Compounds and their manufacturing methods, polyimide compounds and molded articles

Abstract

The purpose of this invention is to provide a novel meta-esterified aromatic diamine, a method for its preparation, and a polyimide synthesis. A compound is represented by the following formula (1): In equation (1), X is one of (a), (b), (c), or (d) below. In formula (1), R1, R2, R3, and R4, and in (a), (b), (c), and (d), R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20, are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms, wherein at least one of R7, R8, R9, and R10 is said alkyl or alkoxy group.

Description

[Technical Field]

[0001] This invention relates to a meta-ester aromatic diamine and its derivatives that can be effectively used as raw materials for high-functionality polymers, primarily polyimide, and various organic compounds, as well as a method for their manufacture. [Previous Technology]

[0002] Regarding printed circuit boards and the like used in the information and communication field, high-speed, high-capacity communication is required, therefore, it is expected to be used in higher frequency bands than before. However, there is a problem of increased transmission loss due to higher frequencies. Transmission loss is divided into the effects of resistive loss and dielectric loss. Among them, resistive loss has the characteristic of becoming heat proportional to frequency, while dielectric loss has the characteristics of being proportional to frequency, dielectric loss tangent, and relative permittivity.

[0003] For materials suitable for use in high-frequency bands, in addition to heat resistance, excellent electrical properties are also required, particularly low dielectric constant and low dielectric loss tangent. Polyimide (PI) or polyamine resins (Non-Patent Literature 1, Non-Patent Literature 2) are known as excellent heat-resistant materials. However, these resins have highly polar amide or amide groups within their molecules, and due to these effects, the dielectric constant (k) of many PIs typically exceeds 3.0. Polyester imide (PEI) is another known PI material with excellent electrical properties (Non-Patent Literature 3). However, it suffers from problems such as lack of thermoplasticity, poor melt flowability, lack of solvent solubility, and deteriorated processability. [Prior Art Documents] [Non-Patent Literature]

[0004] [Non-Patent Literature 1] Pathrick RA et al., Journal of Applied Polymer Science, vol. 132, pp. 41684-41692, 2015. [Non-Patent Literature 2] Akhter Z. et al., Polymer Bulletin, vol. 74, pp. 3889-3906, 2017. [Non-Patent Literature 3] Masatoshi Hasegawa et al., Polymers, vol. 12, pp. 859, 2020. [Non-Patent Literature 4] S. Tamai et al., Polymers, vol. 37, pp. 3683-3692, 1996. [Summary of the Invention]

[0005] [The problem the invention aims to solve]

[0006] As a material with excellent high heat resistance and electrical properties, the reduction of dielectric constant in polyimide (PI) has been proposed. Due to the design diversity of its monomers, i.e., diamines, PI is an attractive material for molecular design aimed at reducing dielectric constant. A fundamental consideration in reducing the dielectric constant of PI is how to dilute (reduce) the concentration of amide groups, which influences the high dielectric constant. To reduce the concentration of amide groups in PI, it is effective to use diamines with three or more aromatic rings instead of dinuclear forms such as oxydianiline, a representative aromatic diamine. Furthermore, introducing an ester group into the PI backbone is effective in reducing the hygroscopicity of PI and reducing its dielectric constant (Non-Patent Document 3). However, in the aromatic diamines described in Non-Patent Document 3, the linearity of the PI backbone increases, which correspondingly impairs the processability of the PI resin. To improve the processability of PI, it is effective to use meta-aromatic diamines as raw materials (Non-Patent Document 4), but this does not help in reducing the dielectric constant of PI.

[0007] Therefore, in order to simultaneously achieve excellent high heat resistance, electrical properties, and processability, it is effective to use meta-ether aromatic diamines as raw materials for PI. However, to produce meta-ether aromatic diamine precursors, stringent reaction conditions of 145°C-150°C / 5 hours, and further 170°C-180°C / 18 hours are required (Non-Patent Document 4). On the other hand, ester-based aromatic diamine precursors can be synthesized under mild reaction conditions of room temperature / 12 hours. In view of the above, the object of the present invention is to provide a meta-ester aromatic diamine compound and its derivatives that can be easily manufactured and can be effectively used as a resin raw material for polyimide resins, etc., as well as an intermediate or raw material for electronic materials or the like. [Means for Solving the Problem]

[0008] The inventors have made efforts to study the problems of aromatic diamines as described above, and as a result, they have produced a novel meta-ester aromatic diamine and a penta-ester aromatic diamine by producing a bis(3-aminobenzoyloxy) compound having a 3-aminobenzoyloxy group and being trinuclear or tetranuclear.

[0009] That is, the present invention provides a compound represented by the following formula (1) and a method for manufacturing the same. [Chemical 1] In formula (1), X is (a), (b), or (c) below. [Chemical 2][Chemical 3][Chemical 4] R1, R2, R3, and R4 in formula (1), and R5, R6, R7, R8, R9, and R10 in (a), (b), and (c) are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms, wherein at least one of R7, R8, R9, and R10 is said alkyl or alkoxy group.

[0010] In addition, the present invention provides a compound represented by the following formula (1') and a method for manufacturing the same. [Chemical 5] In formula (1'), X is as follows (d), [Chemical 6] R1, R2, R3, R4, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms.

[0011] Furthermore, the present invention provides a polyimide compound as a reaction product of the said diamine compound with an acid anhydride and any other diamine compound. [Effects of the Invention]

[0012] The meta-ester aromatic diamine of the present invention exhibits excellent solubility in various solvents. Furthermore, since the meta-ester aromatic diamine of the present invention has a trinuclear or more aromatic ring, the amide concentration of the obtained polyamide can be reduced, and since it has an ester moiety, the hygroscopicity of the obtained polyamide can be reduced. Therefore, it is effective for reducing the dielectric constant of polyamide. Moreover, the meta-ester aromatic diamine of the present invention is preferably used as a polyamide raw material with high processability.

Implementation Method

[0014] One aspect of the present invention relates to a meta-ester aromatic diamine represented by the following formula (1). [Chemical 7] In formula (1), X is (a), (b), or (c) below, [Chemical 8][Chemical 9][Chemical 10] R1, R2, R3, and R4 in formula (1), and R5, R6, R7, R8, R9, and R10 in (a), (b), and (c) are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms, wherein at least one of R7, R8, R9, and R10 is said alkyl or alkoxy group.

