JP2015168621A - Diamine compound and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sulfonic acid ester group-containing diamine compound that is white and is resistant to discoloration and an industrial production method thereof.SOLUTION: This invention provides a diamine compound represented by the following formula (1) where R, R, R, and Rindependently represent H, or a CHgroup.

Description

  The present invention relates to an industrially useful diamine compound containing an ester group and a method for producing the same.

  Diamine compounds are widely used in the fields of organic chemistry and polymer chemistry, and are useful in a wide range of industrial applications such as fine chemicals, medical and agricultural chemical raw materials and resin raw materials, and electronic information materials and optical materials. A compound. In recent years, research on materials using diamine compounds having an ester group as a raw material has been actively conducted. For example, a polyimide copolymer having improved solubility in a solvent can be obtained (see Patent Document 1), and has excellent properties such as heat resistance. A polyimide copolymer having high mechanical strength and low linear expansion coefficient and excellent thermal dimensional stability can be obtained (see Patent Document 2). A heat-resistant insulating material having low thermal expansion and low hygroscopic expansion is obtained. Obtained (see Non-Patent Document 1) and the like have been reported. Therefore, the performance required for these diamine compounds has been diversified and advanced, and materials having excellent transparency, for example, diamine compounds containing sulfonic acid ester groups which are white and difficult to color are desired. ing.

  About the diamine compound containing the sulfonic acid ester group, since there are few report examples and it is difficult to obtain a raw material, it was not suitable as an industrial manufacturing method (refer patent document 3).

US Pat. No. 4,317,902 JP-A-7-133349 JP-A-57-193443 Edited by Japan Polyimide / Aromatic Polymers Research Group, “New Revised Polyimide: Basics and Applications”, NTS Publishing Co., Ltd., August 25, 2010, p. 287-304

  An object of the present invention is to provide a diamine compound containing an ester group which is white and difficult to be colored, and an industrial production method in which the raw material is easily available.

  As a result of intensive studies, the present inventors have found a novel white diamine compound that is difficult to be colored and an industrial production method thereof.

  That is, the diamine compound of the present invention is represented by the following formula (1)

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)
It is a diamine compound shown by these.

  The method for producing a diamine compound of the present invention includes 4-acetamidobenzenesulfonic acid chloride represented by the following formula (2),

The compound represented by the following formula (3) was obtained by esterification under a base.

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)
Obtained by deacetylating the compound represented by the following formula (4),

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)
It is a manufacturing method of the diamine compound shown by following formula (1).

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)

  Although the novel diamine compound of the present invention is a diamine compound that can be produced from readily available raw materials, it becomes a white compound due to the introduction of a rigid sulfonic acid ester group in the compound, and is also oxidized by air. Since it becomes difficult and there is no coloring at the time of manufacture, it is promising as a raw material for polyimide, polyamide, epoxy resin and the like that require transparency. In addition, since this compound contains an ester group, it has excellent solubility in a solvent, improved heat resistance, high mechanical strength, low linear expansion, low thermal expansion, low hygroscopic expansion, and the like. It is promising as a raw material for functional polyimide materials such as base film materials for flexible circuit boards, photosensitive heat-resistant polymers, and liquid crystal alignment films.

1 is a hydrogen nuclear magnetic resonance (hereinafter referred to as “ ¹ H-NMR”) spectrum chart of bis [4- (4-aminobenzenesulfonic acid) phenyl] diphenylmethane obtained in Example 1. FIG. 2 is an infrared spectroscopy (hereinafter referred to as “IR”) spectrum chart of bis [4- (4-aminobenzenesulfonic acid) phenyl] diphenylmethane obtained in Example 1. FIG.

  Below, the diamine compound of this invention and the industrial manufacturing method of the diamine compound are described in detail.

  The diamine compound in the present invention is a diamine compound represented by the following formula (1).

