Compound, method for producing the same, polyimide compound, and molded article

Abstract

The present invention aims to provide a compound and a manufacturing method thereof, a polyimide compound, and a molded article. A compound represented by the following formula (1): In formula (1), X is the following (a), (b), (c), or (d), R1, R2, R3, and R4 in formula (1), and R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 are independently a hydrogen atom, a substitutable alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, wherein at least one of R7, R8, R9, and R 10 is the alkyl group or the 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. In particular, it relates to a compound and its manufacturing method, a polyimide compound, and a molded article. Background Technology

[0002] Printed wiring boards and similar components used in the information and communication field require high-speed, high-capacity communication, thus necessitating their use in higher frequency bands than currently available. However, this increases transmission loss due to higher frequencies. Transmission loss can be categorized into resistive loss and dielectric loss. Resistive loss exhibits a characteristic of increasing in frequency as heat, while dielectric loss is proportional to frequency, the dielectric loss tangent, and the relative permittivity.

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

[0004] [Existing Technical Documents]

[0005] [Non-patent literature]

[0006] Non-patent literature 1: Pathrick RA et al., Journal of Applied Polymer Science, vol. 132, pp. 41684-41692, 2015.

[0007] Non-patent literature 2: Akhter Z. et al., "Polymer Bulletin", vol. 74, pp. 3889-3906, 2017.

[0008] Non-patent literature 3: Masatoshi Hasegawa et al. "Polymers", vol. 12, p. 859, 2020.

[0009] Non-patent literature 4: S. Tamai et al. "Polymer", vol. 37, pp. 3683-3692, 1996. Summary of the Invention

[0010] [The problem the invention aims to solve]

[0011] As a material with excellent 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 its dielectric constant. A fundamental consideration in reducing the dielectric constant of PI lies in how to dilute (reduce) the concentration of imide groups that affect the high dielectric constant. To reduce the concentration of imide 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.

[0012] Therefore, to simultaneously achieve excellent high heat resistance, electrical properties, and processability, it is effective to use meta-ether aromatic diamines as raw materials for polyimide (PI). However, to manufacture 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 readily 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. A method for manufacturing the same is also described.

[0013] [Technical means to solve the problem]

[0014] The inventors have diligently studied the problems of aromatic diamines as described above, and as a result, produced a novel meta-ester aromatic diamine, namely a bis(3-aminobenzoyloxy) compound having a 3-aminobenzoyloxy group and being trinuclear or tetranuclear, and a pentanuclear meta-ester aromatic diamine, thus completing the present invention.

[0015] That is, the present invention provides a compound represented by the following formula (1) and a method for manufacturing the same.

[0016] [Chemistry 1]

[0017]

[0018] In equation (1), X is one of the following (a), (b), or (c):

[0019] [Chemistry 2]

[0020]

[0021] [Chemistry 3]

[0022]

[0023] [Chemistry 4]

[0024]

[0025] R1, R2, R3, and R4 in equation (1), and R5, R6, R7, R8, R9, and R in (a), (b), and (c) 10 Independently comprising hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms, wherein R7, R8, R9, and R 10 At least one of them is an alkyl or alkoxy group.

[0026] In addition, the present invention provides a compound represented by the following formula (1') and a method for manufacturing the same.

[0027] [Chemistry 5]

[0028]

[0029] In equation (1'), X is the following (d),

[0030] [Chemistry 6]

[0031]

[0032] R1, R2, R3, R4, R 11 R 12 R 13 R 14R 15 R 16 R 17 R 18 R 19 and R 20 The atoms are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms.

[0033] 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.

[0034] [The effects of the invention]

[0035] The meta-ester aromatic diamine of the present invention exhibits excellent solubility in various solvents. Furthermore, because the meta-ester aromatic diamine of the present invention has three or more aromatic rings, it can reduce the imide concentration of the obtained polyimide, and because it has an ester moiety, it can reduce the hygroscopicity of the obtained polyimide. Therefore, it is effective for achieving a low dielectric constant in polyimides. Moreover, the meta-ester aromatic diamine of the present invention is preferably used as a polyimide raw material with high processability. Attached Figure Description

[0036] Figure 1 The proton NMR spectrum of the compound prepared in Example 2 is shown. 1 H-nuclear magneticresonance, 1 The 1H-NMR spectrum.

[0037] Figure 2 It is the compound manufactured in Example 2. 1 Enlarged view of H-NMR spectrum.

[0038] Figure 3 The carbon NMR spectrum of the compound prepared in Example 2 ( 13 The C-NMR spectrum.

[0039] Figure 4 It is the compound manufactured in Example 2. 13 Magnified view of the C-NMR spectrum.

[0040] Figure 5 It is the compound produced in Example 4. 1 The H-NMR spectrum.

[0041] Figure 6 It is the compound produced in Example 4. 1 Enlarged view of H-NMR spectrum.

[0042] Figure 7 It is the compound produced in Example 4.13 The C-NMR spectrum.

[0043] Figure 8 It is the compound produced in Example 4. 13 Magnified view of the C-NMR spectrum.