[0015] Another aspect of the present invention relates to a meta-ester aromatic diamine represented by the following formula (1'). [Chemical 11] In formula (1'), X is as follows (d), [Chemical 12] R1, R2, R3, R4, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms.

[0016] The substituted alkyl groups having 1 to 6 carbon atoms, represented by R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20, include, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, cyclopentyl, hexyl, and cyclohexyl. The alkoxy groups having 1 to 3 carbon atoms include: methoxy, ethoxy, and propoxy. R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20 may be different from or the same as each other. Preferably, the atoms are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms. More preferably, in (a), (b), and (d), R1, R2, R3, R4, R5, R6, R11, R12, R13, R14, R15, R16, R17, and R18 may all be hydrogen atoms. In (c), R1, R2, R3, and R4 are preferably hydrogen atoms, and at least one of R7, R8, R9, and R10 is preferably a methyl group.

[0017] Preferably, it is a tetranuclear compound represented by formula (1a) or (1b) below, or a trinuclear compound represented by formula (1c) below. [Chemical 13][Chemical 14] In formulas (1a) and (1b), R1, R2, R3, R4, R5 and R6 are as described above, and preferably hydrogen atoms. [Chemical 15] In formula (1c), R1, R2, R3 and R4 are as described above, and preferably hydrogen atoms, R7, R8, R9 and R10 are as described above, and at least one of them is a methyl group.

[0018] Furthermore, as stated in formula (d), it is preferably represented by the following formula (1d). [Chemical 16] In formula (1d), R1, R2, R3, R4, R11, R12, R13, R14, R15, R16, R17 and R18 are as described above, and preferably hydrogen atoms. R19 and R20 are as described above, and preferably methyl groups.

[0019] In formula (d), the bonding positions of the substituents and aromatic rings are not particularly limited. Preferably, X is a compound having the following structure. [Chemical 17][Chemical 18] R1, R2, R3, R4, R11, R12, R13, R14, R15, R16, R17, and R18 are as described above, and preferably hydrogen atoms. R19 and R20 are as described above, and preferably methyl groups. The asterisk (*) indicates a bond with an oxygen atom.

[0020] The compounds of the present invention are preferably the following compounds. [Chemical 19][Chemical 20][Chemical 21][Chemical 22][Chemical 23][Chemical 24]

[0021] The compound represented by formula (1) can be readily obtained by reducing the two nitro groups of the compound represented by formula (3) below. [Chemical 25] (where R1, R2, R3, R4 and X are as described above)

[0022] The manufacturing method will be described in more detail below.

[0023] The reduction reaction of the nitro group is not particularly limited, and known methods for reducing the nitro group to an amino group can be used. For example, methods for reducing aromatic dinitro compounds include: contact reduction, Bechamp reduction, zinc powder reduction, tin chloride reduction, and hydrazine reduction.

[0024] Solvents that can be used in the reduction reaction include, for example, alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-methoxyethanol, and 2-ethoxyethanol; acetamide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and N,N'-dimethylimidazolidineone; and ether solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol. However, the solvent is not limited to these, as long as it is a solvent that dissolves aromatic dinitro compounds. The amount of solvent can be adjusted appropriately.

[0025] The catalyst used in the reduction reaction may be any catalyst known to be used in the aforementioned reduction reactions. Examples of catalysts that may be used in contact reduction or hydrazine reduction include: palladium, platinum, rhodium, and other noble metal catalysts supported on activated carbon, carbon black, graphite, alumina, etc.; Raney nickel catalysts; and sponge nickel catalysts. There is no particular limitation on the amount of catalyst, but it is typically 0.1 wt% to 10 wt% relative to the aromatic dinitro compound.

[0026] The reaction temperature and time of the reduction reaction can be appropriately selected. For example, the reaction can be carried out at a temperature in the range of 50°C to 150°C, preferably in the range of 60°C to 130°C, for 1 hour to 35 hours, preferably 3 hours to 10 hours. There are no particular limitations on the treatment of the reaction products. For example, the compound represented by the general formula (1) can be obtained by filtering, washing with water, and drying the solid generated after removing the catalyst and cooling. In addition, if further purification is carried out as needed by methods such as crystallization filtration and column separation, a high-purity product can be obtained.

[0027] The compound represented by formula (3) is preferably represented by the following formula. [Chemical 26][Chemical 27][Chemical 28][Chemical 29][Chemical 30][Chemical 31]

[0028] The compound represented by formula (3) can be manufactured by known methods. For example, it can be manufactured by the condensation of the corresponding diol compound with m-nitrobenzoic acid chloride.

[0029] The meta-ester aromatic diamine represented by formula (1) has excellent solubility in various solvents and can be effectively used as a raw material for polyimide. For example, polyimide compounds can be provided by reacting the meta-ester aromatic diamine represented by formula (1) with an acid anhydride.

[0030] The acid anhydride may be a conventionally known acid anhydride that can be used as a raw material for polyimide. For example, it may be at least one acid dianhydride selected from the group consisting of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, benzophenone-3,4,3',4'-tetracarboxylic acid dianhydride, 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 3,3',4,4'-diphenyltetracarboxylic acid dianhydride and oxy-4,4'-diphthalic acid dianhydride.

[0031] There are no particular limitations on the reaction conditions or reaction ratio between the diamine compound and the acid anhydride; they can be appropriately selected according to conventionally known methods. For example, regarding reaction conditions, the reaction can be carried out at a temperature in the range of 25°C to 30°C for 0.5 hours to 24 hours. The reaction ratio can be set to 1.00. The obtained polyimide compound preferably has a number average molecular weight of 2,000 to 200,000, more preferably 10,000 to 50,000. This number average molecular weight is, for example, a value determined by gel permeation chromatography (GPC, tetrahydrofuran, THF).

[0032] As the polyimide compound, any diamine compound other than the diamine compound of the present invention may also be reacted. In the polyimide compound, the proportion of units derived from the diamine compound of the present invention is preferably 10 mol% to 100 mol% relative to the total mol% of units derived from all diamine compounds. Any diamine compound other than the diamine compound of the present invention, such as those selected from 1,4-phenylenediamine, 1,3-phenylenediamine, 1,2-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4 ...3,3'-diamino One or more of the group consisting of aminodiphenyl sulfide, 4,4'-diaminobenzylaniline, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]fluorene, bis[4-(4-aminophenoxy)phenyl]fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9'-bis(4-aminophenoxy)fluorene, and 9,9'-bis[4-(4-aminophenoxy)phenyl]fluorene.

