A polymer for black matrix, its preparation method and application

Abstract

The application discloses a polymer for a black matrix, which is prepared by the following steps: reacting a dianhydride monomer and an esterification reagent to obtain an intermediate, and then reacting the intermediate, a diamine monomer and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone. The polymer has unique structural characteristics, high OD value, good mechanical and thermal properties and photoetching performance, and can better meet the requirements of the industry for the performance of the black matrix when the polymer is applied to the black matrix. Meanwhile, the application also discloses a preparation method and application of the polymer, and the preparation method is simple in process and convenient for industrial popularization and application. The application of the polymer not only provides a new polymer selection for the black matrix, but also can significantly improve the mechanical and thermal properties of the black matrix.

Description

Technical Field

[0001] This invention relates to a polymer for black matrix, particularly an intrinsic resin-based black matrix polymer with high OD value, good mechanical and thermal properties and photolithography properties, its preparation method and uses. Background Technology

[0002] LCD photoresist is a technology-intensive industry with high technological barriers. LCD photoresist includes color photoresist and black photoresist.

[0003] In recent years, with the rapid development of liquid crystal display technology, people have high requirements for the contrast ratio of the devices. A black matrix is ​​placed in the color filter and the dot gap. The black matrix plays a role in blocking light and building a framework for the subsequent coating of red, green and blue photoresists. The quality of the black matrix directly affects the color rendering performance of the color filter.

[0004] To improve the contrast of liquid crystal displays, chromium is used in the black matrix, primarily through chromium deposition on the surface of a glass substrate followed by etching to form patterns. While this method results in high optical density and strong mechanical properties in the black matrix, it also presents challenges such as high cost, the high reflectivity of chromium, and environmental pollution from chromium-containing wastewater. Subsequently, researchers proposed using pigments to prepare photoresist compositions with black matrices. However, the addition of pigments to the photoresist makes it difficult for the pigment to dissolve in the developer, resulting in long development times, poor development effects, and an inability to obtain high-resolution patterns. The introduction of carbon materials and organic dyes significantly reduces the electrical insulation properties of the black matrix. Although some researchers have used non-carbon black colored pigments to prepare black matrices, the poor light shielding of colored pigments necessitates high mixing ratios in the black matrix photoresist compositions. This increases the viscosity of the composition and reduces the strength of the formed film.

[0005] Therefore, extensive research is needed to develop an intrinsic resin-based black matrix to circumvent the aforementioned shortcomings, and to further provide theoretical and technical support and impetus for the domestic production of black matrix photoresists. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a polymer with better mechanical, thermal, and photolithographic properties for use in black matrix applications. Furthermore, this invention also provides a method for preparing the polymer and its applications.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: a polymer, wherein the polymer has the following structural formula:

[0008]

[0009] Where R is H or At least one of the following; n is an integer from 8 to 40.

[0010] The polymer described in this invention has unique structural characteristics, can form high-resolution patterns, has excellent mechanical and thermal properties, and can be used as a positive photoresist for alkaline water development. When applied to a black matrix, it can improve the performance of the black matrix.

[0011] Furthermore, this invention also provides a method for preparing the aforementioned polymer that has simple process steps and is easy to implement industrially. To achieve this objective, the technical solution adopted by this invention is: a method for preparing the polymer as described above, the method comprising the following steps:

[0012] (1) The dianhydride monomer, esterification reagent and acyl chloride reagent are reacted in solvent 1 to obtain the intermediate;

[0013] (2) The intermediate obtained in step (1) is reacted with the diamine monomer and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone in solvent 2 to obtain the polymer.

[0014] The polymer preparation method provided by this invention first reacts a dianhydride monomer and an esterification reagent in solvent 1 to obtain an intermediate, and then reacts the obtained intermediate with a diamine monomer and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone. This method can rapidly and efficiently prepare a polymer with the unique structural characteristics described above, and the preparation method has simple process steps.

[0015] In the preparation method of the polymer of the present invention, the structural formula of the 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone is shown below:

[0016]

[0017] In the preparation method of the polymer described in this invention, the 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone can be purchased directly or prepared using conventional techniques in the art. The preparation methods of the 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone include, but are not limited to, the following two:

[0018] (1) In the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8 dihydroxy-9,10-anthraquinone is nitrated to 1,8 dihydroxy-2,4,5,7 tetranitro-9,10-anthraquinone, and then the nitro group is reduced to an amino group to obtain 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone.

