Imidazole ring diamine monomer and preparation method thereof, intrinsic black polyimide material and preparation method and application thereof

Abstract

The invention provides an imidazole ring diamine monomer and a preparation method thereof, a black polyimide material and a preparation method and application thereof, and relates to the field of polymers. The invention provides a novel imidazole ring diamine monomer, and a synthesis method of the novel imidazole ring diamine monomer comprises the step of carrying out one-pot reaction on terephthalaldehyde, 1, 2-bis (3-hydroxyphenyl) ethane-1, 2-diketone, 1, 4-phenylenediamine and ammonium acetate in a solvent environment and protective gas at 70-90 DEG C to generate the imidazole ring diamine monomer. A novel imidazole ring diamine monomer is introduced into a polyimide material, stable, uniform and deep intrinsic blackening can be realized on the premise of keeping inherent excellent performances such as thermal performance, mechanical performance and chemical stability of polyimide, an important candidate system is provided for high-end electronic information product packaging and aerospace materials, and the application prospect is broad. The method can be applied to brand new scenes such as deep space exploration, 6G communication and brain-computer interfaces.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of polymers, and particularly relates to an imidazole ring diamine monomer and a preparation method thereof, an intrinsic black polyimide material and a preparation method and application thereof. BACKGROUND

[0002] As a typical representative of high-performance polymer materials, polyimide is widely used in aerospace, microelectronic devices, flexible display, new energy and other fields due to its excellent high-temperature resistance, chemical stability, mechanical properties and dielectric properties. With the development of society and the progress of science and technology, the demand for black polyimide is increasing. The molecular chain of black polyimide has a strong charge transfer effect, which can reduce the energy level difference and cause strong intramolecular electron transition in the visible light region, forming a wide spectral band absorption. The front-end application of black polyimide has broken through the traditional packaging field and expanded to three new scenes: space optoelectronic systems, intelligent sensing terminals and new energy equipment.

[0003] However, the existing technology for preparing black polyimide still has the following limitations: (1) physical blending method: adding carbon black, graphene and other light-absorbing fillers to the polyimide matrix to prepare black polyimide, which has problems such as uneven dispersion of fillers, interface defects leading to mechanical decline, etc.; (2) chemical modification method: introducing light-absorbing groups (such as aniline black structure) or metal chelating units to prepare black polyimide, which has problems such as the introduction of light-absorbing groups that may damage the regularity of the molecular chain, the difficulty of synthesis and the possible reduction of thermal performance of by-products.

[0004] Therefore, there is an urgent need to provide a solution to improve the above problems. SUMMARY

[0005] The purpose of the present application is to provide an imidazole ring diamine monomer and a preparation method thereof, an intrinsic black polyimide material and a preparation method and application thereof. The present application enhances the charge transfer effect through molecular design to improve the blackness of polyimide material, and realizes stable, uniform and deep intrinsic blackening under the premise of maintaining the inherent properties of polyimide (temperature resistance, mechanical strength).

[0006] In a first aspect, the present application provides an imidazole ring diamine monomer (APTP) with a structure as shown in formula (I):

[0007]

[0008] In a second aspect, the present application provides a method for synthesizing an imidazole ring diamine monomer with a structure shown in formula (I), comprising: one-pot reaction of terephthaldehyde, 1,2-bis(3-hydroxyphenyl)ethane-1,2-dione, 1,4-benzenediamine, and ammonium acetate in a solvent environment under a protective gas at 70-90°C to generate the imidazole ring diamine monomer.

[0009] Optionally, the solvent comprises a mixed solution of acetonitrile and acetic acid.

[0010] Optionally, the protective gas comprises one of nitrogen, argon, or helium.

[0011] Optionally, the reaction is performed at 70-90°C for 7-9h.

[0012] Optionally, the molar ratio of the terephthaldehyde, 1,2-bis(3-hydroxyphenyl)ethane-1,2-dione, 1,4-benzenediamine, and ammonium acetate is (0.8-1.2):(1.8-2.2):(1.8-2.2):(0.6-1.0).