[0033] Examples of molded articles comprising the polyimide compound of the present invention include materials for high-speed, high-capacity communications. [Examples]

[0034] Hereinafter, examples are shown to illustrate the present invention in more detail, but the present invention is not limited to the following examples. The determination methods and apparatus used in the following examples are as follows. For high performance liquid chromatography (HPLC) determination, Shimadzu SPD-20A was used, and for melting point determination, Yamato MP-21 was used. For 1H nuclear magnetic resonance spectroscopy analysis, Avance III HD 400 (Bruker Biospin) was used, and deuterated dimethyl sulfoxide (DMSO) was used as the determination solvent. For 13C nuclear magnetic resonance spectroscopy analysis, Avance III HD 400 (Bruker Biospin) was used, and deuterated DMSO was used as the determination solvent. For infrared spectroscopy determination, an FT / IR-4700 manufactured by Nippon Spectrophotometer was used, and determination was performed by attenuated total reflection (ATR) method. Xevo g2-XS QTof manufactured by Waters was used in precision quality analysis.

[0035] [Example 1] Synthesis of 2,2'-bis[4-(3-nitrobenzoyloxy)phenyl]hexafluoropropane [Chemical 32] 25.2 g (75 mmol) of bisphenol AF, 200 mL of tetrahydrofuran (THF), and 16.0 g (158 mmol) of triethylamine were added to a 300 mL four-necked flask equipped with a mechanical stirrer and a thermometer and allowed to dissolve at room temperature (pale yellow transparent solution). Upon addition of 25.0 g (158 mmol) of m-nitrobenzoyl chloride (MNBC), a white precipitate was immediately formed. The internal temperature was raised from 25°C to 55°C and then cooled shortly afterward. The mixture was stirred at room temperature for 1 hour under these conditions, and the disappearance of MNBC was confirmed by HPLC. The triethylamine hydrochloride was separated by filtration at room temperature, and the solvent was removed by distillation using an evaporator. The obtained white solid was washed with 300 mL of ion-exchanged water and filtered. The filter cake was then heated and dissolved in 260 mL of acetonitrile. After slow cooling to 5°C, the mixture was filtered and dried to obtain 36.0 g / yield of white needle-like crystals with a melting point (mp) of 195.2°C-196.5°C and an HPLC purity of 98.7%. This product is 2,2'-bis[4-(3-nitrobenzoyloxy)phenyl]hexafluoropropane (hereinafter referred to as dinitropropane 1), represented by formula (a). Time-of-flight mass spectrometry (TOF-MS) (electrospray ionization (ESI)): 633.073 (M) -

[0036] [Example 2] Synthesis of 2,2'-bis[4-(3-aminobenzoyloxy)phenyl]hexafluoropropane [Chemical 33] 22.5 g (35 mmol / purity conversion) of the dinitro group 1 obtained in Example 1, 0.261 g of 5% Pd / C (0.113 g as dry), and 150 mL of THF were added to a 300 mL stainless steel (SUS) autoclave and sealed. Nitrogen purging and hydrogen purging were repeated four times, and soapy water was used to confirm no gas leakage. The temperature was raised to 50°C under a constant hydrogen pressure of 0.8 MPa and stirring at 150 rpm. The stirring speed was increased to 1000 rpm, and the hydrogen inlet valve was opened. While maintaining an internal temperature of 60°C-65°C, the theoretical amount of hydrogen was absorbed over 38 minutes, followed by aging for 10 minutes, confirming that the internal pressure did not decrease. After nitrogen purging, the autoclave was opened, and the used catalyst was hot-filtered. The solvent was removed by distillation from the hydrogenation mother liquor using an evaporator, and the resulting white solid was dissolved in 150 mL of isopropanol by heating. 0.4 g of activated carbon was added, and the mixture was stirred under reflux for 30 minutes. The activated carbon was filtered and separated, and 90 mL of deionized water was added. The resulting precipitate was dissolved by heating, slowly cooled to 5°C, filtered, and dried to obtain a product of 18.5 g / yield of pale yellow needle-like crystals, mp 159.6°C-160.5°C, and HPLC purity of 99.6%. The product was analyzed by 1H-NMR and 13C-NMR. The results are shown in Figures 1-4. The product is 2,2'-bis[4-(3-aminobenzoyloxy)phenyl]hexafluoropropane as represented by formula (b). TOF-MS (ESI): 575.1414(M+H)+

[0037] [Example 3] Synthesis of bis[4-(3-nitrobenzoyloxy)phenyl] benzo[Chemical 34] 12.8 g (51 mmol) of bisphenol S, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added to a 300 mL four-necked flask equipped with a mechanical stirrer and a thermometer, and the temperature was raised to 50°C (white slurry). After adding 25.0 g (158 mmol) of m-nitrobenzoyl chloride (MNBC), the internal temperature immediately rose from 50°C to 70°C, and then cooled shortly afterward. The mixture was stirred at 60°C for 1 hour. The white precipitate was filtered off at 50°C, and the filter cake was washed with methanol. The product was air-dried to obtain a white powder of 27.3 g / yield 95%, mp 252°C-253°C, and HPLC purity 98%. The product is bis[4-(3-nitrobenzoyloxy)phenyl] ion (hereinafter referred to as dinitro 2) as represented by formula (c).

[0038] [Example 4] Synthesis of bis[4-(3-aminobenzoyloxy)phenyl] benzo[Chemical 35] 22.5 g (35 mmol / purity conversion) of the dinitro group 2 obtained in Example 3, 0.261 g of 5% Pd / C (0.113 g as dry), and 150 mL of THF were added to a 300 mL SUS autoclave and sealed. Nitrogen purging and hydrogen purging were repeated four times, and soapy water was used to confirm no gas leakage. The temperature was raised to 50°C under a constant hydrogen pressure of 0.8 MPa and stirring at 150 rpm. The stirring speed was increased to 1000 rpm, and the hydrogen inlet valve was opened. While maintaining an internal temperature of 60°C-65°C, the theoretical amount of hydrogen was absorbed over 85 minutes, followed by aging for 20 minutes, confirming that the internal pressure did not decrease. After nitrogen purging, the autoclave was opened. Since diamine had precipitated, the solvent was directly removed from the hydrogenation mother liquor by distillation using an evaporator, and then dissolved in 350 mL of acetonitrile. 0.4 g of activated carbon was added, and the mixture was stirred under reflux for 30 minutes. The activated carbon was filtered and separated, and 40 mL of deionized water was added. The resulting precipitate was dissolved by heating, slowly cooled to 5°C, filtered, and dried to obtain a pale yellow crystalline powder of 14.5 g / yield (74%), mp 235°C-236°C, and HPLC purity of 94%. The structure of the product was analyzed by 1H-NMR and 13C-NMR. The results are shown in Figures 5-8. The product is bis[4-(3-aminobenzoyloxy)phenyl] phosphate represented by formula (d). TOF-MS (ESI): 489.1106 (M+H)+