[0044] Figure 9 It is the compound manufactured in Example 6. 1 The H-NMR spectrum.

[0045] Figure 10 It is the compound manufactured in Example 6. 1 Enlarged view of H-NMR spectrum.

[0046] Figure 11 It is the compound manufactured in Example 6. 13 The C-NMR spectrum.

[0047] Figure 12 It is the compound manufactured in Example 6. 13 Magnified view of the C-NMR spectrum.

[0048] Figure 13 It is the compound manufactured in Example 8. 1 The H-NMR spectrum.

[0049] Figure 14 It is the compound manufactured in Example 8. 1 Enlarged view of H-NMR spectrum.

[0050] Figure 15 It is the compound manufactured in Example 8. 13 The C-NMR spectrum.

[0051] Figure 16 It is the compound manufactured in Example 8. 13 Magnified view of the C-NMR spectrum.

[0052] Figure 17 It is the Fourier transform-infrared (FT-IR) spectrum of the polyamic acid manufactured in Example 9.

[0053] Figure 18 The FT-IR spectrum is that of the polyimide powder manufactured in Example 9.

[0054] Figure 19 The FT-IR spectrum is that of the polyimide powder manufactured in Example 10.

[0055] Figure 20The FT-IR spectrum is that of the polyimide powder manufactured in Example 11.

[0056] Figure 21 The FT-IR spectrum is that of the polyimide powder manufactured in Example 12.

[0057] Figure 22 The FT-IR spectrum is that of the polyimide powder manufactured in Example 13.

[0058] Figure 23 The FT-IR spectrum is that of the polyimide powder manufactured in Example 14.

[0059] Figure 24 It is the compound manufactured in Example 9. 1 The H-NMR spectrum.

[0060] Figure 25 It is the compound manufactured in Example 9. 1 Enlarged view of H-NMR spectrum.

[0061] Figure 26 It is the compound manufactured in Example 10. 1 The H-NMR spectrum.

[0062] Figure 27 It is the compound manufactured in Example 10. 1 Enlarged view of H-NMR spectrum.

[0063] Figure 28 It is the compound manufactured in Example 10. 13 The C-NMR spectrum.

[0064] Figure 29 It is the compound manufactured in Example 10. 13 Magnified view of the C-NMR spectrum.

[0065] Figure 30 It is the compound manufactured in Example 11. 1 The H-NMR spectrum.

[0066] Figure 31 It is the compound manufactured in Example 11. 1 Enlarged view of H-NMR spectrum.

[0067] Figure 32 It is the compound manufactured in Example 11. 1 The H-NMR spectrum.

[0068] Figure 33 It is the compound manufactured in Example 11. 1 Enlarged view of H-NMR spectrum.

[0069] Figure 34 It is the compound manufactured in Example 11. 13 The C-NMR spectrum.

[0070] Figure 35 It is the compound manufactured in Example 11. 13 Magnified view of the C-NMR spectrum. Detailed Implementation

[0071] One embodiment of the present invention relates to a meta-ester aromatic diamine represented by the following formula (1).

[0072] [Chemistry 7]

[0073]

[0074] In equation (1), X is one of the following (a), (b), or (c):

[0075] [Chemistry 8]

[0076]

[0077] [Chemistry 9]

[0078]

[0079] [Chemistry 10]

[0080]

[0081] R1, R2, R3, and R4 in equation (1), and R5, R6, R7, R8, R9, and R in (a), (b), and (c). 10 Independently comprising hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms, wherein R7, R8, R9, and R 10 At least one of them is an alkyl or alkoxy group.

[0082] Another embodiment of the present invention relates to a meta-ester aromatic diamine represented by the following formula (1').

[0083] [Chemistry 11]

[0084]

[0085] In equation (1'), X is the following (d),

[0086] [Chemistry 12]

[0087]

[0088] R1, R2, R3, R4, R11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 The atoms are independently hydrogen atoms, substituted alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 3 carbon atoms.

[0089] As R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 The substituted alkyl groups having 1 to 6 carbon atoms can be listed as follows: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl. Alkoxy groups having 1 to 3 carbon atoms can be listed as: methoxy, ethoxy, propoxy. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 They may be different or the same. Preferably, they are alkyl groups having 1 to 6 hydrogen atoms or carbon atoms. More preferably, in (a), (b), and (d), R1, R2, R3, R4, R5, R6, R... 11 R 12 R 13 R 14 R 15 R 16 R 17 and R 18 All of them can be hydrogen atoms. In (c) above, R1, R2, R3, and R4 are preferably hydrogen atoms, and R7, R8, R9, and R... 10 At least one of them is preferably methyl.

[0090] Preferably, it is a tetranuclear compound represented by formula (1a) or (1b) below, or a trinuclear compound represented by formula (1c) below.

[0091] [Chemistry 13]

[0092]

[0093] [Chemistry 14]

[0094]

[0095] In formulas (1a) and (1b), R1, R2, R3, R4, R5 and R6 are as described above, and are preferably hydrogen atoms.