[0013] In a third aspect, the present application provides a method for preparing a black intrinsic polyimide (BPI), comprising: condensation polymerization of a diamine and a dianhydride in a high-boiling-point polar solvent, followed by imidization and separation to obtain a black intrinsic polyimide material; the diamine comprises at least 10%-50% of an imidazole ring diamine monomer shown in formula (I) by weight:

[0014]

[0015] Optionally, the diamine further comprises one of a diamino diphenyl ether, a diamino diphenyl, or a diamino diphenyl methane.

[0016] Optionally, the dianhydride comprises one of a diphenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, or a bisphenol A type diether dianhydride.

[0017] Optionally, the molar ratio of the diamine to the dianhydride is 1:1.

[0018] Optionally, the condensation polymerization of the diamine and the dianhydride is performed at 20-30°C.

[0019] Optionally, the high-boiling-point polar solvent comprises one or more of N-methyl pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0020] Optionally, the condensation polymerization is performed in anhydrous high-boiling-point polar solvent for 4-36h.

[0021] Optionally, the imidization comprises thermal imidization or chemical imidization.

[0022] Optionally, the intrinsic black polyimide material includes intrinsic black polyimide film and intrinsic black polyimide powder.

[0023] Optionally, a polyamic acid solution is prepared by polycondensation of diamine and dianhydride in a high-boiling-point polar solvent. The polyamic acid solution is then coated to form a film, and thermal imidization is performed at 80℃-350℃ to obtain an intrinsic black polyimide film.

[0024] Optionally, a polyamic acid solution is prepared by polycondensation of diamine and dianhydride in a high-boiling-point polar solvent. The polyamic acid solution is then diluted and a dehydrating agent and catalyst are added to perform chemical imidization to obtain intrinsic black polyimide powder.

[0025] Optionally, the dehydrating agent includes one of acetic anhydride, propionic anhydride, and butyric anhydride.

[0026] Optionally, the catalyst includes one of trimethylamine, triethylamine, and tripropylamine.

[0027] Optionally, the molar ratio of the dehydrating agent to the catalyst is (2-4):1.

[0028] Fourthly, the present invention also provides an intrinsically black polyimide material prepared by any of the optional preparation methods described in the third aspect above, the molecular chain structure of which is as follows:

[0029]

[0030] Where m:n is (1:9)-(1:1).

[0031] Optionally, the intrinsic black polyimide material has an optical transmittance of ≤10% in the visible light band (380nm~750nm).

[0032] Optionally, the thickness of the intrinsic black polyimide film is 5 μm to 200 μm.

[0033] Fifthly, the present invention also provides an application of an intrinsic black polyimide material prepared by any of the optional preparation methods of the third aspect above or any of the optional intrinsic black polyimide materials of the fourth aspect above, including its use in any of the following fields: flexible circuit substrates or packaging materials in the microelectronics field, wafer processing carriers or photomasks in the semiconductor field, and high-temperature resistant insulating films or satellite thermal control materials in the aerospace field. Attached Figure Description

[0034] Figure 1 The molecular structure diagram of APTP prepared in Example 1 is shown.

[0035] Figure 2Reaction mechanism for preparing diamine monomer APTP by constructing imidazole ring by Debus-Radziszewski reaction;

[0036] Figure 3 FT-IR diagram of intrinsic black polyimide film ABPIx series film prepared for example 2 to example 6;

[0037] Figure 4 FT-IR diagram of intrinsic black polyimide film ABPI prepared for example 2; 10

[0038] Figure 5 Digital photo of intrinsic black polyimide film ABPIx series film prepared for example 2 to example 6;

[0039] Figure 6 UV-vis spectrum of intrinsic black polyimide film ABPIx series film prepared for example 2 to example 6. DETAILED DESCRIPTION

[0040] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application. Unless otherwise defined, the technical terms or scientific terms used herein should be understood as the common meanings thereof by those skilled in the art.

[0041] The present application provides an imidazole ring diamine monomer (APTP) structure as shown in formula (I):

[0042]

[0043] In fact, the electron-rich property of the novel imidazole ring diamine monomer (APTP) can provide electron donor, enhance CTC effect, reduce energy level difference, and broaden absorption spectrum. By introducing such imidazole ring structure to prepare intrinsic black polyimide, the original excellent performance of polyimide (PI) such as thermal performance, mechanical performance and chemical stability can be retained while ensuring the blackness of the material.