[0039] [Example 5] Synthesis of 1-methyl-2,5-bis(3-nitrobenzyloxy)benzene [Chemical 36] 9.3 g (75 mmol) of methylhydroquinone, 200 mL of THF, and 16.0 g (158 mmol) of triethylamine were added to a 300 mL four-necked flask equipped with a mechanical stirrer and a thermometer and allowed to dissolve at room temperature (colorless and transparent solution). Upon addition of 25.0 g (158 mmol) of m-nitrobenzyl chloride (MNBC), a white precipitate was immediately formed. The internal temperature rose from 25°C to 58°C and then cooled shortly afterward. The mixture was stirred at room temperature for 1 hour, and the disappearance of MNBC was confirmed by HPLC. The white precipitate was collected at room temperature and washed with THF. The slurry was washed with 400 mL of deionized water at 60°C for 30 minutes. The mixture was then filtered at 60°C, and the filter cake was washed with methanol. The product was air-dried to obtain a white powder of 24.6 g / yield 78%, mp 198.0℃-199.2℃, and HPLC purity 99.3%. The product is 1-methyl-2,5-bis(3-nitrobenzoyloxy)benzene (hereinafter referred to as dinitro 3) as represented by formula (e).

[0040] [Example 6] Synthesis of 1-methyl-2,5-bis(3-aminobenzoyloxy)benzene [Chemical 37] 22.5 g (35 mmol / purity conversion) of the dinitro group 3 obtained in Example 5, 0.261 g of 5% Pd / C (0.113 g as dry), and 150 mL of THF were added to a 300 mL SUS autoclave and sealed. Nitrogen purging and hydrogen purging were repeated four times, and soapy water was used to confirm no gas leakage. The temperature was raised to 50°C under a constant hydrogen pressure of 0.8 MPa and stirring at 150 rpm. The stirring speed was increased to 1000 rpm, and the hydrogen inlet valve was opened. While maintaining an internal temperature of 60°C-65°C, the theoretical amount of hydrogen was absorbed over 30 minutes, followed by aging for 10 minutes, confirming that the internal pressure did not decrease. After nitrogen purging, the autoclave was opened, and the used catalyst was hot-filtered. The solvent was removed by distillation from the hydrogenation mother liquor using an evaporator. The resulting white solid was dissolved in 500 mL of isopropanol by heating. 0.4 g of activated carbon was added, and the mixture was stirred under reflux for 30 minutes. The activated carbon was filtered and separated, and 500 mL of deionized water was added. The resulting precipitate was dissolved by heating, slowly cooled to 5°C, filtered, and dried to obtain a product with 11.7 g / yield of pale yellow crystalline powder, mp 148°C-150°C, and HPLC purity of 96%. The product was structurally analyzed by 1H-NMR and 13C-NMR. The results are shown in Figures 9-12. The product is 1-methyl-2,5-bis(3-aminobenzoyloxy)benzene as represented by formula (f). TOF-MS (ESI): 363.1336(M+H)+

[0041] [Example 7] Synthesis of 1,2,4-trimethyl-3,6-bis(3-nitrobenzyloxy)benzene [Chemical 38] 11.4 g (75 mmol) of trimethylhydroquinone, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added to a 300 mL four-necked flask equipped with a mechanical stirrer and a thermometer, and allowed to dissolve at room temperature (colorless and transparent solution). Upon addition of 25.0 g (158 mmol) of m-nitrobenzyl chloride (MNBC), a pale yellow precipitate was immediately formed. The viscosity increased as the internal temperature rose from 18°C ​​to 57°C. After heating to 70°C, the viscosity gradually decreased. After 2 hours, the mixture was cooled to 25°C, and the white precipitate was filtered off. The filter cake was washed with methanol. The product was air-dried to obtain a white powder with a yield of 27.3 g / yield of 81%, an mp value of 226.0℃-226.8℃, and an HPLC purity of 99.9%. The product is 1,2,4-trimethyl-3,6-bis(3-nitrobenzoyloxy)benzene (hereinafter referred to as dinitro 4) as represented by the formula (g).

[0042] [Example 8] Synthesis of 1,2,4-trimethyl-3,6-bis(3-aminobenzoyloxy)benzene [Chemical 39] 22.5 g (35 mmol / purity conversion) of the dinitro group 4 obtained in Example 7, 0.261 g of 5% Pd / C (0.113 g as dry), and 150 mL of THF were added to a 300 mL SUS autoclave and sealed. Nitrogen purging and hydrogen purging were repeated four times, and soapy water was used to confirm no gas leakage. The temperature was raised to 50°C under a constant hydrogen pressure of 0.8 MPa and stirring at 150 rpm. The stirring speed was increased to 1000 rpm, and the hydrogen inlet valve was opened. While maintaining an internal temperature of 60°C-65°C, the theoretical amount of hydrogen was absorbed over 50 minutes, followed by aging for 10 minutes, confirming that the internal pressure did not decrease. After nitrogen purging, the autoclave was opened, and the used catalyst was hot-filtered. The solvent was removed by distillation from the hydrogenation mother liquor using an evaporator, and the resulting white solid was dissolved in 500 mL of isopropanol by heating. 0.4 g of activated carbon was added, and the mixture was stirred under reflux for 30 minutes. The activated carbon was filtered and separated, and 500 mL of deionized water was added. The resulting precipitate was dissolved by heating, slowly cooled to 5°C, and the primary crystals were filtered. The filtrate was concentrated to 2 / 3, and the resulting secondary crystals were filtered and combined with the previous primary crystals for drying. A product of 18.9 g / yield (94%), mp 187°C-189°C, and HPLC purity of 97% was obtained as a pale yellow crystalline powder. The structure of the product was analyzed by 1H-NMR and 13C-NMR. The results are shown in Figures 13-16. The product is 1,2,4-trimethyl-3,6-bis(3-aminobenzoyloxy)benzene represented by formula (h). TOF-MS(ESI):391.1643(M+H)+

