JP2023004893A - Anthraquinone derivative tetraamine monomer, intrinsic black polyimide derived therefrom, and method for preparing same - Google Patents

Abstract

To provide an intrinsic black polyimide that has good light shielding performance and excellent mechanical properties, thermal stability, and dielectric properties.SOLUTION: An anthraquinone derivative tetraamine monomer has a structure represented by following General formula I. Only two amine groups of the present anthraquinone derivative tetraamine monomer can undergo a polycondensation reaction, so a linear polymer can be obtained. Intrinsic black polyimide obtained from anthraquinone derivative tetraamine monomer has good light-shielding performance, excellent mechanical properties, thermal stability, and dielectric properties, and has a light transmittance in all wavelength bands of less than 1%.SELECTED DRAWING: Figure 3

Description

The present application relates to the technical field of organic synthesis, in particular, the present application relates to an anthraquinone derivative tetraamine monomer, a method for preparing anthraquinone derivative tetraamine monomer, an intrinsic black polyimide derived from said anthraquinone derivative tetraamine monomer, and said intrinsic black polyimide. relates to the preparation method of

Black polyimide (PI) film has characteristics such as opacity, low light absorption, low light transmittance and low light reflection coefficient, and has important application value in the following fields. (1) Flexible circuit board (FPC) substrate film: black can effectively block light and prevent competitors from cracking the circuit design; (2) Lithium battery: Insulation protection for lithium battery pack connection parts, black polyimide can block light and prevent oxidation of copper; (3) Wireless charging: Wireless charging can be used as coil insulation protection Ultra-thin black polyimide film adhesive is required, but currently black polyimide cannot meet the requirements, so ordinary polyimide is temporarily used, coated with carbon black; (4) Aerospace: satellite When used in antennas, it can eliminate or avoid various stray light interferences to imaging systems and sensors; as a light-absorbing film, it can be used to create optical fixed attenuators and optical terminators.

Currently, there are three main methods for preparing black PI films. (1) adding graphene, perylene black and other organic and inorganic fillers; (2) using special monomers to increase charge transfer complex formation of polyimide molecular chains. For example, Liu et al. (J Polym Res (2019) 26:171) used an electron-rich aromatic diamine monomer, 4,4′-diaminodiphenylamine (NDA), and PMDA to copolymerize, but 100% NDA was used, the color of the polymer was still not black. Therefore, the black color of polyimide due to conjugation is an unattainable black color, and the use of large amounts of special monomers increases the cost of black polyimide films. In addition, a Chinese invention patent application with publication number CN109180936A adopted the method of copolymerization with commercially available diamines to prepare a series of intrinsic black polyimides by adjusting the blending ratio of both. A Chinese invention patent application with publication number CN111574426A designed and synthesized a diamine monomer containing an isoindigo structure, and homopolymerized it with a commercially available dianhydride to prepare a series of intrinsic black polyimides.
However, the above black polyimide preparation method has some drawbacks as follows.

1. The preparation process is complicated and all require pre-modification of the filler to make it more uniformly dispersed in the PI matrix to avoid uneven mechanical properties and pinholes.

2. The introduction of inorganic fillers can improve the mechanical and thermal properties of PI films to some extent, but destroys the insulating properties and breaking strength of PI films, adversely affecting their applications in the electronics industry.

3. The introduction of organic pigments can avoid affecting the electrical properties of PI films, but the low thermal decomposition temperature prevents the use of PI films in high temperature areas, and is easily decomposed by environmental factors, resulting in poor weather resistance. poor.
4. Existing intrinsic black polyimides still lack light transmittance, and cannot be guaranteed to be less than 1% in the entire visible light band.
Therefore, there is a continuing need in the art to develop intrinsic black polyimides and methods for their preparation.

The object of the present application is to provide a novel anthraquinone derivative monomer with a high molar extinction coefficient, by introducing a plurality of auxiliary color groups into the anthraquinone structure and broadening the absorption wavelength, thereby solving the above technical problems. can be solved.
It is also an object of the present application to provide a method for preparing anthraquinone derivative tetraamine monomers.
It is also an object of the present application to provide intrinsic black polyimides synthesized by using anthraquinone derivative tetraamine monomers.
It is also an object of the present application to provide a method for preparing intrinsic black polyimide.

In order to solve the above technical problems, the present application provides the following technical solutions.
In a first aspect, the present application provides anthraquinone derivative tetraamine monomers characterized by having a structure represented by general formula I below.