[0019] (2) In the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8 dihydroxy-4,5-dinitro-9,10-anthraquinone is nitrated to 1,8 dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and then the nitro group is reduced to an amino group to obtain 1,8 dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.

[0020] As a preferred embodiment of the polymer preparation method of the present invention, step (1) is as follows: reacting the dianhydride monomer and the esterification reagent in solvent 1 to obtain a reaction solution; adding the acyl chloride reagent dropwise to the reaction solution under nitrogen atmosphere and ice bath conditions, and obtaining an intermediate after the addition is complete.

[0021] In a preferred embodiment of the polymer preparation method of the present invention, the molar ratio of dianhydride monomer to esterification reagent in step (1) is 1:1 to 1:2. In a more preferred embodiment of the polymer preparation method of the present invention, the molar ratio of dianhydride monomer to esterification reagent in step (1) is 1:2.

[0022] In a preferred embodiment of the polymer preparation method of the present invention, the reaction temperature of the dianhydride monomer and the esterification reagent in solvent 1 in step (1) is 30–90°C. In a more preferred embodiment of the polymer preparation method of the present invention, the reaction temperature of the dianhydride monomer and the esterification reagent in solvent 1 in step (1) is 60°C.

[0023] In a preferred embodiment of the polymer preparation method of the present invention, the reaction time of the dianhydride monomer and the esterification agent in solvent 1 in step (1) is 6-24 h. In a more preferred embodiment of the polymer preparation method of the present invention, the reaction time of the dianhydride monomer and the esterification agent in solvent 1 in step (1) is 10 h.

[0024] In a preferred embodiment of the polymer preparation method of the present invention, the temperature of the ice bath in step (1) is 5-10°C. In a more preferred embodiment of the polymer preparation method of the present invention, the temperature of the ice bath in step (1) is 5°C.

[0025] In a preferred embodiment of the polymer preparation method of the present invention, the molar ratio of the acyl chloride reagent to the dianhydride monomer in step (1) is 2:1 to 2.5:1. In a more preferred embodiment of the polymer preparation method of the present invention, the molar ratio of the acyl chloride reagent to the dianhydride monomer in step (1) is 2.2:1.

[0026] In a preferred embodiment of the polymer preparation method of the present invention, the dropping rate of the acyl chloride reagent in step (1) is 1 to 4 drops / second. In a more preferred embodiment of the polymer preparation method of the present invention, the dropping rate of the acyl chloride reagent in step (1) is 1 drop / second.

[0027] In a preferred embodiment of the polymer preparation method of the present invention, solvent 1 in step (1) is at least one selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran. In a more preferred embodiment of the polymer preparation method of the present invention, solvent 1 in step (1) is N-methylpyrrolidone.

[0028] In a preferred embodiment of the polymer preparation method of the present invention, the acyl chloride reagent in step (1) is at least one selected from SOCl2, AlCl3, BF3, SbCl5, FeBr3, FeCl3, SnCl4, TiCl4, and ZnCl2. In a more preferred embodiment of the polymer preparation method of the present invention, the acyl chloride reagent in step (1) is SOCl2.

[0029] In a preferred embodiment of the polymer preparation method of the present invention, the esterification agent in step (1) is at least one selected from n-butanol, ethanol, isopropanol, n-propanol, tert-butanol, and methanol. In a more preferred embodiment of the polymer preparation method of the present invention, the esterification agent in step (1) is n-butanol.

[0030] In a preferred embodiment of the polymer preparation method of the present invention, the dianhydride monomer in step (1) is at least one selected from the following: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, diphenyl sulfide dianhydride, and bisphenol A type diether dianhydride. In a more preferred embodiment of the polymer preparation method of the present invention, the dianhydride monomer in step (1) is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride.

[0031] In a preferred embodiment of the polymer preparation method of the present invention, the intermediate has the following structural formula:

[0032] Where R is H or At least one of them.

[0033] In a preferred embodiment of the polymer preparation method of the present invention, the molar ratio of diamine monomer, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and intermediate in step (2) is: diamine monomer: 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone: intermediate = 1:1:2 to 1:1:4. In a more preferred embodiment of the polymer preparation method of the present invention, the molar ratio of diamine monomer, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and intermediate in step (2) is: diamine monomer: 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone: intermediate = 1:1:2.