[0043] [Example 9] Synthesis of [1,4-Phenylbenzene bis(propane-2,2-diyl)]bis(4,1-Phenylbenzene)bis(3-nitrobenzene) [Chemical 40] In a 500 mL four-necked flask equipped with a stirrer, thermometer, Diane-Stark apparatus, and Dimroth cooling tube, 26.0 g (72 mmol) of bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added and stirred at 300 rpm (white slurry). Subsequently, 25.0 g (158 mmol) of m-nitrobenzoic acid chloride (MNBC) was added, and the mixture was stirred at 75°C for 3 hours (after the addition of MNCB, the internal temperature rose to 50°C). The mixture was cooled to 25°C, and the white precipitate was filtered through a 110 mm ϕ funnel and No. 5C filter paper. It was then washed with 100 mL of methanol and 200 mL of deionized water. The precipitate was dried under reduced pressure at 90°C and -0.1 MPa for 16 h. The product was obtained as a white powder, yielding 40.6 g of nitrocellulose (88%), with a liquid chromatography (LC) purity (area%) of 98.8% and a melting point (visually) of 208°C-209°C. This product is [1,4-epenylphenylbis(propane-2,2-diyl)]bis(4,1-epenylphenyl)bis(3-nitrobenzoate) (hereinafter referred to as dinitrocellulose 5), as represented by formula (i). TOF-MS (ESI): 643.209 (MH)-

[0044] [Example 10] Synthesis of [1,4-Phenylbis(propane-2,2-diyl)]bis(4,1-Phenyl)bis(3-aminobenzoate) [Chemical 41] 15.0 g (23 mmol) of dinitro 5, 100 mL of dimethyl formamide (DMF), and 1.0 g of Rexroth nickel were added to a 300 mL autoclave and sealed. Nitrogen purging and hydrogen purging were repeated four times. The internal pressure of the autoclave was adjusted to 0.8 MPa for leak checking. After confirming no hydrogen leakage, the hydrogen inlet valve was closed and the autoclave sealed. While stirring at 200 rpm, the autoclave was heated using a preheated mantle heater. When the temperature reached 90°C, the stirring speed was set to 1000 rpm, the hydrogen inlet valve was opened, and the hydrogenation reaction began (this time point is set as reaction start 0 min). The reaction was carried out at a constant pressure of 0.80 MPa and 90±1℃. The reaction was continued using a high flow meter until the hydrogen absorption ceased instantaneously. The hydrogenation time was 50 min. The hydrogen inlet valve was closed, and the mixture was stirred for 60 min. Once no pressure drop was observed, stirring was stopped, and the hydrogen in the autoclave was purged. The autoclave was then purged three times with nitrogen (gauge pressure 0–0.3 MPa). Since the diamine from the opened autoclave had precipitated, the solvent was removed by distillation using an evaporator. 200 mL of acetonitrile was added and heated to dissolve the catalyst, which was then filtered. The filtrate was cooled to 5℃ (a pale grayish-white powder precipitated at approximately 20℃). The powder was filtered using a Kiriyama funnel (110 mm ϕ) and No. 5C filter paper. It was then washed with 30 mL of methanol and 30 mL of deionized water, and dried under reduced pressure at 90 °C and -0.1 MPa for 16 h. The product was obtained as a pale grayish-white powder (7.9 g, yield 97%, LC purity 98.6%, melting point (visual) 284 °C-285 °C). This product is [1,4-epenylphenylbis(propane-2,2-diyl)]bis(4,1-epenylphenyl)bis(3-aminobenzoate), as represented by formula (j). TOF-MS (ESI): 585.276 (M+H)+

[0045] [Example 11] Synthesis of [1,3-Phenylbenzenebis(propane-2,2-diyl)]bis(4,1-Phenylbenzene)bis(3-nitrobenzene) [Chemical 42] In a 500 mL four-necked flask equipped with a stirrer, thermometer, Diane-Stark apparatus, and Deyle cooler, 26.0 g (75 mmol) of bisphenol M, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added, and the mixture was stirred at 300 rpm (colorless and transparent). Subsequently, 25.0 g (158 mmol) of m-nitrobenzoic acid chloride (MNBC) was added, and the mixture was stirred at 60 °C for 2 hours (after the addition of MNCB, the internal temperature rose to 42 °C). The mixture was cooled to 30°C, and the white precipitate was filtered through a Kiriyama funnel (110 mm ϕ) and No. 5C filter paper. It was then washed with 100 mL of methanol and 200 mL of deionized water. The precipitate was dried under reduced pressure at 90°C and -0.1 MPa for 16 h, yielding a white powder with a yield of 82% (18.6 g by weight), LC purity of 99.1%, and a melting point (visually) of 160°C-161°C. This product is [1,3-epenylphenylbis(propane-2,2-diyl)]bis(4,1-epenylphenyl)bis(3-nitrobenzene) (hereinafter referred to as dinitro 6), as represented by formula (k). TOF-MS (ESI): 643.209 (MH)-

[0046] [Example 12] Synthesis of [1,3-Phenylbis(propane-2,2-diyl)]bis(4,1-Phenyl)bis(3-aminobenzoate) [Chemical 43] 17.0 g (26 mmol) of dinitro 6, 120 mL of THF, and 0.1 g of 5% Pd / C (as dry) were added to a 300 mL autoclave, and the autoclave was sealed. Nitrogen purging and hydrogen purging were repeated four times. The internal pressure of the autoclave was adjusted to 0.8 MPa for leak checks. After confirming no hydrogen leakage, the hydrogen inlet valve was closed and the autoclave was sealed. While stirring at 200 rpm, the autoclave was heated using a preheated heating pack. At 60°C, the stirring speed was set to 1000 rpm, the hydrogen inlet valve was opened, and the hydrogenation reaction was started (this time point is set as reaction start 0 min). The reaction was carried out at a constant pressure of 0.80 MPa and 65±1°C. The reaction was carried out using a high flow meter until the hydrogen absorption disappeared instantaneously. The hydrogenation time was 28 min. The hydrogen inlet valve was closed, and the mixture was stirred for 60 min. Stirring was stopped after confirming no pressure drop and the hydrogen in the autoclave was purged. Nitrogen was then used for three purgings (gauge pressure 0–0.3 MPa). The autoclave was opened and the catalyst was filtered. The filtrate was cooled to 5°C, but no crystals precipitated. Therefore, the solvent was distilled off using an evaporator (resulting in a paste). 100 mL of methanol was added and heated to dissolve the paste. After cooling to 10°C, a white powder precipitated. The powder was filtered using a 110 mm ϕ funnel and No. 5C filter paper. The powder was then washed with 50 mL of methanol and 100 mL of deionized water. The powder was dried under reduced pressure at 90°C and -0.1 MPa for 16 h. The product was obtained as a white powder with a yield of 98% (15.0 g by weight), LC purity of 99.5%, and a melting point (visually) of 161–162°C. The product is [1,3-epenylphenylbis(propane-2,2-diyl)]bis(4,1-epenylphenyl)bis(3-aminobenzoate), represented by formula (m). TOF-MS (ESI): 585.276 (M+H)+