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)
Examples of the compound represented by the formula (1) include bis [4- (4-aminobenzenesulfonic acid) phenyl] diphenylmethane, bis [4- (4-aminobenzenesulfonic acid) -3-methylphenyl] diphenylmethane, and bis [4. -(4-aminobenzenesulfonic acid) -3,5-dimethylphenyl] diphenylmethane. The compound represented by the formula (1) is preferably bis [4- (4-aminobenzenesulfonic acid) phenyl] diphenylmethane. Bis [4- (4-aminobenzenesulfonic acid) phenyl] diphenylmethane is preferred because of the availability of raw materials.

  The diamine compound represented by the above formula (1) is a compound that is white and difficult to color. For example, even when stored in an air atmosphere at 40 ° C. for 7 days, there is almost no change in color and no coloring is observed.

  When producing the compound represented by the above formula (1), first, the following formula (2)

4-acetamidobenzenesulfonic acid chloride represented by the following formula (3)

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)
An intermediate compound represented by the following formula (4) of an intermediate can be produced by esterifying the compound represented by formula (1) with a base.

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)
Examples of the compound represented by the formula (3) include bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxy-3-methylphenyl) diphenylmethane, and bis (4-hydroxy-3,5-dimethylphenyl) diphenylmethane. Preferably, it is bis (4-hydroxyphenyl) diphenylmethane from the viewpoint of easy availability of raw materials.

  Examples of the compound represented by the formula (4) include bis [4- (4-acetamidobenzenesulfonic acid) phenyl] diphenylmethane, bis [4- (4-acetamidobenzenesulfonic acid) -3-methylphenyl] diphenylmethane, and bis [4- (4-acetamidobenzenesulfonic acid) -3,5-dimethylphenyl] diphenylmethane. Preferably, it is bis [4- (4-acetamidobenzenesulfonic acid) phenyl] diphenylmethane because of easy availability of raw materials.

  In the esterification reaction, the compound represented by the formula (2) and the compound represented by the formula (3) are reacted in the presence of a base.

  The reaction ratio between the compound represented by the formula (2) and the compound represented by the formula (3) is 0.3% of the compound represented by the formula (3) with respect to 1 mol of the compound represented by the formula (2). It is preferable to use -1.0 mol, More preferably, 0.4-0.6 mol is used. By reducing the amount of the compound represented by the formula (3) to 0.3 mol or more, it is possible to prevent a decrease in yield due to failure to reach the reaction. This is preferable because it reduces the energy for removing the compound represented by) and reduces waste, which is economical.

  Examples of the base preferably used in the esterification reaction include alkali metal hydride, alkaline earth metal hydride, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate. Examples thereof include salts, alkali metal hydrogen carbonates, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal fluorides, and amines.

  Examples of the alkali metal hydride include lithium hydride, sodium hydride, potassium hydride and the like.

  Examples of the alkaline earth metal hydride include beryllium hydride, magnesium hydride, calcium hydride and the like.

  Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.

  Examples of the alkaline earth metal hydroxide include beryllium hydroxide, magnesium hydroxide, calcium hydroxide and the like.

  Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate and the like.

  Examples of the alkaline earth metal carbonate include beryllium carbonate, magnesium carbonate, and calcium carbonate.

  Examples of the alkali metal hydrogen carbonate include sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate and the like.

  Examples of the alkali metal alkoxide include sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide and the like.

  Examples of the alkaline earth metal alkoxide include magnesium diethoxide and magnesium dimethoxide.

  Examples of the alkali metal fluoride include sodium fluoride, potassium fluoride, cesium fluoride and the like.

  As amines, tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, dimethylbenzylamine, N, N, N ′, N′-tetramethyl-1,8-naphthalenediamine, pyridine, pyrrole , Heteroaromatic amines such as uracil, collidine and lutidine, 1,8-diaza-bicyclo [5.4.0] -7-undecene, 1,5-diaza-bicyclo [4.3.0] -5-nonene And cyclic amidines.