[0034] In a preferred embodiment of the polymer preparation method of the present invention, the diamine monomer in step (2) is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole The diamine monomer is selected from at least one of the following: azole, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzoazole), 2,2'-p-phenyl-bis(6-aminobenzoazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine, and 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid. In a more preferred embodiment of the polymer preparation method of the present invention, the diamine monomer in step (2) is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0035] In a preferred embodiment of the polymer preparation method of the present invention, the dianhydride monomer in step (1) is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and the diamine monomer in step (2) is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0036] In a preferred embodiment of the polymer preparation method of the present invention, solvent 2 in step (2) is at least one selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran. In a more preferred embodiment of the polymer preparation method of the present invention, solvent 2 in step (2) is N-methylpyrrolidone.

[0037] In a preferred embodiment of the polymer preparation method of the present invention, the reaction temperature in step (2) is 15-35°C. In a more preferred embodiment of the polymer preparation method of the present invention, the reaction temperature in step (2) is 25°C.

[0038] In a preferred embodiment of the polymer preparation method of the present invention, the reaction time in step (2) is 3-8 hours. In a more preferred embodiment of the polymer preparation method of the present invention, the reaction time in step (2) is 6 hours.

[0039] Finally, the present invention also provides an application of a polymer with the structural characteristics described above in the preparation of a black matrix.

[0040] The polymer provided by this invention, due to its unique structural characteristics, can form high-resolution patterns, has excellent mechanical and thermal properties, and can be used as a positive photoresist for alkaline water development. When applied to a black matrix, it can improve the performance of the black matrix.

[0041] The preparation method of the polymer described in this invention uses readily available raw materials, and the preparation steps and process conditions are simple, making it easy to promote and apply industrially.

[0042] The application of the polymer described in this invention in the preparation of black matrices not only provides a new polymer selection for black matrices, but also significantly improves the mechanical and thermal properties of black matrices. Attached Figure Description

[0043] Figure 1 The structural formula of the polymer described in this invention is as follows;

[0044] Figure 2 The structural reaction formula is an embodiment of the polymer preparation method described in this invention;

[0045] Figure 3 This is a gel permeation chromatography elution curve of the polymer described in Example 1 of the present invention;

[0046] Figure 4 This is a statistical result graph of the molecular weight of the polymer described in Example 1 of the present invention, obtained by gel permeation chromatography.

[0047] Figure 5 This is a gel permeation chromatography elution curve of the polymer described in Example 2 of the present invention;

[0048] Figure 6 This is a statistical result graph of the molecular weight of the polymer described in Example 2 of the present invention, obtained by gel permeation chromatography.

[0049] Figure 7 This is a gel permeation chromatography elution curve of the polymer described in Example 3 of the present invention;

[0050] Figure 8 This is a statistical result graph of the molecular weight of the polymer described in Example 3 of the present invention, obtained by gel permeation chromatography.

[0051] Figure 9 This is a gel permeation chromatography elution curve of the polymer described in Example 4 of the present invention;

[0052] Figure 10 This is a statistical result graph of the molecular weight of the polymer described in Example 4 of the present invention, obtained by gel permeation chromatography.

[0053] Figure 11 This is a gel permeation chromatography elution curve of the polymer described in Example 5 of the present invention;

[0054] Figure 12 This is a statistical result graph of the molecular weight of the polymer described in Example 5 of the present invention, obtained by gel permeation chromatography.

[0055] Figure 13 This is a gel permeation chromatography elution curve of the polymer described in Example 6 of the present invention;

[0056] Figure 14 This is a statistical result graph of the molecular weight of the polymer described in Example 6 of the present invention, obtained by gel permeation chromatography.

[0057] Figure 15 This is a gel permeation chromatography elution curve of the polymer described in Example 7 of the present invention;

[0058] Figure 16 This is a statistical result graph of the molecular weight of the polymer described in Example 7 of the present invention, obtained by gel permeation chromatography.

[0059] Figure 17 This is a gel permeation chromatography elution curve of the polymer described in Example 8 of the present invention;

[0060] Figure 18 This is a statistical result graph of the molecular weight of the polymer described in Example 8 of the present invention, obtained by gel permeation chromatography.