[0044] The present application also provides a synthesis method of an imidazole ring diamine monomer with structure as shown in formula (I), comprising: one-pot reaction of terephthaldehyde, 1,2-bis(3-hydroxyphenyl)ethane-1,2-dione, 1,4-benzenediamine, and ammonium acetate in a solvent environment under 70-90 DEG C protective gas to generate the imidazole ring diamine monomer. ​

[0045] In some embodiments, the molar ratio of terephthaldehyde, 1,2-bis(3-hydroxyphenyl)ethane-1,2-dione, 1,4-benzenediamine, and ammonium acetate is (0.8-1.2):(1.8-2.2):(1.8-2.2):(0.6-1.0).

[0046] In fact, terephthaldehyde, as a key raw material for synthesizing imidazole ring diamine monomer (APTP), mainly provides aldehyde group (-CHO) for the reaction to construct the C2 carbon skeleton of the imidazole ring; 1,2-bis(3-hydroxyphenyl)ethane-1,2-dione, as an α-dicarbonyl compound, participates in cyclization; 1,4-benzenediamine provides amino group (-NH2) to construct N1 / N3 of the imidazole ring and expand the molecular structure as a linking group; ammonium acetate, as an ammonia source, participates in the formation of the imidazole ring. It should be noted that in the process of synthesizing APTP, the amount of raw materials participating in the reaction needs to be controlled to avoid excessive amount leading to other side reactions.

[0047] In some embodiments, the protective gas includes one of nitrogen, argon, or helium. In fact, the amino group is relatively active during the reaction, and inert gas is needed as a protective gas to prevent oxidation and deterioration.

[0048] In some embodiments, the solvent of the reaction includes a mixed solution of acetonitrile and acetic acid. In fact, acetonitrile is necessary as a main solvent to dissolve the reactants and ensure uniform mixing; acetic acid is used as a cosolvent to provide an acidic environment for the reaction to promote cyclization and protonate the amino group to prevent oxidation.

[0049] The present application provides a preparation method of intrinsic black polyimide, comprising: polycondensing and imidizing diamine and dianhydride in a high-boiling-point polar solvent to obtain intrinsic black polyimide material; the diamine includes at least 10%-50% of imidazole ring diamine monomer as shown in formula (I) by weight:

[0050]

[0051] In some embodiments, the diamine further includes one of diaminodiphenyl ether, diaminobiphenyl, and diaminodiphenylmethane. Specifically, in addition to APTP, other diamines used in the reaction are preferably diaminodiphenyl ether (ODA), which can adjust the flexibility of the molecular chain, balance the mechanical properties, and improve the film processing properties.

[0052] In some embodiments, the dianhydride includes one of benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and bisphenol A type diether dianhydride; the molar ratio of the diamine to the dianhydride is 1:1. Specifically, the dianhydride monomer is preferably bisphenol A type diether dianhydride (BPADA), and the molecular structure is as shown in formula (III):

[0053]

[0054] BPADA acts as an electron acceptor to construct the main chain of polyimide with diamine, and can adjust the flexibility of molecular chain and balance the rigid structure of APTP.

[0055] In some embodiments, the anhydrous high-boiling polar solvent includes one or more of N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. In fact, controlling the moisture content of the solvent used can prevent hydrolysis during the reaction, and the high boiling point is suitable for gradient imidization.

[0056] In some embodiments, the diamine and dianhydride are subjected to polycondensation in an anhydrous high-boiling polar solvent at 20-30°C for 4-36h. In fact, selecting a suitable reaction temperature can avoid too low a temperature leading to a too slow reaction rate and a low conversion rate, and too high a temperature can cause pre-imidization.

[0057] In some embodiments, the imidization process includes thermal imidization and chemical imidization. Specifically, the thermal imidization process includes polycondensation of the diamine and dianhydride in a high-boiling polar solvent to obtain a polyamic acid solution, coating the polyamic acid solution to form a film, and subjecting the film to thermal imidization at 80-350°C to obtain a black polyimide film with intrinsic imidazole ring structure (ABPI); the chemical imidization process includes polycondensation of the diamine and dianhydride in a high-boiling polar solvent to obtain a polyamic acid solution, diluting the polyamic acid solution, adding a dehydrating agent and a catalyst to the solution, and subjecting the solution to chemical imidization to obtain a black polyimide powder with intrinsic imidazole ring structure.