[0096] [Chemistry 15]

[0097]

[0098] In formula (1c), R1, R2, R3, and R4 are as described above, and are preferably hydrogen atoms, and R7, R8, R9, and R 10 As described above, and at least one of them is methyl.

[0099] Furthermore, the formula (d) is preferably represented by the following formula (1d).

[0100] [Chemistry 16]

[0101]

[0102] In equation (1d), R1, R2, R3, R4, R 11 R 12 R 13 R 14 R 15 R 16 R 17 and R 18 As described above, and preferably a hydrogen atom. R 19 and R 20 As described above, and preferably methyl.

[0103] In formula (d), there are no particular restrictions on the bonding positions of the substituents to the aromatic ring. Preferably, X is a compound having the following structure.

[0104] [Chemistry 17]

[0105]

[0106] [Chemistry 18]

[0107]

[0108] R1, R2, R3, R4, R 11 R 12 R 13 R 14 R 15 R 16 R 17 and R 18 As described above, and preferably a hydrogen atom. R 19 and R 20 As described above, and preferably methyl. The asterisk (*) indicates a bond with an oxygen atom.

[0109] The compounds of the present invention are particularly preferred to be the following compounds.

[0110] [Chemistry 19]

[0111]

[0112] [Chemistry 20]

[0113]

[0114] [Chemistry 21]

[0115]

[0116] [Chemistry 22]

[0117]

[0118] [Chemistry 23]

[0119]

[0120] [Chemistry 24]

[0121]

[0122] The compound represented by formula (1) can be readily obtained by reducing the two nitro groups of the compound represented by formula (3) below.

[0123] [Chemistry 25]

[0124]

[0125] (In the formula, R1, R2, R3, R4 and X are as described above)

[0126] The manufacturing method will be explained in more detail below.

[0127] 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.

[0128] Solvents that can be used in reduction reactions include, for example, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-methoxyethanol, and 2-ethoxyethanol; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and N,N'-dimethylimidazolidineone; and ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol. However, the list is not limited to these solvents as long as they are solvents that dissolve aromatic dinitro compounds. The amount of solvent can be adjusted appropriately.

[0129] The catalyst used in the reduction reaction may be any known catalyst used in the respective reduction reactions. Examples of catalysts that can be used in contact reduction or hydrazine reduction include: noble metal catalysts such as palladium, platinum, and rhodium 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, which is typically 0.1 wt% to 10 wt% relative to the aromatic dinitro compound.

[0130] 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 after removing the catalyst and cooling it. 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.

[0131] The compound represented by formula (3) is particularly preferably represented by the following formula.

[0132] [Chemistry 26]

[0133]

[0134] [Chemistry 27]

[0135]

[0136] [Chemistry 28]

[0137]

[0138] [Chemistry 29]

[0139]

[0140] [Chemistry 30]

[0141]

[0142] [Chemistry 31]

[0143]

[0144] The compound represented by formula (3) can be manufactured by known methods. For example, it can be manufactured by the condensation of the respective diol compound with m-nitrobenzoyl chloride.

[0145] The meta-ester aromatic diamine represented by formula (1) exhibits excellent solubility in various solvents and can be effectively used as a raw material for polyimides. For example, polyimide compounds can be obtained by reacting the meta-ester aromatic diamine represented by formula (1) with acid anhydrides.

[0146] The acid anhydride may be any previously 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'-diphenylsulfonetetracarboxylic acid dianhydride and oxy-4,4'-diphthalic acid dianhydride.

[0147] 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. The number average molecular weight is, for example, a value determined by gel permeation chromatography (GPC, tetrahydrofuran, THF).

[0148] 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 molar percentage of units derived from all diamine compounds. Examples of any diamine compound other than the diamine compound of the present invention include, for example, 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, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diphenyl sulfone, etc. One or more of the group consisting of aminodiphenyl sulfide, 4,4'-diaminobenzoylaniline, 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]sulfone, bis[4-(4-aminophenoxy)phenyl)sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9'-bis(4-aminophenyl)fluorene, and 9,9'-bis[4-(4-aminophenoxy)phenyl]fluorene.

[0149] Examples of molded products containing the polyimide compounds of the present invention include materials for high-speed, high-capacity communications.

[0150] [Example]

[0151] The present invention will be described in more detail below with reference to the embodiments shown, but the present invention is not limited to the embodiments described below.

[0152] The measurement methods and apparatus used in the following examples are as follows.

[0153] The Shimadzu SPD-20A was used for high performance liquid chromatography (HPLC) determination, and the Yamato MP-21 was used for melting point determination.

[0154] exist 1 The H NMR spectroscopy analysis used Avance III HD 400 (Bruker Biospin), and the solvent used was deuterated dimethyl sulfoxide (DMSO).

[0155] exist 13 The C-NMR spectroscopy analysis used an Avance III HD 400 (Bruker Biospin) instrument, and the solvent used was deuterated DMSO.