[0061] Figure 19 This is a gel permeation chromatography elution curve of the polymer described in Example 9 of the present invention;

[0062] Figure 20 This is a statistical result graph of the molecular weight of the polymer described in Example 9 of the present invention, obtained by gel permeation chromatography.

[0063] Figure 21 This is a gel permeation chromatography elution curve of the polymer described in Example 10 of the present invention;

[0064] Figure 22This is a statistical result graph of the molecular weight of the polymer described in Example 10 of the present invention, obtained by gel permeation chromatography.

[0065] Figure 23 The graph shows the test results of the thermal properties of the polymer described in Example 1 of this invention.

[0066] Figure 24 This is a test image of the photolithographic performance of the polymer described in Example 1 of the present invention;

[0067] Figure 25 This is another photolithographic performance test image of the polymer described in Example 1 of the present invention;

[0068] Figure 26 This is another photolithographic performance test image of the polymer described in Example 1 of the present invention;

[0069] Figure 27 This is a photolithographic performance test image of the polymer described in Example 1 of the present invention;

[0070] Figure 28 This is the NMR spectrum of the polymer described in Example 8 of the present invention. Detailed Implementation

[0071] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0072] The structural formula of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone described in the following examples is as follows:

[0073] .

[0074] The 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone was prepared by one of the following two methods:

[0075] (1) In the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8 dihydroxy-9,10-anthraquinone is nitrated to 1,8 dihydroxy-2,4,5,7 tetranitro-9,10-anthraquinone, and then the nitro group is reduced to an amino group to obtain 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone.

[0076] (2) In the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8 dihydroxy-4,5-dinitro-9,10-anthraquinone is nitrated to 1,8 dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and then the nitro group is reduced to an amino group to obtain 1,8 dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.

[0077] Either of the two methods described above can be used to prepare the 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone described in this application, as detailed in CN202110708909.2. Furthermore, the acquisition of the 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone includes, but is not limited to, the preparation using the two methods described above. Those skilled in the art can obtain it using other conventional preparation methods or other conventional approaches.

[0078] This invention discloses a polymer that can be used in black matrix applications, the structural formula of which is shown in the attached figure. Figure 1 As shown.

[0079] A synthetic route diagram of one embodiment of the polymer described in this invention is attached. Figure 2 As shown, the preparation method of the polymer specifically includes the following steps:

[0080] (1) The dianhydride monomer and the esterification reagent were reacted in solvent 1 to obtain a reaction solution; under nitrogen atmosphere and ice bath conditions, the acyl chloride reagent was added dropwise to the reaction solution. After the addition was completed, an intermediate was obtained.

[0081] The molar ratio of the dianhydride monomer to the esterification reagent is 1:1 to 1:2;

[0082] Solvent 1 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran;

[0083] The reaction temperature of the dianhydride monomer and the esterification reagent in solvent 1 is 30–90 °C.

[0084] The reaction time of the dianhydride monomer and the esterification reagent in solvent 1 is 6-24 h.

[0085] The temperature of the ice bath is 5–10°C;

[0086] The molar ratio of the acyl chloride reagent to the dianhydride monomer is 2:1 to 2.5:1;

[0087] The dropping rate of the acyl chloride reagent is 1 to 4 drops / second;

[0088] The acyl chloride reagent is at least one selected from SOCl2, AlCl3, BF3, SbCl5, FeBr3, FeCl3, SnCl4, TiCl4, and ZnCl2;

[0089] The dianhydride monomer is at least one of the following: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, diphenyl sulfide dianhydride, and bisphenol A type diether dianhydride.

[0090] The esterification reagent is at least one selected from n-butanol, ethanol, isopropanol, n-propanol, tert-butanol, and methanol.

[0091] (2) The intermediate obtained in step (1) is reacted with the diamine monomer and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone in solvent 2 to obtain the polymer;

[0092] The molar ratio of the diamine monomer, 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone, and intermediate is: diamine monomer: 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone: intermediate = 1:1:2 to 1:1:4;

[0093] The diamine monomer is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-5-aminobenzoxazole, etc. At least one of the following: 1,4-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzoazole), 2,2'-p-phenyl-bis(6-aminobenzoazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine, and 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid;

[0094] The solvent 2 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran.