  These bases may be used alone or in combination of two or more. Of these bases, triethylamine and pyridine are particularly preferable because they are liquid and easy to handle, and are easy to remove because of their low boiling point.

  The amount of the base used is preferably 1.0 to 3.0 mol times, more preferably 1.0 to 1.5 mol times the compound represented by the formula (2). By reducing the amount of the base to 1.0 mol times or more, it is possible to prevent a decrease in yield due to failure to achieve the reaction. Since it decreases, it is preferable.

  As a solvent preferably used in the esterification reaction, for example, a sulfoxide compound, a sulfolane compound, an amide compound, a nitrile compound, an ether compound, a hydrocarbon compound, a ketone compound, an ester compound and the like can be preferably used.

  Examples of the sulfoxide compound include dimethyl sulfoxide and diethyl sulfoxide.

  Examples of the sulfolane compound include sulfolane and methyl sulfolane.

  Examples of amide compounds include N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, 1,3-dimethyl. -2-imidazolinodin etc. are mentioned.

  Examples of nitrile compounds include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like.

  Examples of ether compounds include monoglyme, diglyme, triglyme, tetraglyme, diethyl ether, diisopropyl ether, di-n-butyl ether, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran (THF), tetrahydropyran, 1,4-dioxane, 1,3-dioxolane, anisole, morpholine and the like can be mentioned.

  Examples of the hydrocarbon compound include toluene, xylene, mesitylene, n-hexane, n-heptane, cyclohexane, methylcyclohexane, and the like.

  Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and isophorone.

Examples of ester compounds include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, acetic acid. Cyclohexyl, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, γ-butyrolactone, etc.
Among these, acetonitrile, tetrahydrofuran, toluene, acetone, and ethyl acetate are preferable because of their low boiling point and easy removal.

  An esterification solvent may be used independently and may be used in mixture of 2 or more types.

  The usage-amount of an esterification solvent is the range of 0.1-20 weight times normally with respect to the compound shown by Formula (2).

  The esterification reaction is preferably carried out in a nitrogen atmosphere. By carrying out in a nitrogen atmosphere, purity deterioration can be suppressed by preventing oxygen from entering the system.

  The reaction temperature for the esterification reaction is usually preferably 0 to 150 ° C, more preferably 0 to 70 ° C. When the temperature is 0 ° C. or higher, the reaction proceeds rapidly, and when the temperature is 150 ° C. or lower, side reactions can be suppressed and yield reduction can be prevented.

  The reaction time of the esterification reaction is usually in the range of 0.5 to 20 hours.

  After completion of the esterification reaction, crystals are precipitated by adding a crystallization solvent to the reaction mixture, and an intermediate compound is obtained by isolating the crystals. The obtained intermediate may be recrystallized.

  As a crystallization solvent preferably used in the esterification reaction, for example, water, an alcohol compound, or the like can be suitably used.

  Examples of alcohol compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, methoxyethanol, ethoxyethanol, and 1-methoxy-2-propanol. Can be mentioned.

  These crystallization solvents may be used alone or in combination of two or more. Of these crystallization solvents, water, methanol, ethanol, and 2-propanol are particularly preferable because they are available at low cost.

  Moreover, you may use for the following process, without isolating an intermediate body after completion | finish of esterification reaction.

  Next, a diamine compound represented by the following formula (1) can be produced by deacetylating the intermediate compound of the formula (4) obtained above.

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)
As a deacetylation method, deacetylation using an acid is most preferable. By using an acid, hydrolysis of the sulfonic acid ester group is suppressed, and the target product can be obtained in high yield.

  Examples of the acid preferably used for deacetylation include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, boric acid, and fluorinated boronic acid.

  These acids may be used alone or in combination of two or more. Of these acids, hydrochloric acid and sulfuric acid are particularly preferred from the viewpoint of easy post-treatment.