[0156] The infrared spectrophotometer used was the FT / IR-4700 manufactured by Japan Spectrophotometer, and the measurement was performed by attenuated total reflection (ATR) method.

[0157] Xevo g2-XS QTof manufactured by Waters was used in precision quality analysis.

[0158] [Example 1]

[0159] Synthesis of 2,2'-bis[4-(3-nitrobenzoyloxy)phenyl]hexafluoropropane

[0160] [Chemistry 32]

[0161]

[0162] In a 300 mL four-necked flask equipped with a mechanical stirrer and thermometer, 25.2 g (75 mmol) of bisphenol AF, 200 mL of tetrahydrofuran (THF), and 16.0 g (158 mmol) of triethylamine were added and allowed to dissolve at room temperature (resulting in a pale yellow, transparent solution). Upon addition of 25.0 g (158 mmol) of m-nitrobenzoyl chloride (MNBC), a white precipitate 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, and the disappearance of MNBC was confirmed by HPLC. While maintaining room temperature, the triethylamine hydrochloride was filtered and the solvent was removed by distillation using an evaporator. The resulting white solid was washed with 300 mL of deionized water, filtered, and the filter cake was dissolved in 260 mL of acetonitrile by heating. The sample was slowly cooled to 5°C, filtered, and dried to obtain a product of 36.0 g / yield (76%) of white needle-like crystals, with a melting point (mp) of 195.2°C-196.5°C and an HPLC purity of 98.7%. The product is 2,2'-bis[4-(3-nitrobenzoyloxy)phenyl]hexafluoropropane (hereinafter referred to as dinitropropane 1), as represented by formula (a). Time-of-flight mass spectrometry (TOF-MS) (electrospray ionization (ESI)): 633.073 (M). -

[0163] [Example 2]

[0164] Synthesis of 2,2'-bis[4-(3-aminobenzoyloxy)phenyl]hexafluoropropane

[0165] [Chemistry 33]

[0166]

[0167] 22.5 g (35 mmol / purity conversion) of the dinitrocellulose 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 no decrease in internal pressure. After nitrogen purging, the autoclave was opened, and the used catalyst was hot-filtered. The solvent was removed from the hydrogenation mother liquor by distillation using an evaporator. 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 off, 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 18.5 g of pale yellow needle-like crystals (92% yield), mp 159.6°C–160.5°C, and HPLC purity 99.6%. 1 H-NMR and 13 The product was subjected to structural analysis by C-NMR. The results are shown below. Figures 1-4 The product is 2,2'-bis[4-(3-aminobenzoyloxy)phenyl]hexafluoropropane, represented by formula (b). TOF-MS (ESI): 575.1414 (M+H) +

[0168] [Example 3]

[0169] Synthesis of bis[4-(3-nitrobenzoyloxy)phenyl]sulfone

[0170] [Chemistry 34]

[0171]

[0172] In a 300 mL four-necked flask equipped with a mechanical stirrer and thermometer, 12.8 g (51 mmol) of bisphenol S, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added, 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 252-253 °C, and HPLC purity of 98%. The product is bis[4-(3-nitrobenzoyloxy)phenyl]sulfone (hereinafter referred to as dinitro 2) represented by formula (c).

[0173] [Example 4]

[0174] Synthesis of bis[4-(3-aminobenzoyloxy)phenyl]sulfone

[0175] [Chemistry 35]

[0176]

[0177] 22.5 g (35 mmol / purity conversion) of the dinitrocellulose 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 the vessel was 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 no decrease in internal pressure. 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 upon heating. Add 0.4 g of activated carbon and stir under reflux for 30 minutes. Filter the activated carbon and add 40 mL of deionized water. Dissolve the resulting precipitate by heating, cool slowly to 5°C, filter, and dry to obtain a pale yellow crystalline powder of 14.5 g / yield (74%), mp 235-236°C, and HPLC purity of 94%. 1 H-NMR and 13 The product was subjected to structural analysis by C-NMR. The results are shown below. Figures 5-8 The product is bis[4-(3-aminobenzoyloxy)phenyl] sulfone, represented by formula (d).

[0178] TOF-MS (ESI): 489.1106 (M+H) +

[0179] [Example 5]

[0180] Synthesis of 1-methyl-2,5-bis(3-nitrobenzoxy)benzene

[0181] [Chemistry 36]

[0182]

[0183] In a 300 mL four-necked flask equipped with a mechanical stirrer and thermometer, 9.3 g (75 mmol) of methylhydroquinone, 200 mL of THF, and 16.0 g (158 mmol) of triethylamine were added and allowed to dissolve at room temperature (resulting in a colorless, transparent solution). Upon addition of 25.0 g (158 mmol) of m-nitrobenzoyl chloride (MNBC), a white precipitate immediately formed. The internal temperature rose from 25 °C to 58 °C, 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, followed by slurry washing 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 °C–199.2 °C, and HPLC purity of 99.3%. The product is 1-methyl-2,5-bis(3-nitrobenzoyloxy)benzene (hereinafter referred to as dinitro 3) as represented by formula (e).