[0095] The structural formula of the intermediate obtained in step (1) above is:

[0096] Where R is H or At least one of them.

[0097] The reaction temperature in step (2) is 15-35℃;

[0098] The reaction time for step (2) is 3-8 hours.

[0099] Example 1

[0100] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0101] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 60°C under a nitrogen atmosphere for 6 hours to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 5°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0102] (2) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and an intermediate in a molar ratio of 1:1:4, add them to N,N-dimethylformamide, and react at 25°C for 6 hours to obtain the reaction product; uniformly introduce the obtained reaction product into deionized water, let it stand to separate into layers, remove the upper layer, break up the resin, soak and wash it in deionized water, filter it, repeat the process several times, and dry it to obtain solid resin, which is the polymer described in this example.

[0103] The structural formula of the polymer obtained in this embodiment is:

[0104]

[0105] Example 2

[0106] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0107] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 70°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 6°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0108] (2) Take 2,2-bis(4-hydroxy-3-aminophenyl)propane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and intermediate in a molar ratio of 1:1:2 and add them to N-methylpyrrolidone. React at 25°C for 6 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times, and the resin is dried to obtain a solid resin, which is the polymer described in this example.

[0109] The structural formula of the polymer obtained in this embodiment is:

[0110]

[0111] Example 3

[0112] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0113] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:1 and add them to N,N-dimethylacetamide. React in an oil bath at 60°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 5°C, add SbCl5 dropwise to the reaction solution. The molar ratio of SbCl5 to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2.1:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0114] (2) Take 1,4-bis(4-aminophenoxy)benzene, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and intermediate in a molar ratio of 1:1:2 and add them to N-methylpyrrolidone. React at 25°C for 6 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times, and the resin is dried to obtain the solid resin, which is the polymer described in this example.

[0115] The structural formula of the polymer obtained in this embodiment is:

[0116]

[0117] Example 4

[0118] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0119] (1) Take 3,3',4,4'-benzophenone tetracarboxylic dianhydride and ethanol in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 80°C under a nitrogen atmosphere for 8 hours to obtain a reaction solution. Under an ice bath at 7°C under a nitrogen atmosphere, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-benzophenone tetracarboxylic dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0120] (2) Take 3,3'-dihydroxybenzidine, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and intermediate in a molar ratio of 1:1:3, add them to dimethyl sulfoxide, and react at 25°C for 6 hours to obtain the reaction product; uniformly introduce the obtained reaction product into deionized water, let it stand to separate into layers, remove the upper layer, break up the resin, replace it with deionized water for soaking and washing, filter, repeat several times, and dry it to obtain solid resin; that is, the polymer described in this example.

[0121] The structural formula of the polymer obtained in this embodiment is:

[0122]

[0123] Example 5

[0124] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0125] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-propanol in a molar ratio of 1:2 and add them to N,N-dimethylformamide. React in an oil bath at 90°C for 10 hours under a nitrogen atmosphere to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 5°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0126] (2) Take 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and intermediate in a molar ratio of 1:1:4, add them to N-methyl-2-pyrrolidone, and react at 15°C for 6 hours to obtain the reaction product; uniformly introduce the obtained reaction product into deionized water, let it stand to separate into layers, remove the upper layer, break up the resin, replace it with deionized water for soaking and washing, filter, repeat several times, and dry it to obtain solid resin, which is the polymer described in this example.

[0127] The structural formula of the polymer obtained in this embodiment is:

[0128]

[0129] Example 6

[0130] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0131] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and methanol in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 60°C for 12 hours under a nitrogen atmosphere to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 10°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2:1. After the addition is completed at 4 drops / second, the intermediate is obtained.

[0132] (2) Take 1,4-bis(3-aminophenoxy)benzene, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and intermediate in a molar ratio of 1:1:4, add them to N-methylpyrrolidone, and react at 35°C for 6 hours to obtain the reaction product; uniformly introduce the obtained reaction product into deionized water, let it stand to separate into layers, remove the upper layer, break up the resin, replace it with deionized water for soaking, washing and filtering, repeat several times, and dry it to obtain solid resin, which is the polymer described in this example.