[0058] In some embodiments, the dehydrating agent used includes one of acetic anhydride, propionic anhydride, and butyric anhydride; the catalyst used includes one of trimethylamine, triethylamine, and tripropylamine; and the molar ratio of the dehydrating agent to the catalyst is (2-4):1.

[0059] Embodiment 1:

[0060] This embodiment 1 provides a method for synthesizing the imidazole structure diamine monomer APTP, which includes:

[0061] Into a 250 mL three-necked flask, 2,5-dihydroxyterephthalic acid (2.68 g, 20.00 mmol), 1,2-bis(3-hydroxyphenyl)ethane-1,2-dione (9.69 g, 40.00 mmol), 1,4-phenylenediamine (4.33 g, 40.00 mmol), ammonium acetate (12.33 g, 16.00 mmol) were added, 80 mL of acetonitrile and 15 mL of acetic acid were added as solvents, and the flask was placed in a magnetic stirrer and heated to 80°C while stirring to dissolve. Nitrogen was charged to ensure that the phenylenediamine and the product would not be oxidized in the reaction system. The temperature was raised to 80°C, and the stirring speed was adjusted to moderate to prevent the solution from splashing onto the wall of the reaction vessel and causing mass loss. The reaction was carried out for 8 h. The solid on the filter cake was collected by vacuum filtration and washed repeatedly with hot water three times. Recrystallization was performed with ethanol / water to obtain light green crystals, which were dried in a vacuum drying oven at 50°C for 12 h to obtain the diamine monomer APTP. The reaction process is shown below:

[0062]

[0063] Figure 1 A molecular structure diagram of the imidazole ring structure diamine monomer prepared in Example 1.

[0064] Example 2:

[0065] This example 2 provides a intrinsic black polyimide film ABPI 10 The preparation method of the film comprises the following steps:

[0066] S1: Preparation of polyamic acid (PAA) solution: In a dry nitrogen environment, 0.10 g of imidazole ring diamine monomer APTP prepared in Example 1 (0.1314 mmol), 0.2369 g of diamino diphenyl ether ODA (1.1829 mmol), and 5.0 mL of anhydrous N,N-dimethylacetamide solvent (anhydrous DMAc) were sequentially added to a 25 mL three-necked flask, wherein the molar ratio of APTP to ODA was 1:9. The diamine monomer was completely dissolved by magnetic stirring, and then 0.6841 g of bisphenol A type diether dianhydride BPADA (1.3143 mmol) was added to the flask in four batches, with an interval of 30 min each time, and DMAc was added to the system at the same time to a total solvent amount of 4.65 g (solid content 18 wt%). The stirring was continued for 12 h, and the system was vacuum degassed for 30 min to eliminate micropore defects, and a black-green polyamic acid PAA solution was prepared.

[0067] S2: Film forming process: The PAA solution was coated on the surface of a clean glass substrate by a casting method, and the thickness was controlled at 30±10 μm.

[0068] S3: Gradient thermal imidization: after removing the solvent at 80 °C for 4 h, the imidization ring-closing reaction was completed by following the temperature program: 150 °C for 1 h, 200 °C for 1 h, 250 °C for 0.5 h, 300 °C for 1.5 h, 350 °C for 0.5 h.

[0069] S4: Film peeling and post-treatment: after the programmed temperature rise ended, it was cooled to room temperature, immersed in boiling deionized water (100 °C, 10 min) to induce the film to peel off the substrate, and vacuum dried at 60 °C for 24 h to obtain the intrinsic imidazole ring structure black polyimide film ABPI 10 Film.

[0070] Example 3:

[0071] This example 3 provides a kind of intrinsic black polyimide film ABPI 20 The preparation method of the film, different from example 2, is that in step S1, 25 mL three-necked flask is sequentially added imidazole ring diamine monomer APTP (0.2000 g, 0.2629 mmol) prepared in example 1, diamino diphenyl ether ODA (0.2105 g, 1.0515 mmol) and 5.3 mL anhydrous N,N-dimethylacetamide solvent (anhydrous DMAc), wherein the molar ratio of APTP to ODA is 2:8. Stirring by magnetic force until the diamine monomer is completely dissolved, then add bisphenol A type diether dianhydride BPADA (0.6841 g, 1.3143 mmol) in 4 batches, with an interval of 30 min each time, and simultaneously supplement DMAc to the total solvent amount of the system is 4.9865 g (solid content 18 wt%); In step S4, the intrinsic imidazole ring structure black polyimide film ABPI 20 Film.