[0184] [Example 6]

[0185] Synthesis of 1-methyl-2,5-bis(3-aminobenzoyloxy)benzene

[0186] [Chemistry 37]

[0187]

[0188] 22.5 g (35 mmol / purity conversion) of the dinitrocellulose 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 no decrease in internal pressure. 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. Add 0.4 g of activated carbon and stir under reflux for 30 minutes. Filter the activated carbon and add 500 mL of deionized water. Dissolve the resulting precipitate by heating, cool slowly to 5°C, filter, and dry to obtain a product containing 11.7 g of pale yellow crystalline powder (61% yield), mp 148-150°C, and HPLC purity of 96%. 1 H-NMR and 13 The product was subjected to structural analysis by C-NMR. The results are shown below. Figures 9-12 The product is 1-methyl-2,5-bis(3-aminobenzoyloxy)benzene as represented by formula (f).

[0189] TOF-MS (ESI): 363.1336 (M+H) +

[0190] [Example 7]

[0191] Synthesis of 1,2,4-trimethyl-3,6-bis(3-nitrobenzoxy)benzene

[0192] [Chemistry 38]

[0193]

[0194] In a 300 mL four-necked flask equipped with a mechanical stirrer and thermometer, 11.4 g (75 mmol) of trimethylhydroquinone, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added and allowed to dissolve at room temperature (resulting in a colorless, transparent solution). Upon addition of 25.0 g (158 mmol) of m-nitrobenzoyl 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. Air drying yielded a product with 27.3 g of white powder (81% yield), mp 226.0 °C–226.8 °C, and 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 formula (g).

[0195] [Example 8]

[0196] Synthesis of 1,2,4-trimethyl-3,6-bis(3-aminobenzoyloxy)benzene

[0197] [Chemistry 39]

[0198]

[0199] 22.5 g (35 mmol / purity conversion) of the dinitrocellulose 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 no decrease in internal pressure. 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. Add 0.4 g of activated carbon and stir under reflux for 30 minutes. Filter the activated carbon and add 500 mL of deionized water. Dissolve the resulting precipitate by heating, then slowly cool to 5°C and filter the primary crystals. Concentrate the filtrate to 2 / 3, filter the resulting secondary crystals, combine with the primary crystals, and dry. A product of 18.9 g / yield (94%), pale yellow crystalline powder, mp 187-189°C, and HPLC purity of 97% is obtained. 1 H-NMR and 13The product was subjected to structural analysis by C-NMR. The results are shown below. Figures 13-16 The product is 1,2,4-trimethyl-3,6-bis(3-aminobenzoyloxy)benzene as represented by formula (h).

[0200] TOF-MS (ESI): 391.1643 (M+H) +

[0201] [Example 9]

[0202] Synthesis of [1,4-phenylenebis(propane-2,2-diyl)]bis(4,1-phenylene)bis(3-nitrobenzene)

[0203] [Chemistry 40]

[0204]

[0205] 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-nitrobenzoyl 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 110mm diameter Kiriyama funnel using No. 5C filter paper. It was then washed with 100mL of methanol and 200mL of deionized water. The precipitate was dried under reduced pressure at 90°C and -0.1MPa for 16 hours. The product was obtained as a white powder containing 40.6g of nitrocellulose, with a yield of 88%, a liquid chromatography (LC) purity (area%) of 98.8%, and a melting point (visually) of 208°C-209°C. The product is [1,4-phenylenebis(propane-2,2-diyl)]bis(4,1-phenylene)bis(3-nitrobenzoate) (hereinafter referred to as dinitrocellulose 5) as represented by formula (i). TOF-MS (ESI): 643.209 (MH) -

[0206] [Example 10]

[0207] Synthesis of [1,4-phenylenebis(propane-2,2-diyl)]bis(4,1-phenylene)bis(3-aminobenzoate)

[0208] [Chemistry 41]

[0209]

[0210] Add 15.0 g (23 mmol) of dinitrocellulose 5, 100 mL of dimethylformamide (DMF), and 1.0 g of Rexroth nickel to a 300 mL autoclave, and seal the vessel. Repeat the nitrogen purging and hydrogen purging four times, adjusting the internal pressure of the autoclave to 0.8 MPa for leak checks. After confirming no hydrogen leakage, close the hydrogen inlet valve and seal the vessel. While stirring at 200 rpm, heat using a preheated mantle heater. When the temperature reaches 90 °C, set the stirring speed to 1000 rpm, open the hydrogen inlet valve, and begin the hydrogenation reaction (set the time point as reaction start 0 min). The reaction is carried out at a constant pressure of 0.80 MPa and 90 ± 1 °C. Continue the reaction using a high flow meter until the hydrogen is absorbed and disappears instantaneously. The hydrogenation time is 50 min. Close the hydrogen inlet valve, stir for 60 minutes, and stop stirring after confirming no pressure drop. After purging the hydrogen from the autoclave, perform three nitrogen purgings (gauge pressure 0–0.3 MPa). Open the autoclave. Since diamine has precipitated, remove the solvent by distillation using an evaporator. Add 200 mL of acetonitrile and heat to dissolve. Filter the catalyst. Cool the filtrate to 5°C (a pale grayish-white powder precipitates at approximately 20°C). Filter the powder using a 110 mm φ Kiriyama funnel and No. 5C filter paper. Wash with 30 mL of methanol and 30 mL of deionized water. Dry under reduced pressure at 90°C and -0.1 MPa for 16 hours. The product is obtained as 7.9 g of pale grayish-white powder, with a yield of 97%, LC purity of 98.6%, and a melting point (visually) of 284°C–285°C. The product is [1,4-phenylenebis(propane-2,2-diyl)]bis(4,1-phenylene)bis(3-aminobenzoate) as represented by formula (j).

