced. The method for producing 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene of the present invention is an industrially excellent production method. The 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene obtained by the production method of the present invention can be used in electronic information materials, optical materials, composite materials and the like.

FIG. 1 is a ¹ H-NMR chart (solvent: heavy DMSO) of 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene obtained in Example 1. FIG. 2 is an IR absorption spectrum chart of 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene obtained in Example 1. FIG. 3 is an IR absorption spectrum chart of the polyimide polymer obtained in the reference example.

The details of the present invention will be described below.
The diamine 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene of the present invention is a novel compound, and by using it as a diamine component of a polyimide resin, it has high strength, high elasticity and high adhesion. It is possible to obtain a highly functional polyimide resin having properties, high toughness, heat resistance, and high optical properties. 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene is useful in a wide range of industrial applications such as fine chemicals, medical and agricultural chemical raw materials, resin raw materials, electronic information materials, and optical materials. be.

In the present invention, 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene is produced by subjecting 9-fluorenone to a condensation reaction of 2-methyl-6-ethylaniline.

The 2-methyl-6-ethylaniline used in the condensation reaction is preferably 2.0 to 10 mol times, more preferably 2.0 to 5.0 mol times, the number of moles of 9-fluorenone. It is good. Producing the desired 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene by multiplying 2-methyl-6-ethylaniline by 2.0 mol times or more of 9-fluorenone. Can be done. Further, by reducing the amount of 2-methyl-6-ethylaniline to 10 mol times or less, the labor for removing unreacted 2-methyl-6-ethylaniline from the reaction solution can be reduced.

The condensation reaction of 9-fluorenone and 2-methyl-6-ethylaniline is carried out in the presence of an acid catalyst. As acid catalysts, hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, boric acid, hydrofluoric acid, etc., heteropolyacid protonic acid, boron trifluoride, boron trifluoride-diethyl ether complex, boron trichloride, boron tribromide , Magnesium Chloride, Magnesium Bromide, Aluminum Trichloride, Aluminum Bromide, Zinc Chloride, Tin Chloride (IV), Iron (III) Chloride, Antimon Fluoride (V), Antimon Chloride (V), Phosphorus Trichloride, Phyllochloride Phosphorus, phosphorus oxychloride, titanium tetrachloride, titanium trichloride, vanadyl chloride (VOCl ₂ ), zirconium chloride, hafnium chloride, tetraisopropoxytitanium, scandium trifluoromethanesulfonate (III), niobium trichloride and niobium pentachloride, etc. Organic acids such as Lewis acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, valeric acid, methanesulphonic acid, paratoluenesulphonic acid, trifluoromethanesulfonic acid, and solid acids such as active clay, silica alumina, and zeolite. Is exemplified. The acid catalyst may also be used in the form of a salt of 2-methyl-6-ethylaniline.

The amount of the acid catalyst is preferably 0.1 to 10 mol times, more preferably 0.5 to 3 mol times, the number of moles of 9-fluorenone. By using an acid catalyst 0.5 mol times or more, the condensation reaction can be efficiently promoted. Further, by using an acid catalyst 10 mol times or less, the amount of alkali used for neutralization in a subsequent step can be reduced.

The condensation reaction of 9-fluorenone and 2-methyl-6-ethylaniline is preferably carried out in an aprotic polar solvent having an amide bond and having a boiling point of 170 ° C. or higher. When a solvent other than an aprotic polar solvent having a boiling point of 170 ° C. or higher having an amide bond is used, the condensation reaction does not occur and 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene is not produced. Examples of the aprotic polar solvent having an amide bond having a boiling point of 170 ° C. or higher include N-methylpyrrolidone (boiling point 202 ° C.) and N-ethylpyrrolidone (boiling point 218 ° C.). Among them, the solvent preferably used is N-methylpyrrolidone.

The amount of the aprotic polar solvent used is preferably 1 to 20 times by mass, more preferably 2 to 10 times by mass with respect to the mass of 9-fluorenone. By using an aprotic polar solvent 1 mass times or more, the reaction promoting effect of the solvent is exhibited. Further, by using an aprotic polar solvent 20 times by mass or less, high productivity can be ensured while exhibiting a reaction promoting effect.