In one embodiment, only two amine groups in the anthraquinone derivative tetraamine monomer can undergo polycondensation reactions, thus obtaining linear polymers.

In a second aspect, the present application provides a process for the preparation of an anthraquinone derivative tetraamine monomer according to the first aspect, the process comprising the steps of 1,8-dihydroxy-9 in the presence of concentrated sulfuric acid and concentrated nitric acid. ,10-anthraquinone is nitrated to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, followed by reduction of the nitro group to an amino group and 1,8-dihydroxy-2,4 , 5,7-tetraamino-9,10-anthraquinone.

In another embodiment, the present application provides a method for preparing an anthraquinone derivative tetraamine monomer according to the first aspect, the method comprising the steps of: 1,8-dihydroxy- Nitration of 4,5-dinitro-9,10-anthraquinone to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone followed by reduction of the nitro group to an amino group and 1, comprising obtaining 8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.

In a third aspect, the application includes structural units derived from the anthraquinone derivative tetraamine monomers, structural units derived from the diamine monomers, and structural units derived from the anhydride monomers of the first aspect. In the intrinsic black polyimide, the structural unit derived from the anthraquinone derivative tetraamine monomer is 4%-100 of the total number of moles of the structural unit derived from the anthraquinone derivative tetraamine monomer and the structural unit derived from the diamine monomer. % of intrinsic black polyimide. In a preferred embodiment, the structural unit derived from the anthraquinone derivative tetraamine monomer accounts for 4% to 80% of the total number of moles of the structural unit derived from the anthraquinone derivative tetraamine monomer and the structural unit derived from the di-amine monomer. occupy. In a preferred embodiment, the structural unit derived from the anthraquinone derivative tetraamine monomer accounts for 4% to 10% of the total number of moles of the structural unit derived from the anthraquinone derivative tetraamine monomer and the structural unit derived from the diamine monomer. Occupy

In one embodiment of the first aspect, the total number of moles of amine groups participating in the reaction of said anthraquinone derivative tetraamine monomer and said diamine monomer and the carboxylic anhydride groups participating in the reaction of said anhydride monomer are to the total molar ratio is 1:1. In this embodiment, due to the presence of intramolecular hydrogen bonds in the anthraquinone derivative tetraamine monomer, the amine groups at the ortho and para positions have different activities, and only the two ortho amine groups can participate in the copolymerization reaction. can.

In one embodiment of the first aspect, the anhydride monomers are 4,4′-(acetylene-1,2-diyl)diphthalic anhydride, pyromellitic dianhydride, 3,3′,4, 4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, 4,4'-oxydiphthalic anhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, naphthalene-1 , 4,5,8-tetracarboxylic dianhydride and diphenyl sulfide dianhydride.

In one embodiment of the first aspect, 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-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-aminobenzoxazole) and 2, one or more of 2′-p-phenyl-bis(6-aminobenzoxazole).
In a fourth aspect, the present application provides a method for preparing an intrinsic black polyimide according to the third aspect, characterized in that said method comprises the following steps.

(1) Under anhydrous and oxygen-free conditions, the anthraquinone derivative tetraamine monomer and the diamine monomer according to the first aspect are mixed in a predetermined weight ratio and stirred until dissolved to form a homogeneous solution, and then After adding the acid anhydride monomer and stirring and reacting in a cold water bath for a predetermined time, a black polyamic acid solution is obtained;
(2) imidizing a black polyamic acid solution to obtain an intrinsic black polyimide;

In one embodiment of the fourth aspect, the imidization of the black polyamic acid solution is carried out by uniformly applying the black polyamic acid solution to a dry and clean glass plate by an automatic film coating machine after defoaming, and then lifting the black polyamic acid solution. The imidization reaction is carried out by a thermal imidization method such that the temperature curing procedure is 80° C./3 hours, 100° C./1 hour, 200° C./2 hours, 300° C./4 hours.

Compared with the prior art, the beneficial effect of the present application is that the black polyimide of the present application has good light shielding performance, good mechanical properties, thermal stability and dielectric properties, and the light transmittance in the whole wavelength band is less than 1%.

1 shows the ultraviolet absorption spectrum of the anthraquinone derivative tetraamine monomer according to Example 1. FIG. 2 shows the infrared spectrum of the anthraquinone derivative tetraamine monomer according to Example 1. FIG. 3 shows the hydrogen nuclear magnetic spectrum of the anthraquinone derivative tetraamine monomer according to Example 1. FIG. FIG. 4 shows an optical photograph of the polyimide according to Example 3 on white A4 paper.