  The amount of the acid used is preferably 1.0 to 20.0 mole times, more preferably 2.0 to 10.0 mole times the amount of the compound represented by formula (4). By reducing the amount of the base to 2.0 mol times or more, a decrease in yield due to unreachable reaction can be prevented, and by setting the amount to 10.0 mol times or less, energy required for acid removal is reduced, and waste is also reduced. Since it decreases, it is preferable.

  As a solvent preferably used for the deacetylation reaction, for example, an alcohol compound, an ether compound, a hydrocarbon compound, a nitrile compound, or the like can be suitably used.

  Examples of alcohol compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, methoxyethanol, ethoxyethanol, and 1-methoxy-2-propanol. Can be mentioned.

  Examples of the ether compound include glyme, diglyme, tetrahydrofuran, dioxane and the like.

  Examples of the hydrocarbon compound include toluene, xylene, mesitylene, hexane, cyclohexane, heptane, methylcyclohexane and the like.

  Examples of nitrile compounds include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like.

  Among these, tetrahydrofuran, 2-propanol, and toluene are preferable because of their low boiling point and easy removal.

  The solvent for the deacetylation reaction may be used alone or in combination of two or more.

  The amount of solvent used is usually in the range of 0.1 to 20 times the weight of the compound represented by the formula (4).

  The deacetylation reaction is preferably performed in a nitrogen atmosphere. By carrying out in a nitrogen atmosphere, purity deterioration can be suppressed by preventing oxygen from entering the system.

  The reaction temperature for deacetylation is usually preferably 0 to 150 ° C, more preferably 50 to 120 ° C. When the temperature is 50 ° C. or higher, the reaction proceeds rapidly, and when the temperature is 120 ° C. or lower, side reactions can be suppressed and yield reduction can be prevented.

  The reaction time of the deacetylation reaction is usually in the range of 0.5 to 20 hours.

  After the deacetylation reaction, the reaction solution is neutralized, and then a crystal is precipitated by adding a crystallization solvent to the neutralization solution. By isolating this, the diamine compound represented by the formula (1) is obtained. can get. The obtained compound may be recrystallized.

  As a crystallization solvent preferably used for the deacetylation reaction, for example, water, alcohol compounds, hydrocarbon compounds and the like can be suitably used.

  Examples of alcohol compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, methoxyethanol, ethoxyethanol, 1-methoxy-2-propanol, and the like. Is mentioned.

  Examples of the hydrocarbon compound include toluene, xylene, mesitylene, n-hexane, n-heptane, cyclohexane, methylcyclohexane, and the like.

  These crystallization solvents may be used alone or in combination of two or more. Of these crystallization solvents, water, methanol, ethanol, 2-propanol, and toluene are particularly preferable for improving the purity of the present compound.

  The diamine compound represented by the formula (1) obtained as described above is a white compound despite the fact that it is a diamine compound by introducing a rigid sulfonic acid ester group into the compound, and is based on air. Less susceptible to oxidation and no coloration during manufacturing. Moreover, coloring at the time of storage can be suppressed.

  This diamine compound is promising as a raw material for polyimide, polyamide, epoxy resin, and the like that require transparency. In addition, since it contains an ester group, it has excellent functionality such as improved solubility in solvents, improved heat resistance, high mechanical strength, low linear expansion, low thermal expansion, and low hygroscopic expansion. It is promising as a raw material for polyimide raw materials, such as base film materials for flexible circuit boards, photosensitive heat-resistant polymers, and liquid crystal alignment films.

  Hereinafter, specific examples will be described.

In Example 1, the content of bis [4- (4-aminobenzenesulfonic acid) phenyl] diphenylmethane in the diamine compound, that is, the chemical purity of bis [4- (4-aminobenzenesulfonic acid) phenyl] diphenylmethane is high speed. This is a liquid chromatography method (hereinafter abbreviated as “HPLC”) analyzed under the following analysis conditions (HPLC area%).
Column: YMC-Pack ODS-AM303 4.6φ × 250mm
-Column temperature: 40 ° C
・ Mobile phase:
A: 0.05% (v / v) phosphoric acid aqueous solution B: Acetonitrile (gradient) 0 min. A: B = 50: 50
5 min. A: B = 50: 50
30 min. A: B = 10: 90
・ Flow rate: 1 ml / min
・ Injection volume: 0.5 μl
・ Detection: Ultraviolet (UV) detection, wavelength 254nm
Analysis time: 30 minutes Preparation of analysis sample: 0.05 g of sample was weighed and dissolved in 25 ml of acetonitrile.