[0133] The structural formula of the polymer obtained in this embodiment is:

[0134]

[0135] Example 7

[0136] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0137] (1) Take 3,3,4,4-diphenylsulfone tetracarboxylic acid dianhydride and n-butanol in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 70°C for 24 hours under a nitrogen atmosphere to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 5°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3,4,4-diphenylsulfone tetracarboxylic acid dianhydride is 2.5:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0138] (2) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and intermediate in a molar ratio of 1:1:3 and add them to N-ethyl-2-pyrrolidone. React at 25°C for 8 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the resin is dried to obtain the solid resin, which is the polymer described in this example.

[0139] The structural formula of the polymer obtained in this embodiment is:

[0140]

[0141] Example 8

[0142] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0143] (1) Take 3,3,4,4-diphenylsulfone tetracarboxylic acid dianhydride and n-butanol in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 60°C under a nitrogen atmosphere for 12 hours to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 6°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3,4,4-diphenylsulfone tetracarboxylic acid dianhydride is 2:1. After the addition is completed at 3 drops / second, an intermediate is obtained.

[0144] (2) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and intermediate in a molar ratio of 1:1:2 and add them to N-methylpyrrolidone. React at 15°C for 8 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the resin is dried to obtain the solid resin, which is the polymer described in this example.

[0145] The structural formula of the polymer obtained in this embodiment is:

[0146]

[0147] Example 9

[0148] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0149] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and isopropanol in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 30°C under a nitrogen atmosphere for 6 hours to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 10°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0150] (2) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and intermediate in a molar ratio of 1:1:2 and add them to N,N-dimethylformamide. React at 25°C for 3 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the resin is dried to obtain the solid resin, which is the polymer described in this example.

[0151] The structural formula of the polymer obtained in this embodiment is:

[0152]

[0153] Example 10

[0154] One embodiment of the polymer of the present invention includes the following steps in its preparation method:

[0155] (1) Take diphenyl sulfide dianhydride and n-butanol in a molar ratio of 1:1 and add them to N-methylpyrrolidone. React in an oil bath at 80°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 8°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to diphenyl sulfide dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0156] (2) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and intermediate in a molar ratio of 1:1:4 and add them to N-methylpyrrolidone. React at 25°C for 6 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times, and the resin is dried to obtain the solid resin, which is the polymer described in this example.

[0157] The structural formula of the polymer obtained in this embodiment is:

[0158]

[0159] Example 11

[0160] Gel permeation chromatography (GPC) detection test of the polymer described in this invention

[0161] The polymers described in Examples 1-10 were used as test subjects. Gel permeation chromatography (GPC) data for each group of polymers were tested. The test method was as follows: During the experiment, the column was filled with a solvent containing the sample to be tested, ensuring it occupied all voids between the carrier particles and the cavities within the particles. Then, a sample solution prepared with the same solvent was added from the column head, followed by elution with the same solvent. The eluent was collected at the micro-end of the column, and the volume and concentration of the eluent were calculated. The total volume of the collected eluent was called the elution volume. The elution volume of the solute is related to its molecular weight; the larger the molecular weight, the smaller the elution volume. If the sample is polydisperse, a series of fractions with decreasing molecular weights can be collected according to the order of elution.

[0162] The elution curve of the polymer described in Example 1 is attached. Figure 3As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 4 As shown.

[0163] The elution curve of the polymer described in Example 2 is attached. Figure 5 As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 6 As shown.

[0164] The elution curve of the polymer described in Example 3 is attached. Figure 7 As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 8 As shown.

[0165] The elution curve of the polymer described in Example 4 is attached. Figure 9 As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 10 As shown.

[0166] The elution curve of the polymer described in Example 5 is attached. Figure 11 As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 12 As shown.

[0167] The elution curve of the polymer described in Example 6 is attached. Figure 13 As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 14 As shown.

[0168] The elution profile of the polymer described in Example 7 is attached. Figure 15 As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 16 As shown.

[0169] The elution curve of the polymer described in Example 8 is attached. Figure 17 As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 18 As shown.

[0170] The elution curve of the polymer described in Example 9 is attached. Figure 19 As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 20 As shown.

[0171] The elution profile of the polymer described in Example 10 is attached. Figure 21 As shown in the attached figure, the molecular weight statistics of this polymer are as follows. Figure 22 As shown.