Black polyimide has aroused the interest of many research teams at home and abroad due to its broad potential application prospects. For example, a Chinese invention patent with publication number CN105860112B discloses that by blending a PI precursor polyamic acid (PAA) solution with a polyacrylonitrile solution, both the excellent mechanical properties of PI and an opaque black film after PAN pre-oxidation are achieved. It was disclosed that a black film with a A Chinese invention patent with publication number CN105482115B reported a method of adding a black filler such as carbon black or carbon fiber powder and a coupling agent to a polyamic acid solution, followed by degassing and casting to form a film. A Chinese invention patent application with publication number CN108017910A reported a method of adding carbon black pigment into a polyamic acid solution, adding a flocculant after filtering, then defoaming and casting to form a film. The Chinese invention patent application with publication number CN110387040A describes conductive nanoparticles such as transition metal nitrides, transition metal carbides, transition metal borides and noble metals, as well as graphene, carbon-based nanomaterials, black pigments, black dyes, etc. in polyamic acid solution. We reported a method of forming a film by adding it to, defoaming, and casting, and the shielding property was greatly improved. A Chinese invention patent application with publication number CN108976447A reported a method to prepare ultra-thin black polyimide films by adding carbon black with different particle sizes into a polyamic acid solution, followed by defoaming and coating.

Intrinsic black polyimide not only has excellent light-shielding properties, but also can improve mechanical, thermal, and electrical properties by adjusting the type and amount of monomer used. Therefore, it is of great importance to continuously develop new preparation methods for intrinsic black polyimides.
In one embodiment, the present application provides novel anthraquinone derivative tetraamine monomers having a structure represented by general formula I below.

In one embodiment, the present application provides a method for preparing the above anthraquinone derivative tetraamine monomer, the method comprising converting 1,8-dihydroxy-9,10-anthraquinone to 1,8-dihydroxy-9,10-anthraquinone in the presence of concentrated sulfuric acid and concentrated nitric acid. nitration to 8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone followed by reduction of the nitro group to an amino group and 1,8-dihydroxy-2,4,5,7-tetraamino -9,10-anthraquinone.

In another embodiment, a method for preparing an anthraquinone derivative tetraamine monomer comprises converting 1,8-dihydroxy-4,5-dinitro-9,10-anthraquinone to 1,8-dihydroxy in the presence of concentrated sulfuric acid and concentrated nitric acid. -2,4,5,7-tetranitro-9,10-anthraquinone followed by reduction of the nitro group to an amino group, 1,8-dihydroxy-2,4,5,7-tetraamino-9, including obtaining 10-anthraquinone.

In one embodiment, the application also provides an intrinsic black polyimide formed by reacting the above anthraquinone derivative tetraamine monomer, diamine monomer and anhydride monomer. In such embodiments, the content of the anthraquinone derivative tetraamine monomer is preferably 4%-100% of the total moles of all amine monomers. In a first aspect, when the content of the anthraquinone derivative tetraamine monomer is less than 4% of the total moles of all amine monomers, the prepared polyimide exhibits a yellow to dark green color instead of pure black. In another aspect, when the content of anthraquinone derivative tetraamine monomer exceeds 10% of the total moles of all amine monomers, the LAB value of the resulting intrinsic black polyimide film does not change significantly. Therefore, in one preferred embodiment, the content of anthraquinone derivative tetraamine monomer is preferably 4%-10% of the total moles of all amine monomers.

The present application also includes first reacting an anthraquinone derivative tetraamine monomer, a diamine monomer and an anhydride monomer to obtain a polyamic acid solution, and then imidizing the polyamic acid solution to obtain an intrinsic black polyimide. It relates to a method for preparing the above black intrinsic polyimide.
Example

The application is further described and explained below with reference to examples. Unless otherwise specified, all chemical raw materials used are commercially available. Those skilled in the art can appreciate that the following examples are merely illustrative.
In the examples below, the characterization methods used are as follows.
Hydrogen nuclear magnetic resonance spectrum ( ¹ H NMR):