[0047] [Comparative Example 1] Synthesis of 1,4-bis(4-aminobenzoyloxy)benzene / hydroquinone-type p-diamine [Chemical 44] Hydroquinone 8.3 g (75 mmol) and acetonitrile 200 mL and triethylamine 16.0 g (158 mmol) were added to a 300 mL four-necked flask equipped with a mechanical stirrer and thermometer, and heated to 45 °C to dissolve it (reddish-brown transparent solution). After adding 25.0 g (158 mmol) of m-nitrobenzoyl chloride (PNBC), a white precipitate was immediately formed. The internal temperature rose from 45 °C to 68 °C, and then cooled shortly afterward (light white-green slurry). The mixture was stirred at 45 °C for 1 hour under these conditions, and the disappearance of PNBC was confirmed by HPLC. After cooling to room temperature, the white precipitate was filtered off, and the filter cake was washed with methanol. The product was air-dried to obtain a white powder of 22.4 g / yield 73%, mp 263℃-264.5℃, and HPLC purity 99.6%. This product is the compound represented by the stated formula (n) (hereinafter referred to as dinitrosol(n)). [Chem. 45] 22.5 g (53 mmol / purity conversion) of the dinitrosol(n) and 0.130 g of 5% Pd / C (0.056 g as dry) and 150 mL of methyl cellosolve (MC) were added to a 300 mL SUS autoclave and sealed. Nitrogen purging and hydrogen purging were repeated 4 times and confirmed to be free of gas leakage using soapy water. The temperature was raised to 70℃ under a constant hydrogen pressure of 0.8 MPa and stirring at 150 rpm. The stirring speed was increased to 1000 rpm and the hydrogen inlet valve was opened. While maintaining an internal temperature of 85℃~90℃, the theoretical amount of hydrogen was absorbed over 42 minutes, followed by aging for 20 minutes to confirm that the internal pressure did not decrease. After nitrogen purging, the autoclave was opened, and 1 L of DMF was added to the white mousse-like slurry, which was then dissolved at reflux temperature. The used catalyst was hot-filtered, and the filtrate was slowly cooled and the resulting precipitate was collected at 5℃. 200 mL of γ-butyrolactone was added to the filter cake and heated to 165℃ to dissolve it. The precipitate was then slowly cooled to 30℃ and collected. The filter cake was washed with methanol and air-dried to obtain a product of 12.6 g / yield (71%), mp > 300℃, and HPLC purity of 96% as a peach-white powder. This product is 1,4-bis(4-aminobenzoyloxy)benzene represented by formula (p).

[0048] [Comparative Example 2] Synthesis of 2,5-bis(4-aminobenzoyloxy)toluene / Methylhydroquinone type p-diamine [Chemical 46] 9.3 g (75 mmol) of methylhydroquinone, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added to a 300 mL four-necked flask equipped with a mechanical stirrer and a thermometer, and kept at room temperature to dissolve (pale yellow transparent solution). After adding 25.0 g (158 mmol) of m-nitrobenzoyl chloride (PNBC), a white precipitate was immediately formed. The internal temperature was raised from 19°C to 39°C, and then heated to 80°C (white slurry). The mixture was stirred for 1 hour under these conditions, and the disappearance of PNBC was confirmed by HPLC. After cooling to room temperature, the white precipitate was filtered off, and the filter cake was washed with methanol. The product was air-dried to obtain a white powder of 24.8 g / yield (98%), mp 269℃-270.5℃, and HPLC purity of 98%. This product is the compound represented by formula (q) (hereinafter referred to as dinitrosol(q)) [Chem. 47]. 10.6 g (25 mmol / purity conversion) of the dinitrosol(q), 0.065 g of 5% Pd / C (0.028 g as dry), and 180 mL of methyl cellosolve (MC) were added to a 300 mL SUS autoclave and sealed. Four nitrogen purgings and four hydrogen purgings were repeated, and no gas leakage was confirmed using soapy water. The temperature was raised to 70℃ under a constant hydrogen pressure of 0.8 MPa and stirring at 150 rpm. The stirring speed was increased to 1000 rpm, and the hydrogen inlet valve was opened. While maintaining an internal temperature of 90℃~95℃, the theoretical amount of hydrogen was absorbed over 42 minutes, followed by aging for 20 minutes to confirm that the internal pressure did not decrease. After nitrogen purging, the autoclave was opened, and the used catalyst was hot-filtered. 45 mL of ion-exchanged water (white slurry) was added, and the mixture was heated to reflux temperature to dissolve it. The mixture was cooled to 20℃, and the resulting precipitate was filtered and dried to obtain a product of 7.5 g / yield (83%), mp 271.5℃-273℃, and LC purity of 96%, which is a light yellow powder. This product is 2,5-bis(4-aminobenzoyloxy)toluene represented by the formula (r).

[0049] Solubility of Diamines The melting points and solubility in various solvents of the diamines obtained in the examples and comparative examples are shown in Table 1 below. In Table 1 below, ++ indicates soluble at room temperature, ++ indicates soluble after heating, + indicates partially soluble after heating, and - indicates insoluble in solvent. Among the para-type diamines, especially the unsubstituted hydroquinone type para-diamine (melting point > 300°C, Comparative Example 1), it is only soluble in N,N-dimethylformamide (DMF) when heated. The methyl hydroquinone type para-diamine (melting point 272°C-273°C, Comparative Example 2), which has a methyl group on the central benzene ring, is also barely soluble in highly polar solvents such as methyl cellosol (MC) or dimethyl sulfoxide (DMSO) when heated. On the other hand, the meta-type diamines have relatively low melting points and high solubility relative to various solvents. In particular, the bisphenol AF type is easily soluble in a variety of solvents. This confirms the effectiveness of the present invention.