In the condensation reaction of 9-fluorenone and 2-methyl-6-ethylaniline, water is by-produced, but it is preferable to remove it while reacting. For this purpose, a method in which an azeotropic solvent is allowed to coexist in the reaction system to continuously remove by-product water is preferably used. Examples of the azeotropic solvent include cyclohexane, methylcyclohexane, benzene, toluene, xylene and the like, and toluene or xylene is preferably used. The amount of this azeotropic solvent used is preferably 0.5 to 10 times by mass with respect to the mass of 9-fluorenone.

The condensation reaction is preferably carried out in an oxygen-free, inert atmosphere. Specifically, this can be done by aerating nitrogen gas, which is substantially free of oxygen, into the reaction system. When performed in the presence of oxygen, 2-methyl-6-ethylaniline is oxidized and colored, which remains in 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene and is colored. It may end up.

The reaction temperature is preferably 80 to 200 ° C. More preferably, it is 120 to 180 ° C. If the reaction temperature is lower than 80 ° C, it will take a long time to complete the reaction, and if it is higher than 200 ° C, 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene will be added to 9-. A dimer reacted with fluorenone is produced, and the yield of 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene is reduced.

The reaction time depends on the reaction temperature, but is preferably 3 to 100 hours, more preferably 5 to 80 hours. At the end of the reaction, 9-fluorenone was completely consumed, and the residual amount of the imine compound in which one molecule of 2-methyl-6-ethyl-4-aniline was condensed with the intermediate 9-fluorenone was analyzed by liquid chromatography of the reaction solution. The time point can be set to be 10 area% or less, more preferably 2.0 area% or less of the total peak area excluding the peak area of aniline.

After completion of the condensation reaction, 9,9-bis (3-methyl-5-ethyl) produced as a method for separating 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene from the reaction solution The acid salt of -4-aminophenyl) fluorene may be once filtered off from the reaction solution by filtration, and this may be neutralized and desalted with an alkali in an organic solvent, or the reaction solution after the reaction is completed may be directly used. It may be neutralized with an alkali to separate the generated organic phase and aqueous phase. In any case, 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene can be obtained from the obtained organic phase.

As the alkali to be used, an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is used, and the salt generated by neutralization can be extracted to the aqueous phase side and removed. Further, the amount of alkali used can be the same equivalent as or more than the acid catalyst used in the condensation reaction.

As a method for isolating 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene from the obtained organic phase, a concentrated crystallization method for concentrating the organic phase or adding a poor solvent to the organic phase is added. The poor solvent crystallization method is preferably used.

In the concentrated crystallization method, an aprotonic polar solvent having an amide bond and having a boiling point of 170 ° C. or higher and / or anilines are distilled off, and 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene is distilled off. , 9,9-Bis (3-methyl-5-ethyl-4-aminophenyl) fluorene can be obtained by concentrated crystallization.

Concentration may be carried out under normal pressure or reduced pressure, but if 2-methyl-6-ethylaniline is to be distilled off at normal pressure, a high temperature condition of 200 ° C. or higher is required, whereby 2-methyl Since -6-ethylaniline is oxidized and colored, and the recovery rate of 2-methyl-6-ethylaniline decreases, it is preferable to carry out the treatment under reduced pressure at a temperature of 150 ° C. or lower. The preferred degree of decompression is 0.13 to 20 kPa.

After concentrated crystallization, the slurry obtained by cooling is solid-liquid separated to obtain 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene. Since the crystallization mother liquor may adhere to the surface of the obtained 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene, the obtained 9,9-bis (3) -Methyl-5-ethyl-4-aminophenyl) Fluolene is thoroughly rinsed and washed, or by reslurry washing with a solvent, high-purity 9,9-bis (3-methyl-5-ethyl-4-) Aminophenyl) Fluolene can be obtained.