Nuclear magnetic resonance ( ¹ H NMR) spectra of reaction products and intermediates were obtained on a Bruker AVANCE III HD 400/500, Germany. Sample preparation method: In a clean, dry glass NMR tube, completely dissolve approximately 10 mg of sample in approximately 0.5 mL of deuterated reagent. The highly soluble product dissolves in deuterated chloroform (CDCl ₃ ) as solvent at room temperature, while the less soluble product uses deuterated dimethyl sulfoxide (DMSO-d6) as solvent. DMSO-d6 tends to solidify at lower room temperature and needs to be blown with a hair dryer before adding the sample. When tested at room temperature, tetramethylsilane (TMS) is used as internal standard and the chemical shift is 0 ppm.
Fourier transform infrared spectroscopy (FT-IR):

In a dry environment, ATR mode of a Nicolet iS5 (ThermoFisher Scientific, Inc., USA) Fourier Transform Infrared Spectrometer (FTIR) was used for testing, and prior to testing, the monomer (4NADA) was first placed in a vacuum oven at 80°C. Leave it in for 2 hours to remove moisture. The scan range is set to 4000-650 cm ⁻¹ , the resolution is set to 2 cm ⁻¹ , the number of scans is set to 32, and the average value is automatically obtained.
Ultraviolet Visible Spectrum (UV-Vis):

The light transmittance of the intrinsic black polyimide film is analyzed with a Japan Shimadzu UV-2600 spectrophotometer, the scan range is set at 360-800 cm ⁻¹ . The UV absorbance of the monomer is also analyzed with a Nippon Shimadzu UV-2600 spectrophotometer to detect the absorbance of dilute solutions. The monomer concentration is 30 μM and the solvent of choice is N,N-dimethylformamide.
CIELAB color space:

The reflectance of the prepared intrinsic black polyimide film is tested with LAMBDA 950 UV/Vis/NIR spectrophotometer from PerkinElmer, USA. By combining the built-in conversion formulas with the relative spectral function distribution of the CIE standard illuminant D65 used and the CIE 1976 standard chromaticity observer, the L ^* , a ^* , b ^* parameter values are obtained by gamut conversion calculations. The illuminant employed is standard illuminant D65 and the observation angle is 10°.
Thermal Performance Analysis (TGA & DMA & TMA):

Thermogravimetric analysis of intrinsic black polyimide films was performed on a TA Discovery 550 Thermogravimetric Analyzer (TGA) under nitrogen protection, with a gas flow rate of 50 mL/min and a temperature of 20°C/min from room temperature to 120°C. After rising and dwelling for 15 minutes, the temperature was increased from 50°C to 800°C at 10°C/min.

Glass transition temperature (Tg) was performed on a TA Q800 dynamic thermomechanical analyzer (DMA) by cutting intrinsic black polyimide film into rectangular strips of equal width (0.5 cm) and setting the loading frequency to 1 Hz. , the temperature is increased from 30° C. to 500° C. at a rate of 5° C./min under nitrogen protection.

The thermal dimensional stability of intrinsic black polyimide films was analyzed on a TAQ 400 thermomechanical analyzer (TMA) in tensile mode by measuring the change in strip size with increasing temperature. Intrinsic black polyimide film was prepared into a long strip of uniform width (0.5 cm), static load was 0.05 N, heating rate was 10°C/min, heating range was room temperature to 400°C, nitrogen flow was 50 mL. / min. The programmed heating step is divided into two parts, the first step is heating at the same rate and then cooling to relieve residual internal stress in the film during thermal imidization, the second step is The steps record curve data for heating up to 400°C.
Mechanical property analysis:

The mechanical properties of the intrinsic black polyimide film were measured by a Sansi Taijie SUST CMT1104 electronic universal testing machine. The samples were cut into 1 cm wide rectangular strips, the pull speed was 5 mm/min, and multiple valid test results were averaged according to ASTM D882-02 test standard.
Dielectric performance analysis:

The dielectric properties of intrinsic black polyimide films were measured by a Canadian Keysight N5227B network analyzer, and rectangular samples with side lengths greater than 3*4 mm were prepared for dielectric constant and dielectric loss tests. After the sample was dried at 80° C. for 2 hours, it was placed on the sensor and the test frequency was selected for testing. The test frequencies were 24 GHz, 40 GHz, and 60 GHz, the sample thickness was 25 microns, and the medium was air.
Monomer Synthesis Example Example 1

Add 1,8-dihydroxy-9,10-anthraquinone (1.0 mmol) to a three-necked flask, add 5 ml of concentrated sulfuric acid and 4 ml of concentrated nitric acid at 0° C., stir vigorously mechanically for 4 hours, and add crushed ice. The solvent was removed by suction filtration and the solid material was washed with water/saturated sodium bicarbonate solution and dried in vacuo overnight to give yellow crude product 1.