[0211] TOF-MS (ESI): 585.276 (M+H) +

[0212] [Example 11]

[0213] Synthesis of [1,3-phenylenebis(propane-2,2-diyl)]bis(4,1-phenylene)bis(3-nitrobenzene)

[0214] [Chemistry 42]

[0215]

[0216] In a 500 mL four-necked flask equipped with a stirrer, thermometer, Dean-Stark apparatus, and Deutsche cooler, 26.0 g (75 mmol) of bisphenol M, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added and stirred at 300 rpm (the mixture was colorless and transparent). Then, 25.0 g (158 mmol) of m-nitrobenzoyl chloride (MNBC) was added, and the mixture was stirred at 60 °C for 2 hours (the internal temperature rose to 42 °C after the addition of MNCB). The mixture was cooled to 30 °C, and the white precipitate was filtered through a 110 mm φ Kiriyama funnel using No. 5C filter paper. The precipitate 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 hours, 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. The product is [1,3-phenylenebis(propane-2,2-diyl)]bis(4,1-phenylene)bis(3-nitrobenzene) (hereinafter referred to as dinitro 6), represented by formula (k). TOF-MS (ESI): 643.209 (MH) -

[0217] [Example 12]

[0218] Synthesis of [1,3-phenylenebis(propane-2,2-diyl)]bis(4,1-phenylene)bis(3-aminobenzoate)

[0219] [Chemistry 43]

[0220]

[0221] 17.0 g (26 mmol) of dinitrocellulose 6, 120 mL of THF, and 0.1 g of 5% Pd / C (as dry) were added to a 300 mL autoclave, and the vessel was sealed. The autoclave was purged with nitrogen four times and hydrogen four times. The internal pressure was adjusted to 0.8 MPa for a leak check. After confirming no hydrogen leakage, the hydrogen inlet valve was closed and the vessel sealed. The vessel was stirred at 200 rpm while being heated using a preheated heating pack. When the temperature reached 60 °C, the stirring speed was set to 1000 rpm, and the hydrogen inlet valve was opened to begin the hydrogenation reaction (the 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 continued using a high flow meter until the hydrogen was absorbed and disappeared instantaneously. At this point, the hydrogenation time was 28 min. Close the hydrogen inlet valve, stir for 60 minutes, and stop stirring after confirming no pressure drop. After purging the hydrogen from the autoclave, perform three nitrogen purgings (gauge pressure 0–0.3 MPa). Open the autoclave and filter the catalyst. Cool the filtrate to 5°C, but no crystals precipitate. Therefore, remove the solvent by distillation using an evaporator (to remove the paste). Add 100 mL of methanol and heat to dissolve. After cooling to 10°C, a white powder precipitates. Filter using a 110 mm φ Kiriyama funnel with No. 5C filter paper. Wash with 50 mL of methanol and 100 mL of deionized water. Dry under reduced pressure at 90°C and -0.1 MPa for 16 hours. The product is obtained as a white powder with a yield of 98% (15.0 g by weight), LC purity of 99.5%, and melting point (visual) of 161°C–162°C. The product is [1,3-phenylenebis(propane-2,2-diyl)]bis(4,1-phenylene)bis(3-aminobenzoate) as represented by formula (m). TOF-MS (ESI): 585.276 (M+H) +

[0222] [Comparative Example 1]

[0223] Synthesis of 1,4-bis(4-aminobenzoyloxy)benzene / hydroquinone-type p-diamine

[0224] [Chemistry 44]

[0225]

[0226] In a 300 mL four-necked flask equipped with a mechanical stirrer and thermometer, 8.3 g (75 mmol) of hydroquinone, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added and heated to 45 °C to dissolve them (resulting in a reddish-brown transparent solution). Upon addition of 25.0 g (158 mmol) of p-nitrobenzoyl chloride (PNBC), a white precipitate immediately formed. The internal temperature rose from 45 °C to 68 °C, and then cooled shortly afterward (resulting in a pale greenish-white 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 product with a white powder yield of 22.4 g / yield (73%), mp 263 °C–264.5 °C, and HPLC purity of 99.6%. This product is the compound represented by formula (n) (hereinafter referred to as dinitro (n)).