As the solvent for the rinse and reslurry, an alcohol solvent, an aromatic hydrocarbon solvent, an ether solvent, an ester solvent or an amide solvent may be used, but an alcohol solvent or an aromatic hydrocarbon solvent is preferable. A solvent is used. The alcohol solvent is methanol, ethanol and isopropyl alcohol, and the aromatic hydrocarbon solvent is toluene and xylene. The reflux may be carried out at room temperature or at a temperature at which the solvent refluxes.

The amount of rinse liquid used is preferably 0.1 to 10 times by mass with respect to 9-fluorenone, and the amount of reslurry liquid used in the reslurry is preferably 1.0 to 30 times by mass with respect to 9-fluorenone. Be done.

In the anti-solvent crystallization method, a solvent containing at least one selected from water, alcohols and lower aliphatic ketones is mixed with the obtained organic phase, and 9,9-bis (3-methyl-5-ethyl) is mixed. By crystallizing -4-aminophenyl) fluorene, 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene is obtained in high yield.

The alcohols used in the antisolvent crystallization method are alcohols having 1 to 6 carbon atoms and / or glycols having 2 to 3 carbon atoms, such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol and. Primary alcohols such as 1-hexanol, secondary alcohols such as isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, and cyclohexanol, tertiary butanol, tertiary pentanol, ethylene Glycols and propylene glycols are mentioned. Methanol, ethanol and isopropanol are preferred.

The lower aliphatic ketones are aliphatic ketones having 3 to 9 carbon atoms, and examples thereof include acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, diisopropyl ketone, dibutyl ketone, and methyl butyl ketone. Acetone, methyl ethyl ketone, and methyl isopropyl ketone are preferred.

In the anti-solvent crystallization method, the amount of the solvent used is preferably 0.5 to 30 times by mass, more preferably 1.0 to 5 times by mass with respect to the mass of 9-fluorenone.

After crystallization, the obtained slurry is solid-liquid separated to obtain 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene in high yield. Since the crystallization mother liquor may adhere to the surface of the obtained 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene, the obtained 9,9-bis (3) -Methyl-5-ethyl-4-aminophenyl) Fluolene is thoroughly rinsed and washed, or by reslurry washing with a solvent, high-purity 9,9-bis (3-methyl-5-ethyl-4-) Aminophenyl) Fluolene can be obtained.

As the solvent for the rinse and reslurry, an alcohol solvent, an aromatic hydrocarbon solvent, an ether solvent, an ester solvent or an amide solvent may be used, but an alcohol solvent or an aromatic hydrocarbon solvent is preferable. A solvent is used. Examples of the alcohol-based solvent include methanol, ethanol and isopropyl alcohol, and examples of the aromatic hydrocarbon-based solvent include toluene and xylene. The reflux may be carried out at room temperature or at a temperature at which the solvent refluxes.

The amount of rinse liquid used is preferably 0.1 to 10 times by mass with respect to the mass of 9-fluorenone, and the amount of reslurry liquid used in the reslurry is 1.0 to 30 mass with respect to the mass of 9-fluorenone. Fluorenone is preferably used.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to Examples. The analytical values of 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene obtained in the present specification were measured by the following method.

(Chemical purity)
9,9-bis (3-methyl-5-ethyl) with respect to the area obtained by subtracting the peak area of aniline from the total peak area measured by liquid chromatography (CLASS-VP manufactured by Shimadzu Corporation) under the following conditions. The fraction of the peak area of -4-aminophenyl) fluorene (HPLC area%) was measured and used as the chemical purity (%).
-Column: YMC-Pack ODS-AM303 4.6φ x 250 mm
-Column temperature: 40 ° C
-Mobile phase: A 0.1% (v / v) aqueous phosphoric acid solution was used as the composition (A) and acetonitrile was used as the composition (B), and the composition was changed according to the composition (A / B) shown in the gradient below.
・ Gradient time (minutes) Composition (A / B)
0 60/40
10 45/55
15 20/80
25 20/80
30 60/40
40 60/40
・ Flow rate: 1 ml / min
・ Injection amount: 10 μl
-Detection: UV 254 nm
-Analysis time: 40 minutes-Analysis sample preparation: Weigh 0.02 g of sample and dilute to about 40 ml of acetonitrile However, as long as the same results as the analysis results based on the above analysis conditions are obtained, the analysis conditions are limited. is not.