The crude product 1 is purified by silica gel chromatography (short column) eluting with the eluent (methanol) to give the yellow product 1,8-dihydroxy-2,4,5,7-tetranitro-9,10 - an anthraquinone is obtained.

The above yellow product (1 mmol) was weighed and dissolved in ethanol in a flask, Na ₂ S.9H ₂ O (8 mmol) was weighed, dissolved to saturation with distilled water and added to the flask. The mixture was refluxed for 12 hours; after cooling to room temperature, it was poured into the prepared ice-water mixture with constant stirring. After filtration, washing with water and vacuum drying overnight gave the black desired product 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.

The ultraviolet absorption spectrum and infrared spectrum of the above monomer were measured, and the results are shown in FIGS. 1 and 2, respectively. As shown in FIG. 1, the monomer exhibits strong absorption in the visible light band of 400-700 nm, and at the same time, the half-width reaches nearly 150 nm. It becomes black. As shown in FIG. 2, the infrared absorption peaks at 3500-3200 cm ⁻¹ can belong to the ortho-amino group and the para-amino group in turn, and both the peak shift and the peak broadening are due to the intramolecular hydrogen bonding in the latter. This indicates that there is a difference in reactivity between the two amino groups. At the same time, the carbonyl peak appearing at 1567 cm ⁻¹ indicates that there are various hydrogen bonds within the molecule, that is, the carbonyl group forms intramolecular hydrogen bonds with the hydroxyl group and the para-amino group. Due to this unusual hydrogen bonding, the carbonyl peak that normally appears around 1700 cm ^-1 was lowered to 1567 cm ^-1 .
This activity difference between amino groups is also confirmed in FIG. 3, that is, the NMR peaks of the ortho-amino hydrogen appear at higher fields.
The molar extinction coefficient of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone according to Example 1 was also measured.

ここで、Ａは紫外分光光度計で測定される紫外吸光度、εはモル吸光係数、ｂは吸収セルの厚さ、ｃは測定しようとする液体のモル濃度である。 The method for calculating the molar extinction coefficient is as follows.
The molar absorption coefficient refers to the absorption coefficient at a concentration of 1 mol/L and is represented by ε. The calculation formula is as follows.

Here, A is the ultraviolet absorbance measured with an ultraviolet spectrophotometer, ε is the molar extinction coefficient, b is the thickness of the absorption cell, and c is the molar concentration of the liquid to be measured.

Therefore, when combined with the ultraviolet absorption spectrum of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, the molar extinction coefficient at the maximum absorption wavelength λmax is about 10 ⁵ L/(mol· cm), where the molarity of the liquid to be measured is 30 μM, the thickness of the absorption cell is 1 cm, the absorbance at the maximum absorption wavelength is 0.296, and the diluted solution is still dark blue. , indicating that the molar extinction coefficient is sufficiently strong.
Example 2

Add 1,8-dihydroxy-4,5-dinitro-9,10-anthraquinone (1.0 mmol) to a three-necked flask, add 3 ml of concentrated sulfuric acid and 2 ml of concentrated nitric acid at 0° C., and stir vigorously for 4 hours. After washing, it was poured into crushed ice, the solvent was removed by suction filtration, the solid material was washed with water/saturated sodium bicarbonate solution and dried in vacuo overnight to give yellow crude product 1.

The crude product 1 was dissolved in methanol and then recrystallized by adding cyclohexane to give the yellow product 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone.

The above yellow product (1 mmol) was weighed and dissolved in N,N-dimethylformamide in a flask, and 0.01 g of palladium on carbon was weighed and added to the flask. The mixture was refluxed and reacted under hydrogen atmosphere at standard atmospheric pressure for 12 hours; after cooling to room temperature, it was poured into prepared water with constant stirring. After filtration, washing with water and vacuum drying overnight gave the black desired product 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.
The ultraviolet absorption spectrum and infrared spectrum of the above monomer were measured, and the results are shown in FIGS. 1 and 2, respectively.
The purification and reduction means described above can be used interchangeably with the purification and reduction means of Example 1.

Preparation example of intrinsic black polyimide Example 3
This example relates to the synthesis of intrinsic black polyimide PI-1.