[0227] [Chemistry 45]

[0228]

[0229] Add 22.5 g (converted from 53 mmol / purity) of the aforementioned dinitrocellulose (n) and 0.130 g of 5% Pd / C (0.056 g as dry) and 150 mL of methyl cellosolve (MC) to a 300 mL SUS autoclave, and seal the vessel. Repeat the nitrogen purging and hydrogen purging four times, confirming no gas leakage using soapy water. Heat to 70 °C under a constant hydrogen pressure of 0.8 MPa and stirring at 150 rpm. Increase the stirring speed to 1000 rpm and open the hydrogen inlet valve. While maintaining the internal temperature at 85 °C–90 °C, absorb the theoretical amount of hydrogen over 42 minutes, then mature for 20 minutes, confirming no pressure drop. After nitrogen purging, open the autoclave and add 1 L of DMF to the white mousse-like slurry, dissolving it at reflux temperature. The used catalyst was hot-filtered, and the filtrate was slowly cooled. The resulting precipitate was collected at 5°C. 200 mL of γ-butyrolactone was added to the filter cake and heated to 165°C to dissolve it. The mixture was then slowly cooled to 30°C, and the resulting precipitate was collected. The filter cake was washed with methanol and air-dried to obtain a product with a peach-white powder content of 12.6 g / yield (71%), mp > 300°C, and HPLC purity of 96%. The product is 1,4-bis(4-aminobenzoyloxy)benzene as represented by formula (p).

[0230] [Comparative Example 2]

[0231] Synthesis of 2,5-bis(4-aminobenzoyloxy)toluene / methylhydroquinone type p-diamine

[0232] [Chemistry 46]

[0233]

[0234] In a 300 mL four-necked flask equipped with a mechanical stirrer and thermometer, 9.3 g (75 mmol) of methylhydroquinone, 200 mL of acetonitrile, and 16.0 g (158 mmol) of triethylamine were added and kept at room temperature to dissolve (a pale yellow, transparent solution). Upon addition of 25.0 g (158 mmol) of p-nitrobenzoyl chloride (PNBC), a white precipitate immediately formed. The internal temperature was raised from 19 °C to 39 °C, and then further 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 °C–270.5 °C, and HPLC purity of 98%. The product is the compound represented by formula (q) (hereinafter referred to as dinitro (q)).

[0235] [Chemistry 47]

[0236]

[0237] Add 10.6 g (25 mmol / purity conversion) of the dinitrocellulose (q) and 0.065 g of 5% Pd / C (0.028 g as dry) and 180 mL of methyl cellosolve (MC) to a 300 mL SUS autoclave, and seal the vessel. Repeat nitrogen purging and hydrogen purging four times, confirming no gas leakage using soapy water. Heat to 70 °C under a constant hydrogen pressure of 0.8 MPa and stirring at 150 rpm. Increase the stirring speed to 1000 rpm and open the hydrogen inlet valve. While maintaining an internal temperature of 90 °C–95 °C, absorb the theoretical amount of hydrogen over 42 minutes, then mature for 20 minutes, confirming no pressure drop. After nitrogen purging, open the autoclave and hot-filter the used catalyst. Add 45 mL of ion-exchanged water (white slurry) and heat to reflux temperature to dissolve it. The product was cooled to 20°C, filtered, and dried to obtain a light yellow powder (7.5 g / yield 83%), with a mp value of 271.5°C-273°C and an LC purity of 96%. The product is 2,5-bis(4-aminobenzoyloxy)toluene as represented by formula (r).

[0238] Solubility of diamine

[0239] 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.

[0240] Among para-diamines, particularly unsubstituted hydroquinone-type para-diamines (melting point > 300°C, Comparative Example 1), dissolve only in N,N-dimethylformamide (DMF) when heated. Methylhydroquinone-type para-diamines with a methyl group on the central benzene ring (melting point 272°C-273°C, Comparative Example 2) also barely dissolve in highly polar solvents such as methyl cellosolve (MC) or dimethyl sulfoxide (DMSO) when heated. On the other hand, meta-diamines generally have lower melting points and higher solubility relative to various solvents. Bisphenol AF type, in particular, readily dissolves in a variety of solvents. This demonstrates the effectiveness of the present invention.

[0241] [Table 1]

[0242]

[0243] [Example 13]

[0244] Polyimide was synthesized by polymerization of the diamine compound (bisphenol AF type m-diamine, formula (b)) obtained in Example 2 with pyromellitic acid dianhydride (PMDA).

[0245] [Chemistry 48]

[0246]

[0247] 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). 1.44 g (6.60 mmol) of pyromellitic dianhydride (PMDA) was added under a nitrogen stream, and the mixture was stirred for 2 hours. During this time, the stirring speed was increased from 300 rpm to 400 rpm and then from 400 rpm to 500 rpm as the viscosity increased. 0.50 g (3.8 mmol) of isoquinoline was added, and the mixture was stirred for another 4 hours. 0.5 g of the polymerization solution was taken and injected into 30 mL of methanol. The resulting white precipitate was filtered, dried, and the formation of polyamic acid was confirmed by FT-IR. The results are presented in… Figure 17 middle.