[0072] Example 4:

[0073] This example 4 provides a kind of intrinsic black polyimide film ABPI 30The preparation method of the film is different from that of Example 2 in that in step S1, the imidazole ring diamine monomer APTP (0.3000 g, 0.3943 mmol) prepared in Example 1, diamino diphenyl ether ODA (0.1842 g, 0.9200 mmol), and 5.7 mL of anhydrous N,N-dimethylacetamide solvent (anhydrous DMAc) are sequentially added to a 25 mL three-necked flask, wherein the molar ratio of APTP to ODA is 3:7. Stirring by magnetic force until the diamine monomer is completely dissolved, then add the bisphenol A type diether dianhydride BPADA (0.6841 g, 1.3143 mmol) in 4 batches with an interval of 30 min, and simultaneously supplement DMAc to a total solvent amount of 5.3223 g (solid content 18 wt%) in the system; the intrinsic imidazole ring structure black polyimide film ABPI is prepared in step S4 30 Film.

[0074] Example 5:

[0075] This Example 5 provides an intrinsic black polyimide film ABPI 40 The preparation method of the film is different from that of Example 2 in that in step S1, the imidazole ring diamine monomer APTP (0.3000 g, 0.3943 mmol) prepared in Example 1, diamino diphenyl ether ODA (0.1842 g, 0.9200 mmol), and 5.7 mL of anhydrous N,N-dimethylacetamide solvent (anhydrous DMAc) are sequentially added to a 25 mL three-necked flask, wherein the molar ratio of APTP to ODA is 3:7. Stirring by magnetic force until the diamine monomer is completely dissolved, then add the bisphenol A type diether dianhydride BPADA (0.6841 g, 1.3143 mmol) in 4 batches with an interval of 30 min, and simultaneously supplement DMAc to a total solvent amount of 5.3223 g (solid content 18 wt%) in the system; the intrinsic imidazole ring structure black polyimide film ABPI is prepared in step S4 40 Film.

[0076] Example 6:

[0077] This Example 6 provides an intrinsic black polyimide film ABPI 50The preparation method of the thin film differs from that of Example 2 in that in step S1, the imidazole ring diamine monomer APTP (0.5000 g, 0.6572 mmol) prepared in Example 1, the diamino diphenyl ether ODA (0.1316 g, 0.6572 mmol), and 6.4 mL of anhydrous N,N-dimethylacetamide solvent (anhydrous DMAc) are sequentially added to a 25 mL three-necked flask, wherein the molar ratio of APTP to ODA is 5:5. Stirring by magnetic force until the diamine monomer is completely dissolved, then add the bisphenol A type diether dianhydride BPADA (0.6841 g, 1.3143 mmol) in 4 batches with an interval of 30 min, and simultaneously supplement DMAc to a total solvent amount of 5.9937 g (solid content 18 wt%) in the system; the intrinsic imidazole ring structure black polyimide film ABPI is prepared in step S4 50 thin film.

[0078] Comparative Example:

[0079] The present comparative example provides a preparation method of a colorless polyimide (CPI) thin film ODA-BPADA thin film, which differs from Example 2 in that in step S1, diamino diphenyl ether ODA (0.2632 g, 1.3143 mmol) and 4.4 mL of anhydrous N,N-dimethylacetamide solvent (anhydrous DMAc) are sequentially added to a 25 mL three-necked flask, stirring by magnetic force until the diamine monomer is completely dissolved, then add the bisphenol A type diether dianhydride BPADA (0.6841 g, 1.3143 mmol) in 4 batches with an interval of 30 min, and simultaneously supplement DMAc to a total solvent amount of 4.32 g (solid content 18 wt%) in the system. Stirring for 12 h, vacuum degassing for 30 min to eliminate micropore defects, to prepare a light yellow polyamic acid PAA solution; in step S3, during gradient thermal imidization, after heating at 80°C for 6 hours to remove the solvent, the imidization ring closure reaction is completed according to the following program: 100°C for 1 h, 150°C for 1 h, 200°C for 1 h, and 250°C for 1 h; the ODA-BPADA thin film is prepared in step S4.