1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and ODA (4,4′-diaminodiphenyl ether) in a molar ratio of 4:96, and PMDA (pyromellitic dianhydride) A black polyimide film was prepared by the method) and had a solids content of 15.3%. The ratio of the total number of moles of amine groups participating in the reaction in the anthraquinone derivative tetraamine monomer and the diamine monomer to the total number of moles of carboxylic anhydride groups participating in the reaction in the acid anhydride monomer is 1: was 1.

In a 100 mL 3-neck round-bottom flask equipped with a nitrogen inlet, mechanical stirrer, and cold water bath, under conditions of sufficient water and oxygen exclusion and nitrogen protection, 0.36 mmol of the desired monomer, 5.64 mmol of ODA, and 10 ml of DMAc was added and stirred until dissolved to form a homogeneous solution; a total of 6 mmol of PMDA was added to the above solution three times, stirred in a cold water bath for 14 hours, reacted, and then reached a certain viscosity. A black polyamic acid solution with

After defoaming, the above polyamic acid solution was uniformly coated on a dry and clean glass plate using an automatic film coating machine, and imidization reaction was carried out by employing a thermal imidization method. The procedure for temperature programmed curing is as follows: 80°C/3 hours, 100°C/1 hour, 200°C/2 hours, 300°C/4 hours.
Example 4
This example relates to the synthesis of intrinsic black polyimide PI-2.

1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and ODA (4,4'-diaminodiphenyl ether) in a molar ratio of 6:94, and PMDA (pyromellitic dianhydride) A black polyimide film was prepared by the method) and had a solids content of 15.3%. The ratio of the total number of moles of amine groups participating in the reaction in the anthraquinone derivative tetraamine monomer and the diamine monomer to the total number of moles of carboxylic anhydride groups participating in the reaction in the acid anhydride monomer is 1: was 1.

In a 100 mL 3-neck round-bottom flask equipped with a nitrogen inlet, mechanical stirrer, and cold water bath, under conditions of sufficient water and oxygen exclusion and nitrogen protection, 0.36 mmol of the desired monomer, 5.64 mmol of ODA, and 10 ml of DMAc was added and stirred until dissolved to form a homogeneous solution; a total of 6 mmol of PMDA was added to the above solution three times, stirred in a cold water bath for 14 hours, reacted, and then reached a certain viscosity. A black polyamic acid solution with

After defoaming, the above polyamic acid solution was uniformly coated on a dry and clean glass plate using an automatic film coating machine, and imidization reaction was carried out by employing a thermal imidization method. The procedure for temperature programmed curing is as follows: 80°C/3 hours, 100°C/1 hour, 200°C/2 hours, 300°C/4 hours.
Example 5
This example relates to the synthesis of intrinsic black polyimide PI-3.

1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and ODA (4,4'-diaminodiphenyl ether) in a molar ratio of 8:92, and PMDA (pyromellitic dianhydride) A black polyimide film was prepared by the method) and had a solids content of 15.3%. The ratio of the total number of moles of amine groups participating in the reaction in the anthraquinone derivative tetraamine monomer and the diamine monomer to the total number of moles of carboxylic anhydride groups participating in the reaction in the acid anhydride monomer is 1: was 1.

In a 100 mL 3-neck round-bottom flask equipped with a nitrogen inlet, mechanical stirrer, and cold water bath, under conditions of sufficient water and oxygen exclusion and nitrogen protection, 0.36 mmol of the desired monomer, 5.64 mmol of ODA, and 10 ml of DMAc was added and stirred until dissolved to form a homogeneous solution; a total of 6 mmol of PMDA was added to the above solution three times, stirred in a cold water bath for 14 hours, reacted, and then reached a certain viscosity. A black polyamic acid solution with

After defoaming, the above polyamic acid solution was uniformly coated on a dry and clean glass plate using an automatic film coating machine, and imidization reaction was carried out by employing a thermal imidization method. The procedure for temperature programmed curing is as follows: 80°C/3 hours, 100°C/1 hour, 200°C/2 hours, 300°C/4 hours.
Example 6
This example relates to the synthesis of intrinsic black polyimide PI-4.

1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and ODA (4,4′-diaminodiphenyl ether) in a molar ratio of 10:90, and PMDA (pyromellitic dianhydride) A black polyimide film was prepared by the method) and had a solids content of 15.3%. The ratio of the total number of moles of amine groups participating in the reaction in the anthraquinone derivative tetraamine monomer and the diamine monomer to the total number of moles of carboxylic anhydride groups participating in the reaction in the acid anhydride monomer is 1: was 1.