[0248] 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 off, and 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 was obtained (yield 84%). The synthesis of polyimide was confirmed by FT-IR. The results are shown below. Figure 18 The obtained polyimide is soluble in N-methylpyrrolidinone (NMP) at room temperature.

[0249] [Example 14]

[0250] 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 below. Figure 19 The obtained polyimide is soluble in NMP at room temperature.

[0251] [Example 15]

[0252] In Example 9, PMDA was replaced with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). Otherwise, Example 9 was repeated to synthesize polyimide by polymerizing the diamine compound obtained in Example 2 with 6FDA. The FT-IR spectrum of the obtained polyimide powder is shown below. Figure 20 The obtained polyimide is soluble in NMP at room temperature.

[0253] [Example 16]

[0254] 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 below. Figure 21 The obtained polyimide is soluble in NMP at room temperature.

[0255] [Example 17]

[0256] 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 below. Figure 22 The obtained polyimide is soluble in NMP at room temperature.

[0257] [Example 18]

[0258] 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 below. Figure 23 The obtained polyimide is soluble in NMP at room temperature.

[0259] [Industry availability]

[0260] The meta-ester aromatic diamine of the present invention can be preferably used as a novel polyimide raw material, greatly expanding the possibilities of polyimides derived from the compound, and is expected to be a material with excellent high heat resistance and electrical properties.

Claims

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

2. A compound represented by the following formula (1'): In equation (1'), X is as follows (d). R1, R2, R3, and R4 are hydrogen atoms, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 They are independently hydrogen atoms, 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 equation (1), X is (c) below. In formula (1), R1, R2, R3, and R4 are hydrogen atoms, and in (c), R9 is a hydrogen atom, R7, R8, and R... 10 Each is an alkyl group having 1 to 6 carbon atoms, and they are independent of each other.

4. The compound according to 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 according to claim 2, wherein, In equation (d), R1, R2, R3, and R4 are hydrogen atoms, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 Each is an alkyl group consisting of 1 to 6 hydrogen atoms or carbon atoms, which are independent of each other.

6. The compound according to claim 2 or 5, wherein, In equation (d), X is any of the following structures: R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 As described above, in the formula The indicated area represents the bond with an oxygen atom.

7. A method for manufacturing a compound, said compound being represented by the following formula (1): In equation (1), X is the following (a). In formula (1), R1, R2, R3, and R4 are hydrogen atoms, and in formula (a), R5 and R6 are independently hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, or alkoxy groups with 1 to 3 carbon atoms. The manufacturing method includes the step of reducing two nitro groups of the compound represented by formula (2) below to obtain the compound represented by formula (1). In the formula, R1, R2, R3, R4, and X are as described above.

8. A method for manufacturing a compound, said compound being represented by the following formula (1): In equation (1), X is (c) below. In formula (1), R1, R2, R3, and R4 are hydrogen atoms, and in (c), R9 is a hydrogen atom, R7, R8, and R... 10 Each is an alkyl group having 1 to 6 carbon atoms independently. The manufacturing method includes the step of reducing two nitro groups of the compound represented by formula (2) below to obtain the compound represented by formula (1). In the formula, R1, R2, R3, R4, and X are as described above.

9. The method for manufacturing the compound according to claim 7, wherein, In formula (a), R5 and R6 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.

10. A method for manufacturing a compound, said compound being represented by the following formula (1'): In equation (1'), X is as follows (d). R1, R2, R3, and R4 are hydrogen atoms, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 Each of the following is independently composed of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. The manufacturing method includes the step of reducing two nitro groups of the compound represented by formula (2) below to obtain the compound represented by formula (1'). In the formula, R1, R2, R3, R4, and X are as described above.

11. The method for producing the compound according to claim 10, wherein, R1, R2, R3, and R4 are hydrogen atoms, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 Each is an alkyl group consisting of 1 to 6 hydrogen atoms or carbon atoms, which are independent of each other.

12. The method for producing the compound according to claim 10 or 11, wherein, In equation (d), X is any of the following structures: R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 As described above, in the formula The indicated area represents the bond with an oxygen atom.

13. A polyimide compound, which is the reaction product of the compound as described in any one of claims 1 to 6 with an acid anhydride.

14. The polyimide compound according to claim 13, 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'-diphenylsulfonetetracarboxylic dianhydride, and oxy-4,4'-diphthalic dianhydride.

15. The polyimide compound according to claim 13 or 14, wherein the number average molecular weight is 2,000 to 200,000.

16. The polyimide compound according to claim 13 or 14, wherein the product is a reaction product of the compound according to any one of claims 1 to 6, an acid anhydride, and a diamine compound other than the compound according to claims 1 to 6, wherein, The proportion of units derived from the compounds described in any one of claims 1 to 6 is 10 mol% to 100 mol% relative to the total molar ratio of units derived from the compounds other than those described in claims 1 to 6.

17. A molded article comprising the polyimide compound as described in any one of claims 13 to 16.

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