[0080] Figure 2 The reaction mechanism for preparing the diamine monomer APTP by constructing an imidazole ring using the Debus-Radziszewski reaction. Further, R1 is benzaldehyde, which can further undergo the reactions described in Examples 2 to 6 above to form a symmetrical structure.

[0081] The Fourier infrared spectrum analyzer is used to analyze the ABPI 10 , ABPI 20 , ABPI 30 , ABPI 40 , ABPI50 Five kinds of thin films were characterized by infrared to verify the structure of the target product, and the characterization results are shown in Figure 3 . The spectrum analysis is taken as an example of ABPI 10 , and the FT-IR spectrum of ABPI 10 is shown in Figure 4 .

[0082] As can be seen from Figure 4 , the thin film has obvious O-H stretching vibration at 3500cm -1 -3750cm -1 , which shows that the APTP monomer is well introduced into the PI chain. It can also be clearly seen that there are obvious peak values at 1776cm -1 and 1718cm -1 , which are obviously the stretching vibration of the C=O double bond in the imide ring. And due to the introduction of the electron-rich diamine, the C=O double bond originally at 1750cm -1 moves to a low frequency, which further indicates the successful preparation of ABPI.

[0083] Figure 5 The digital photos of the ODA-BPADA thin film prepared by the comparative example under sufficient light and the ABPI x series of five kinds of thin films prepared by examples 2 to 6 are shown in .

[0084] The CTC effect is the main reason for the absorption of traditional polyimide in the visible light region (yellow or dark color). The CPI thin film realizes transparency by inhibiting the CTC effect; the black polyimide thin film ABPI with intrinsic imidazole ring structure realizes intrinsic blackness (without filler) by strengthening the CTC effect. As can be seen from Figure 5 , the unmodified copolymer ODA-BPADA thin film prepared by the comparative example has good optical transmittance, and the text behind can be clearly seen. The ABPI X series of five kinds of thin films prepared by examples 2 to 6 all present good blackness, which can effectively resist visible light irradiation. And from Figure 5 , it can be found that only 10% copolymerization doping is needed to achieve good light shielding effect.

[0085] The optical properties of the ODA-BPADA thin film prepared by the comparative example and the ABPI x series of five kinds of thin films prepared by examples 2 to 6 were further tested using a UV-visible spectrophotometer, as shown in Figure 6 , and the results are summarized in table 1.

[0086] Table 1: ODA-BPADA thin film and ABPI xUV-vis spectral test results of the series of films

[0087]

[0088] T 600 The transmittance at 600 nm; λ0is the cut-off wavelength.

[0089] From Figure 6 As can be seen from Table 1, the cut-off wavelength (λ0) of all ABPI films is in the range of 571 nm to 652 nm, and the transmittance at 600 nm (T 600 ) is less than 0.7%.

[0090] The ODA-BPADA film prepared from the comparative example and the ABPI x films prepared from Examples 2 to 6 were subjected to color test, and the test data are collected in Table 2.

[0091] A standard color space was proposed by the International Commission on Illumination (CIE) in 1976, aiming to quantify the human visual perception of color. In the CIELAB parameters, L* = 0 represents black, L* = 100 represents diffuse white, positive a* represents red, and negative a* represents green. Positive b* represents yellow, and negative b* represents blue. c* represents color saturation: The light source was standard D65, the illumination angle was 10°, and the film size was 5 cm x 5 cm.

[0092] Table 2: ODA-BPADA film and ABPI x Color space diagram results of the series of films

[0093] PI film Light source / Angle L* a* b* c* ODA-BPADA D65 / 10° 88.7 0.2 86.4 86.4 ABPI 10 ]]> D65 / 10° 28.07 -0.36 0.67 0.76 ABPI 20 ]]> D65 / 10° 28.05 -0.79 0.86 1.17 ABPI 30 ]]> D65 / 10° 27.03 -0.1 1.05 1.05 ABPI 40 ]]> D65 / 10° 25.92 -0.41 1.44 1.5 ABPI 50 ]]> D65 / 10° 25.01 -0.2 1.08 1.09

[0094] As can be seen from Table 2, all ABPI films exhibit low L* and c* values. The L* and c* values of the ODA-BPADA film are as high as 88.6 and 86.3. The L* and c* values of the ABPIx series of films are reduced to the range of 25.01-28.07 and 0.76-1.5, respectively, which indicates that the introduction of APTP has a great effect on the color blackening of the film.