In a 100 mL 3-neck round-bottom flask equipped with a nitrogen inlet, mechanical stirrer, and cold water bath, under conditions of sufficient water and oxygen exclusion and nitrogen protection, 0.36 mmol of the desired monomer, 5.64 mmol of ODA, and 10 ml of DMAc was added and stirred until dissolved to form a homogeneous solution; a total of 6 mmol of PMDA was added to the above solution three times, stirred in a cold water bath for 14 hours, reacted, and then reached a certain viscosity. A black polyamic acid solution with

After defoaming, the above polyamic acid solution was uniformly coated on a dry and clean glass plate using an automatic film coating machine, and imidization reaction was carried out by employing a thermal imidization method. The procedure for temperature programmed curing is as follows: 80°C/3 hours, 100°C/1 hour, 200°C/2 hours, 300°C/4 hours.
Example 7

1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and ODA (4,4′-diaminodiphenyl ether) in a molar ratio of 80:20, and PMDA (pyromellitic dianhydride) A black polyimide film was prepared by the method) and had a solids content of 15.3%. The ratio of the total number of moles of amine groups involved in the reaction of the tetraamine monomer and the diamine monomer to the total number of moles of the carboxylic acid anhydride groups involved in the reaction of the acid anhydride monomer is 1:1. there were.

In a 100 mL 3-neck round-bottom flask equipped with a nitrogen inlet, mechanical stirrer, and cold water bath, under conditions of sufficient water and oxygen exclusion and nitrogen protection, 0.36 mmol of the desired monomer, 5.64 mmol of ODA, and 10 ml of DMAc was added and stirred until dissolved to form a homogeneous solution; a total of 6 mmol of PMDA was added to the above solution three times, stirred in a cold water bath for 14 hours, reacted, and then reached a certain viscosity. A black polyamic acid solution with

After defoaming, the above polyamic acid solution was uniformly coated on a dry and clean glass plate using an automatic film coating machine, and imidization reaction was carried out by employing a thermal imidization method. The procedure for temperature programmed curing is as follows: 80°C/3 hours, 100°C/1 hour, 200°C/2 hours, 300°C/4 hours.

Compared to the intrinsic black polyimide of Example 6, the intrinsic black polyimide of Example 7 has lower optical properties, increased modulus, decreased elongation at break and tensile strength, and little change in dielectric properties. I didn't.
Comparative example 1
This example relates to the synthesis of PMDA-ODA type PI membranes.

A Kapton-type polyimide film was prepared with ODA (4,4'-diaminodiphenyl ether) and PMDA (pyromellitic dianhydride) in a molar ratio of 1:1 with a solids content of 15.1%. The ratio of the total number of moles of amine groups in the diamine monomer to the total number of moles of carboxylic anhydride groups in the anhydride monomer was 1:1.

To a 100 mL 3-necked round-bottom flask equipped with a nitrogen inlet, mechanical stirrer, and cold water bath, under conditions of sufficient water and oxygen exclusion and nitrogen protection, 6 mmol of ODA and 10 mL of DMAc were added to dissolve and homogenize. A total of 6 mmol of PMDA was added to the above solution three times, and stirred in a cold water bath for 14 hours to react, after which a pale yellow polyamic acid solution with a certain viscosity was obtained. rice field.

After defoaming, the above polyamic acid solution was uniformly coated on a dry and clean glass plate using an automatic film coating machine, and imidization reaction was carried out by employing a thermal imidization method. The procedure for temperature programmed curing is as follows: 80°C/3 hours, 100°C/1 hour, 200°C/2 hours, 300°C/4 hours.
Comparative example 2
Comparative Example 2 is a bright surface doped black film purchased from Ningbo Imayama, part number BY112.
Comparative example 3
Comparative Example 3 is a matte doped black film, part number BY112, purchased from Ningbo Imayama.
Characterization

The UV absorption spectra and LAB values, dielectric properties, thermal properties and mechanical properties of the polyimides according to Examples 3-6 and Comparative Examples 1-3 were measured, and the test results are shown in Tables 1-4 below.

Table 1 Transmittance T ₆₀₀ (%) and LAB values at 600 nm of the polyimides of Examples 3-6 and Comparative Examples 1-3.