[0172] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution index (PDI) of the polymers described in Examples 1-10 are shown in Table 1 below:

[0173] Table 1. Detection results of Mw, Mn, and PDI of the polymers obtained in Examples 1-10.

[0174] Group Mw Mn PDI Example 1 30171 12873 2.3 Example 2 14114 9191 1.5 Example 3 55298 15923 3.5 Example 4 26268 12063 2.2 Example 5 21758 12510 1.7 Example 6 23232 12624 1.8 Example 7 64294 30588 2.1 Example 8 37505 23908 1.6 Example 9 14593 9429 1.5 Example 10 13730 8882 1.5

[0175] Example 12

[0176] Mechanical and thermal property tests of the polymer described in this invention

[0177] 1. Mechanical properties of the polymer described in this invention

[0178] The polymers described in Examples 1-10 and Comparative Examples 1-4 were used as test subjects to test the mechanical properties of the polymers obtained in each group. The polymers described in Comparative Examples 1-4 are as follows:

[0179] The preparation method of the polymer described in Comparative Example 1 includes the following steps:

[0180] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 60°C under a nitrogen atmosphere for 6 hours to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 5°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0181] (2) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diaminodiphenyl ether and the intermediate obtained in step (1) in a molar ratio of 1:1:4 and add them to N,N-dimethylformamide. React at 25°C for 6 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times, and the solid resin is obtained by vacuum drying, which is the polymer described in this comparative example.

[0182] The polymer structure described in Comparative Example 1 is as follows:

[0183]

[0184] The preparation method of the polymer described in Comparative Example 2 includes the following steps:

[0185] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 60°C under a nitrogen atmosphere for 6 hours to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 5°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0186] (2) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diaminodiphenyl ether and the intermediate obtained in step (1) in a molar ratio of 1:1:4 and add them to N,N-dimethylformamide. React at 25°C for 6 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times, and the solid resin is obtained by vacuum drying, which is the polymer described in this comparative example.

[0187] The structural formula of the polymer described in Comparative Example 2 is:

[0188]

[0189] The preparation method of the polymer described in Comparative Example 3 includes the following steps:

[0190] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:1.2 and add them to N-methylpyrrolidone. React in an oil bath at 60°C under a nitrogen atmosphere for 6 hours to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 5°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0191] (2) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and the intermediate obtained in step (1) in a molar ratio of 1:1:4, add them to N,N-dimethylformamide, and react at 25°C for 6 hours to obtain the reaction product; uniformly introduce the obtained reaction product into deionized water, let it stand to separate into layers, remove the upper layer, break up the resin, replace it with deionized water for soaking, washing and filtering, repeat several times, and dry it to obtain solid resin, which is the polymer described in this comparative example.

[0192] The structural formula of the polymer described in Comparative Example 3 is:

[0193]

[0194] The preparation method of the polymer described in Comparative Example 4 includes the following steps:

[0195] (1) Take 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:1.5 and add them to N-methylpyrrolidone. React in an oil bath at 60°C under a nitrogen atmosphere for 6 hours to obtain a reaction solution. Under a nitrogen atmosphere and an ice bath at 5°C, add thionyl chloride dropwise to the reaction solution. The molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is 2:1. After the addition is completed at 1 drop / second, an intermediate is obtained.

[0196] (2) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and the intermediate obtained in step (1) in a molar ratio of 1:1:4 and add them to N,N-dimethylformamide. React at 25°C for 6 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the resin is dried to obtain the solid resin, which is the polymer described in the comparative example.

[0197] The structural formula of the polymer described in Comparative Example 4 is:

[0198]

[0199] The polymers from Examples 1-10 and Comparative Examples 1-4 were respectively mixed with carbon black particles to obtain photoresist solutions. The mechanical properties of each group were then tested. The specific test methods were as follows:

[0200] OD value test: Place the black sample under the optical densitometer, zero it first and then measure the OD value. Move the position of the photoresist coating and measure four times, and take the average value.

[0201] Tensile property test:

[0202]

[0203] CTE test:

[0204]

[0205] DMA test:

[0206]

[0207]

[0208] The test results are shown in Table 2.

[0209] Table 2 shows the mechanical test results of the polymers described in Examples 1-10.