[0050] [Table 1] Example 2 Example 4 Example 6 Example 8 Comparative Example 1 Comparative Example 2 m-diamine p-Diamine X= Melting point ℃ 160-161 235-236 148-150 187-189 >300 272-273 methanol +++ - + + - Isopropanol ++ - + + - - MC +++ ++ +++ +++ - ++ Acetonitrile +++ ++ +++ +++ - + acetone +++ ++ +++ +++ - + Ethyl acetate +++ ++ +++ +++ - + chloroform ++ - +++ +++ - + THF +++ + +++ +++ - + Toluene ++ - + + - + m-cresol +++ +++ +++ +++ - + DMSO +++ +++ +++ +++ + ++ DMF +++ +++ +++ +++ ++ +++ Sample 30 mg / solvent 2 mL, +++ soluble at room temperature, ++ soluble upon heating, + partially soluble upon heating, - insoluble

[0051] [Example 13] Polyimide was synthesized by polymerization of the diamine compound (bisphenol AF type m-diamine, formula (b)) obtained in Example 2 and pyromellitic acid dianhydride (PMDA) [Chemical 48]. 3.78 g (6.58 mmol) of the diamine compound (bisphenol AF type m-diamine, formula (b)) obtained in Example 2 and 20 mL of m-cresol were added to a 100 mL separable flask equipped with a mechanical stirrer, thermometer, and condenser, and allowed to dissolve at room temperature (golden yellow viscous solution). Under a nitrogen flow, 1.44 g (6.60 mmol) of pyromellitic acid dianhydride (PMDA) was added, and the mixture was stirred for 2 hours. During this time, as the viscosity increased, the stirring speed was increased from 300 rpm to 400 rpm and from 400 rpm to 500 rpm. 0.50 g (3.8 mmol) of isoquinoline was added, and the mixture was stirred for 4 hours. 0.5 g of the polymerization solution was collected and injected into 30 mL of methanol. The resulting white precipitate was filtered, dried, and the formation of polyamide was confirmed by FT-IR. The results are shown in Figure 17. 30 mL of m-cresol was added to the viscous polymerization solution, and the mixture was heated to 190 °C and stirred for 14 hours. After cooling to room temperature, the polymerization solution was injected into 300 mL of methanol. The resulting precipitate was filtered, the filter cake was washed with methanol, and then heated using a vacuum dryer (180 °C / 8 hours). 3.8 g of a yellow powder (84% yield) was obtained. The synthesis of polyamide was confirmed by FT-IR. The results are shown in Figure 18. The obtained polyamide is soluble in N-methylpyrrolidinone (NMP) at room temperature.

[0052] [Example 14] In Example 9, PMDA was replaced with 4,4'-oxydiphthalic anhydride (ODPA). Otherwise, Example 9 was repeated to synthesize polyimide by polymerizing the diamine compound obtained in Example 2 with ODPA. The FT-IR spectrum of the obtained polyimide powder is shown in Figure 19. The obtained polyimide is soluble in NMP at room temperature.

[0053] [Example 15] In Example 9, PMDA was replaced with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and Example 9 was repeated otherwise, polyimide was synthesized by polymerization of the diamine compound obtained in Example 2 with 6FDA. The FT-IR spectrum of the obtained polyimide powder is shown in Figure 20. The obtained polyimide is soluble in NMP at room temperature.

[0054] [Example 16] In Example 9, the diamine compound obtained in Example 2 was replaced with the diamine compound (bisphenol S-type m-diamine) obtained in Example 4, and PMDA was replaced with 4,4'-oxyphthalic anhydride (ODPA). Otherwise, Example 9 was repeated to synthesize polyimide by polymerizing the diamine compound obtained in Example 4 with ODPA. The FT-IR spectrum of the obtained polyimide powder is shown in Figure 21. The obtained polyimide is soluble in NMP at room temperature.

[0055] [Example 17] In Example 9, the diamine compound obtained in Example 2 was replaced with the diamine compound (methylhydroquinone type m-diamine) obtained in Example 6, and PMDA was replaced with 4,4'-oxyphthalic anhydride (ODPA). Otherwise, Example 9 was repeated to synthesize polyimide by polymerizing the diamine compound obtained in Example 6 with ODPA. The FT-IR spectrum of the obtained polyimide powder is shown in Figure 22. The obtained polyimide is soluble in NMP at room temperature.

[0056] [Example 18] In Example 9, the diamine compound obtained in Example 2 was replaced with the diamine compound (trimethylhydroquinone type m-diamine) obtained in Example 8, and PMDA was replaced with 4,4'-oxyphthalic anhydride (ODPA). Otherwise, Example 9 was repeated to synthesize polyimide by polymerizing the diamine compound obtained in Example 8 with ODPA. The FT-IR spectrum of the obtained polyimide powder is shown in Figure 23. The obtained polyimide is soluble in NMP at room temperature. [Industrial Applicability]

[0057] The meta-ester aromatic diamine of the present invention can be preferably used as a novel polyimide raw material, which greatly expands the possibilities of the field of polyimides derived from this compound, and can be expected to be a material with excellent high heat resistance and electrical properties. [Simplified Explanation of the Diagram]