Table 2 Thermal property data and mechanical property data of polyimides of Examples 3-6 and Comparative Examples 1-3

Table 3 Mechanical property data of polyimides of Examples 3-6 and Comparative Examples 1-3

Table 4 Dielectric property data of polyimides of Examples 3-6 and Comparative Examples 1-3

From the above data, when the anthraquinone derivative tetraamine monomers described in this disclosure account for 4% or more of the total amine monomer moles, the prepared black polyimides have good light blocking performance and excellent mechanical properties. It is found to have properties, thermal stability, and dielectric properties, and an optical transmittance of less than 1% over the entire wavelength range.

The above description of the embodiments is provided so that those skilled in the art can easily understand and apply the present application. It will be apparent to those skilled in the art that various modifications can be readily made to these examples, and that the general principles described herein can be applied to other examples without creative effort. . Accordingly, the present application is not limited to the examples herein, and those skilled in the art will appreciate improvements and modifications made without departing from the scope and spirit of this application based on the disclosure herein. , are within the scope of this application.

Claims (10)

An anthraquinone derivative tetraamine monomer characterized by having a structure represented by general formula I below.

A method of preparing an anthraquinone derivative tetraamine monomer according to claim 1, said method comprising converting 1,8-dihydroxy-9,10-anthraquinone to 1,8-dihydroxy in the presence of concentrated sulfuric acid and concentrated nitric acid. -2,4,5,7-tetranitro-9,10-anthraquinone followed by reduction of the nitro group to an amino group, 1,8-dihydroxy-2,4,5,7-tetraamino-9, A process for preparing an anthraquinone derivative tetraamine monomer comprising obtaining 10-anthraquinone. A method of preparing the anthraquinone derivative tetraamine monomer of claim 1, said method comprising the steps of: 1,8-dihydroxy-4 in the presence of concentrated sulfuric acid and concentrated nitric acid; ,5-dinitro-9,10-anthraquinone is nitrated to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, followed by reduction of the nitro group to an amino group and 1,8 - a process for the preparation of anthraquinone derivative tetraamine monomer, comprising obtaining dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone. 2. An intrinsic black polyimide comprising a structural unit derived from the anthraquinone derivative tetraamine monomer according to claim 1, a structural unit derived from a diamine monomer, and a structural unit derived from an acid anhydride monomer, wherein the anthraquinone derivative tetraamine A structural unit derived from an amine monomer accounts for 4% to 100% of the total number of moles of a structural unit derived from the anthraquinone derivative tetraamine monomer and a structural unit derived from the diamine monomer. . The structural unit derived from the anthraquinone derivative tetraamine monomer accounts for 4% to 10% of the total number of moles of the structural unit derived from the anthraquinone derivative tetraamine monomer and the structural unit derived from the diamine monomer. The intrinsic black polyimide according to claim 4. The ratio of the total number of moles of amine groups involved in the reaction of the anthraquinone derivative tetraamine monomer and the diamine monomer to the total number of moles of carboxylic anhydride groups involved in the reaction of the acid anhydride monomer is 1:1. The intrinsic black polyimide according to claim 4, characterized by: The acid anhydride monomers include 4,4′-(acetylene-1,2-diyl)diphthalic anhydride, pyromellitic dianhydride, and 3,3′,4,4′-biphenyltetracarboxylic dianhydride. , 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 2,2′-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 4,4′-oxydiphthalic anhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid 5. The intrinsic black polyimide of claim 4, which is one or more of dianhydride and diphenyl sulfide dianhydride. The diamine monomers include 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-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-aminobenzoxazole) and 2,2′-p-phenyl-bis(6 -aminobenzoxazole). 5. A method of preparing an intrinsic black polyimide according to claim 4, said method comprising the steps of:
(1) Under anhydrous and oxygen-free conditions, the anthraquinone derivative tetraamine monomer and diamine monomer described in claim 1 are mixed in a predetermined weight ratio, stirred until dissolved to form a homogeneous solution, and then acid is added. After adding the anhydride monomer and stirring and reacting in a cold water bath for a predetermined time, a black polyamic acid solution is obtained;
(2) imidizing a black polyamic acid solution to obtain an intrinsic black polyimide;
A method for preparing an intrinsic black polyimide, characterized by: For imidization of the black polyamic acid solution, after defoaming, the black polyamic acid solution is uniformly applied on a clean glass plate dried by an automatic film coating machine, and the temperature-rising curing procedure is performed at 80 ° C./3. 100° C./1 hour, 200° C./2 hours, 300° C./4 hours. Method.

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