[0210]

[0211] As shown in Table 2, compared with Comparative Examples 1 to 4, the polymers described in Examples 1 to 10 of the present invention all have high OD values ​​and good mechanical properties.

[0212] 2. Thermal properties of the polymer described in this invention

[0213] Using the polymer described in Example 1 as the test object, its thermal properties were tested. The specific test method is as follows:

[0214] Td test:

[0215]

[0216] The test results are attached. Figure 23 As shown.

[0217] From the appendix Figure 23 It is known that the polymer described in this invention has good thermal properties.

[0218] The polymers in Examples 2-10 have similar thermal properties, which will not be described again here.

[0219] Example 12

[0220] The photolithographic properties of the polymer described in this invention

[0221] Using the polymer described in Example 1 as the test object, the photolithography properties of the polymer of the present invention were tested. The specific test method is as follows:

[0222] The obtained polymer, solvent inhibitor, crosslinking agent, coupling agent, and solvent were stirred and mixed. The completely dissolved mixture was then pressure filtered to remove insoluble matter, and degassed under vacuum to obtain a photoresist solution. Exposure was then performed on a contact lithography machine (Shenzhen Lanxingyu Electronics Technology Co., Ltd., URE-2000 / 35), followed by alkaline development.

[0223] The test results are attached. Figures 24-27 As shown.

[0224] From the appendix Figures 24-27 It is known that the polymer described in this invention has a high-resolution pattern (5 μm).

[0225] The polymers in Examples 2-10 have similar photolithographic properties, which will not be described in detail here.

[0226] Example 13

[0227] NMR spectrum of the polymer described in this invention

[0228] Using the polymer described in Example 8 as the test object, the NMR spectrum of the polymer of the present invention was tested. The specific test method was as follows: clean the NMR tube, dry the sample and the NMR tube, transfer the sample into the NMR tube (the solution for NMR needs to be dissolved before transfer), and test on the instrument.

[0229] The test results are attached. Figure 28 As shown.

[0230] From the appendix Figure 28 It can be concluded that the polymer synthesis was successful.

[0231] Examples 2-10 have similar NMR spectra, which will not be described again here.

[0232] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polymer, characterized in that, The structural formula of the polymer is: 。 2. The method for preparing the polymer according to claim 1, characterized in that, The method includes the following steps: (1) The dianhydride monomer and the esterification reagent are reacted in solvent 1 to obtain a reaction solution; under nitrogen atmosphere and ice bath conditions, the acyl chloride reagent is added dropwise to the reaction solution. After the addition is complete, an intermediate is obtained. (2) The intermediate obtained in step (1) is reacted with the diamine monomer and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone in solvent 2 to obtain the polymer; In step (1), the molar ratio of the dianhydride monomer to the esterification reagent is 1:1 to 1:2; the dropping rate of the acyl chloride reagent is 1 to 4 drops / second; the reaction temperature of the dianhydride monomer and the esterification reagent in solvent 1 is 30 to 90 °C, and the reaction time is 6 to 24 h; the molar ratio of the acyl chloride reagent to the dianhydride monomer is 2:1 to 2.5:1; the acyl chloride reagent is at least one of SOCl2, AlCl3, SbCl5, FeCl3, SnCl4, TiCl4, and ZnCl2; and the esterification reagent is n-butanol. The dianhydride monomer is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride; The diamine monomer in step (2) is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

3. The method for preparing the polymer according to claim 2, characterized in that, Step (1) satisfies at least one of the following conditions: (1a) The temperature of the ice bath conditions is 5~10℃; (1b) The solvent 1 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran.

4. The method for preparing the polymer according to claim 2, characterized in that, The structural formula of the intermediate is: 。 5. The method for preparing the polymer according to claim 2, characterized in that, In step (2), the molar ratio of diamine monomer, 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone and intermediate is: diamine monomer: 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone: intermediate = 1:1:2~1:1:

4.

6. The method for preparing the polymer according to claim 2, characterized in that, Step (2) satisfies at least one of the following conditions: (2a) The solvent 2 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran; (2b) The reaction temperature in step (2) is 15-35 °C; (2c) The reaction time of step (2) is 3-8 h.

7. The use of the polymer prepared by the method according to claim 1 or any one of claims 2 to 6 in the preparation of a black matrix.

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