[0095] Although the embodiments of the present application have been described in detail above, it is obvious to those skilled in the art that various modifications and changes can be made to the embodiments. However, it should be understood that such modifications and changes are within the scope and spirit of the present application as described in the claims. Moreover, the present application described herein can have other embodiments and can be implemented or realized in various ways.

Claims

1. An imidazole ring diamine monomer having a structure as shown in formula (I): ###0001### 2. A method of synthesizing the imidazole ring diamine monomer of claim 1, wherein, The imidazole ring diamine monomer is prepared by one-pot reaction of terephthaldehyde, 1,2-bis(3-hydroxyphenyl)ethane-1,2-dione, 1,4-benzenediamine and ammonium acetate in a solvent environment under a protective gas at 70-90℃.

3. The method of claim 2, wherein, The solvent comprises a mixture of acetonitrile and acetic acid; and / or, the protective gas comprises one of nitrogen, argon or helium; and / or, the reaction time is 7-9 hours; and / or, the molar ratio of terephthaldehyde, 1,2-bis(3-hydroxyphenyl)ethane-1,2-dione, 1,4-benzenediamine and ammonium acetate is (0.8-1.2):(1.8-2.2):(1.8-2.2):(0.6-1.0).

4. A method for producing an intrinsically black polyimide, characterized by, The intrinsic black polyimide material is prepared by condensation polymerization of diamines and dianhydrides in a high-boiling polar solvent, followed by imidization and separation; the diamines comprise at least 10%-50% of the imidazole ring diamine monomer having a structure as shown in formula (I) by weight:

5. The preparation method according to claim 4, characterized in that, The diamines further comprise one of diamino diphenyl ether, diamino diphenyl and diamino diphenyl methane; and / or, the dianhydrides comprise one of diphenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and bisphenol A type diether dianhydride; and / or, the molar ratio of the diamines to the dianhydrides is 1:1; and / or, the condensation polymerization of diamines and dianhydrides is carried out at 20-30℃; and / or, the high-boiling polar solvent comprises one or more of N-methyl pyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide; and / or, the condensation polymerization is carried out in anhydrous high-boiling polar solvent for 4-36 hours; and / or, the imidization comprises thermal imidization or chemical imidization.

6. The preparation method according to claim 4 or 5, characterized in that, The intrinsic black polyimide material comprises an intrinsic black polyimide film or an intrinsic black polyimide powder.

7. The preparation method according to claim 6, characterized in that, The intrinsic black polyimide film is prepared by coating a polyamic acid solution prepared by condensation polymerization of diamines and dianhydrides in a high-boiling polar solvent, followed by thermal imidization at 80-350℃; and / or, the intrinsic black polyimide powder is prepared by chemical imidization of a polyamic acid solution prepared by condensation polymerization of diamines and dianhydrides in a high-boiling polar solvent, followed by dilution of the polyamic acid solution, addition of a dehydrating agent and a catalyst.

8. The preparation method according to claim 7, characterized in that, The dehydrating agent comprises one of acetic anhydride, propionic anhydride and butyric anhydride; and / or, the catalyst comprises one of trimethylamine, triethylamine and tripropylamine; and / or, the molar ratio of the dehydrating agent to the catalyst is (2-4):

1.

9. An intrinsically black polyimide material produced by the production method according to any one of claims 4 to 8, characterized in that, The structure of the molecular chain is as shown in formula (II): ###0002### In formula (II), m:n is (1:9)-(1:1); and / or, the optical transmittance of the intrinsic black polyimide material in the visible light band (380-750 nm) is ≤10%; and / or, the thickness of the intrinsic black polyimide film is 5-200 μm.

10. Use of an intrinsically black polyimide material produced according to the production process according to any one of claims 4 to 8 or of an intrinsically black polyimide material according to claim 9, characterized in that The intrinsic black polyimide material is used in any of the following fields: flexible circuit substrate or packaging material in the field of microelectronics, wafer processing carrier or photolithography mask in the field of semiconductors, high-temperature resistant insulation film or satellite thermal control material in the field of aerospace.

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