  The chemical purity of the intermediate bis [4- (4-acetamidobenzenesulfonic acid) phenyl] diphenylmethane was also analyzed under the HPLC analysis conditions.

Example 1
In a 200 ml four-necked flask equipped with a thermometer, condenser and stirrer, 10.0 g (0.028 mol) of bis (4-hydroxyphenyl) diphenylmethane, 14.4 g (0.062 mol) of 4-acetamidobenzenesulfonic acid chloride Then, 70 g of tetrahydrofuran was charged, and the system was purged with nitrogen. To this, 6.2 g (0.062 mol) of triethylamine was added dropwise at around 30 ° C. This mixture was stirred at 50 ° C. for 4 hours to carry out an esterification reaction. After the reaction was completed, water was added, followed by extraction and liquid separation. Bis [4- (4-acetamidobenzenesulfonic acid) phenyl] diphenylmethane in the obtained organic layer had an HPLC purity of 99.2%.

  To the obtained organic layer, 21.9 g (0.210 mol) of 35% hydrochloric acid was added, followed by stirring at 65 ° C. for 5 hours for deacetylation reaction. After the completion of the reaction, 12.8 g (0.210 mol) of 28% aqueous ammonia was added to neutralize, followed by extraction and liquid separation. The diamine compound in the obtained organic layer had an HPLC purity of 95.8%. The hydrolysis of the sulfonic acid ester group at the time of deacetylation was 0.2%.

  The obtained organic layer was concentrated, 30 g of methanol was added and cooled to 5 ° C., and 10 g of water was added dropwise. The precipitated crystals were filtered and dried to obtain 16.4 g of a white crystalline diamine compound. The obtained diamine compound had an HPLC purity of 97.1% and a yield of 87.1%.

FIG. 1 shows a hydrogen nuclear magnetic resonance ( ¹ H-NMR) spectrum chart of the diamine compound obtained in Example 1, and FIG. 2 shows an infrared (IR) absorption spectrum chart. ¹ H-NMR was performed under the measurement conditions described in the figure.

  Based on the above results, the obtained diamine compound was identified as bis [4- (4-aminobenzenesulfonic acid) phenyl] diphenylmethane.

(Reference Example 1)
In Example 1, except that 25.0 g (0.300 mol) of a 48% aqueous sodium hydroxide solution was used instead of 35% hydrochloric acid during the deacetylation reaction, and the reaction was performed at 70 ° C. for 5 hours, Example 1 When carried out in the same manner, hydrolysis of the sulfonate group at the time of deacetylation was 99% or more, and the HPLC purity of the target product was 1% or less, and the target product was hardly obtained.

(Reference Example 2)
When the diamine compound obtained in Example 1 was stored at 40 ° C. for 7 days in an air atmosphere, there was almost no change in color and no coloring was observed. For comparison, when 4,4′-diaminodiphenyl ether was stored under the same conditions, the color changed from an initial ocher color to a light brown color after 7 days of storage, and coloring was observed.

Claims (3)

A diamine compound represented by the following formula (1).

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.) 4-acetamidobenzenesulfonic acid chloride represented by the following formula (2);

Obtained by reacting a compound represented by the following formula (3) with a base,

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)
Obtained by deacetylating an intermediate represented by the following formula (4),

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.)
The manufacturing method of the diamine compound shown by following formula (1).

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent H or CH ₃ group.) The manufacturing method of the diamine compound of Claim 2 which deacetylates the intermediate body of the said Formula (4) using an inorganic acid.

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