[0013] Figure 1 is a 1H-NMR spectrum of the compound prepared in Example 2. Figure 2 is an enlarged view of the 1H-NMR spectrum of the compound prepared in Example 2. Figure 3 is a 13C-NMR spectrum of the compound prepared in Example 2. Figure 4 is an enlarged view of the 13C-NMR spectrum of the compound prepared in Example 2. Figure 5 is a 1H-NMR spectrum of the compound prepared in Example 4. Figure 6 is an enlarged view of the 1H-NMR spectrum of the compound prepared in Example 4. Figure 7 is a 13C-NMR spectrum of the compound prepared in Example 4. Figure 8 is an enlarged view of the 13C-NMR spectrum of the compound prepared in Example 4. Figure 9 is a 1H-NMR spectrum of the compound prepared in Example 6. Figure 10 is an enlarged view of the 1H-NMR spectrum of the compound prepared in Example 6. Figure 11 is a 13C-NMR spectrum of the compound prepared in Example 6. Figure 12 is an enlarged view of the 13C-NMR spectrum of the compound prepared in Example 6. Figure 13 is a 1H-NMR spectrum of the compound prepared in Example 8. Figure 14 is an enlarged view of the 1H-NMR spectrum of the compound prepared in Example 8. Figure 15 is a 13C-NMR spectrum of the compound prepared in Example 8. Figure 16 is an enlarged view of the 13C-NMR spectrum of the compound prepared in Example 8. Figures 17-1 and 17-2 are Fourier translation-infrared spectroscopy (FT-IR) spectra and peak lists of the polyamide prepared in Example 13. Figures 18-1 and 18-2 are FT-IR spectra and peak lists of the polyimide powder prepared in Example 13. Figures 19-1 and 19-2 are FT-IR spectra and peak lists of the polyimide powder prepared in Example 14. Figures 20-1 and 20-2 are FT-IR spectra and peak lists of the polyimide powder prepared in Example 15. Figures 21-1 and 21-2 are FT-IR spectra and peak lists of the polyimide powder prepared in Example 16. Figures 22-1 and 22-2 are FT-IR spectra and peak lists of the polyimide powder prepared in Example 17. Figures 23-1 and 23-2 are FT-IR spectra and peak lists of the polyimide powder prepared in Example 18. Figure 24 is a 1H-NMR spectrum of the compound prepared in Example 9. Figure 25 is an enlarged view of the 1H-NMR spectrum of the compound prepared in Example 9. Figure 26 is a 1H-NMR spectrum of the compound prepared in Example 10. Figure 27 is an enlarged view of the 1H-NMR spectrum of the compound prepared in Example 10.Figure 28 is a 13C-NMR spectrum of the compound prepared in Example 10. Figure 29 is an enlarged view of the 13C-NMR spectrum of the compound prepared in Example 10. Figure 30 is a 1H-NMR spectrum of the compound prepared in Example 11. Figure 31 is an enlarged view of the 1H-NMR spectrum of the compound prepared in Example 11. Figure 32 is a 1H-NMR spectrum of the compound prepared in Example 11. Figure 33 is an enlarged view of the 1H-NMR spectrum of the compound prepared in Example 11. Figure 34 is a 13C-NMR spectrum of the compound prepared in Example 11. Figure 35 is an enlarged view of the 13C-NMR spectrum of the compound prepared in Example 11.

Claims

1. A compound represented by the following formula (1): In formula (1), X is as follows (a), R1, R2, R3 and R4 in formula (1) are hydrogen atoms, R5 and R6 in (a) are hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms.

2. A compound represented by the following formula (1'): In formula (1'), X is as follows (d), R1, R2, R3, R4, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms.

3. A compound represented by the following formula (1): In formula (1), X is (c) below, R1, R2, R3 and R4 in formula (1) are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms; R9 in (c) above is a hydrogen atom, and R7, R8 and R10 are independently alkyl groups having 1 to 6 carbon atoms.

4. The compound as claimed in claim 1, wherein, In formula (a), R5 and R6 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.

5. The compound as claimed in claim 3, wherein, In formula (1), R1, R2, R3 and R4 are hydrogen atoms, R9 in formula (c) is a hydrogen atom, and R7, R8 and R10 are alkyl groups with 1 to 6 carbon atoms.

6. The compound as claimed in claim 2, wherein, In formula (1'), R1, R2, R3, and R4 are hydrogen atoms, and in formula (d), R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20 are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, which are independent of each other.

7. The compound as claimed in claim 2, wherein, In the above formula (1'), X is any of the following structures: R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 are as described above, where * indicates a bond with an oxygen atom.

8. A method for manufacturing a compound, the compound being represented by the following formula (1): In formula (1), X is as follows (a), R1, R2, R3, and R4 in formula (1) are hydrogen atoms, R5 and R6 in (a) are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms, the method comprising the step of reducing two nitro groups of a compound represented by the following formula (2) to obtain the compound represented by formula (1), wherein R1, R2, R3, R4, and X are as described above.

9. A method for manufacturing a compound, the compound being represented by the following formula (1): In formula (1), X is as follows (c), R1, R2, R3, and R4 in formula (1) are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms; R9 in the above (c) is a hydrogen atom, and R7, R8, and R10 are independently alkyl groups having 1 to 6 carbon atoms; The manufacturing method comprises the step of reducing two nitro groups of a compound represented by the following formula (2) to obtain the compound represented by formula (1), wherein R1, R2, R3, R4, and X are as described above.

10. A method for manufacturing the compound as claimed in claim 8, wherein, In formula (a), R5 and R6 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.

11. A method for manufacturing the compound as claimed in claim 9, wherein, In formula (1), R1, R2, R3 and R4 are hydrogen atoms, R9 in formula (c) is a hydrogen atom, and R7, R8 and R10 are alkyl groups with 1 to 6 carbon atoms.

12. A method for manufacturing a compound, the compound being represented by the following formula (1'): In formula (1'), X is as follows (d), R1, R2, R3, R4, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms, the method comprising the step of reducing two nitro groups of a compound represented by formula (2) to obtain the compound represented by formula (1'), wherein R1, R2, R3, R4 and X are as described above.

13. The manufacturing method as described in claim 12, wherein, In formula (1'), R1, R2, R3, and R4 are hydrogen atoms, and in formula (d), R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20 are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, which are independent of each other.

14. The manufacturing method as described in claim 12 or claim 13, wherein, In the above formula (1'), X is any of the following structures: R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 are as described above, where * indicates a bond with an oxygen atom.

15. A polyimide compound, which is the product of the reaction of any one of claims 1 to 7 with an acid anhydride.

16. The polyimide compound as claimed in claim 15, wherein, The anhydride is selected from at least one of the following groups: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, benzophenone-3,4,3',4'-tetracarboxylic dianhydride, 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, and oxy-4,4'-diphthalic dianhydride.

17. The polyimide compound as claimed in claim 15, having a number average molecular weight of 2,000 to 200,000.

18. The polyimide compound of claim 15 is a reaction product of a compound as described in any one of claims 1 to 7, an anhydride, and a diamine compound other than those described in claims 1 to 7, wherein, The proportion of units derived from any one of claims 1 to 7 is 10 mol% to 100 mol% relative to the total number of units derived from the diamine compounds other than those described in claims 1 to 7.

19. A molded article comprising the polyimide compound as described in claim 15.

20. A molded article comprising the polyimide compound as described in claim 18.

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