(Example 1)
9-Fluorenone 15.0 g (0.083 mol), N-methylpyrrolidone 30.25 g, toluene 30.25 g and 35% hydrochloric acid 17 in a 300 mL four-necked flask equipped with a thermometer, dropping funnel, condenser and stirrer. .37 g (0.166 mol) was charged. The solution was cooled to 15 ° C. or lower under stirring with a nitrogen purge, and 22.51 g (0.166 mol) of 2-methyl-6-ethylaniline was added dropwise. After the heat generation had subsided, the temperature was raised to 90 to 110 ° C., and the water and toluene in the system were azeotropically heated. After the distillation had subsided, 15.0 g of N-methylpyrrolidone was further added, the temperature was raised to 140 ° C., and the mixture was aged with stirring for 20 hours to carry out a condensation reaction.

After the condensation reaction, the reaction solution was cooled to room temperature and the slurry solution was filtered. The filtered cake was rinsed with 15.0 g of isopropanol twice.

Subsequently, the cake obtained in a solution containing 66.0 g of isopropanol, 66.0 g of water, and 13.87 g (0.166 mol) of a 48% caustic soda aqueous solution was added, and the cake was stirred at 60 ° C. for 3 hours to desalinate. bottom. This was cooled to room temperature, the crystals were filtered, and rinsed twice with a mixed solution of 10 g of isopropanol and 10 g of water. The obtained cake was vacuum dried overnight at a temperature of 60 ° C. and a reduced pressure of 0.01 kPa or less, and 28.3 g of 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorenone (yield 79%). / 9-Fluorenone) was acquired. The chemical purity by liquid chromatography analysis was 98.4%.

FIG. 1 shows a ¹ H-NMR chart (solvent: heavy DMSO, 500 MHz) of 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene obtained in Example 1 in FIG. , The IR absorption spectrum chart of 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene obtained in Example 1 is shown.

(Reference example)
In a 200 mL four-necked flask equipped with a thermometer, a cooling tube and a stirrer, 4.33 g of 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene obtained in Example 1, N-methyl. 32.9 g of pyrrolidone was added and heated at 60 ° C. to completely dissolve 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene. 3.10 g of 4,4'-oxydiphthalic acid dianhydride was added thereto in portions. The mixture was aged for 4 hours while still warmed at 60 ° C., cooled to room temperature, and stirred overnight. 20.0 g of ortho-dichlorobenzene was added thereto, and the mixture was heated at 185 to 190 ° C. for 4 hours, and the produced water was azeotropically distilled off together with ortho-dichlorobenzene. This was cooled to obtain about 30 ml of a polyimide solution. N-Methylpyrrolidone was added to this polyimide solution to prepare 80 ml of a uniform solution.

The above solution was added dropwise to a flask of 500 g of methanol to reprecipitate the polymer. After filtering this, the wet cake of the obtained polymer was dissolved again in N-methylpyrrolidone to prepare an 80 ml solution. It was added dropwise to 500 g of methanol again, reprecipitated, and filtered to obtain a wet cake of the polymer. This was dried under reduced pressure overnight at a temperature of 80 ° C. and a reduced pressure of 0.01 kPa or less to obtain 6.35 g of a polymer powder.

The IR spectrum chart of the obtained polyimide polymer powder is shown in FIG.
The viscosity of the 20% by mass N-methylpyrrolidone (NMP) solution of this polyimide polymer powder was 450 mPa · sec (E-type viscometer, 25 ° C.).

Claims (3)

9,9-Bis (3-methyl-5-ethyl-4-aminophenyl) fluorene. In an aprotonic polar solvent having an amide bond and having a boiling point of 170 ° C. or higher, 9-fluorenone and 2-methyl-6-ethylaniline are reacted in the presence of an acid catalyst, 9,9-bis (3-methyl-5-). Ethyl-4-aminophenyl) Fluorenone production method. The method for producing 9,9-bis (3-methyl-5-ethyl-4-aminophenyl) fluorene according to claim 2, wherein the aprotic polar solvent is N-methylpyrrolidone or N-ethylpyrrolidone.

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