CN113563212A - Anthraquinone derivative tetramine monomer, black intrinsic polyimide derived from anthraquinone derivative tetramine monomer and preparation method of black intrinsic polyimide - Google Patents
Anthraquinone derivative tetramine monomer, black intrinsic polyimide derived from anthraquinone derivative tetramine monomer and preparation method of black intrinsic polyimide Download PDFInfo
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Abstract
The application relates to an anthraquinone derivative quaternary amine monomer, which is characterized by having a structure shown by the following general formula I:
only two amino groups in the anthraquinone derivative quaternary amine monomer can be subjected to polycondensation reaction, so that a linear polymer can be obtained. The application also relates to a preparation method of the anthraquinone derivative quaternary amine monomer. The application also provides black intrinsic polyimide derived from the anthraquinone derivative tetramine monomer and a preparation method thereof. The black polyimide disclosed by the invention has good shading performance, good mechanical property, thermal stability and dielectric property, and the optical transmittance of all bands is less than 1%.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to an anthraquinone derivative quaternary amine monomer, a preparation method of the anthraquinone derivative quaternary amine monomer, black intrinsic polyimide derived from the anthraquinone derivative quaternary amine monomer and a preparation method of the black intrinsic polyimide.
Background
The black Polyimide (PI) film has the characteristics of non-transparency, low light absorptivity, low light transmittance, low light reflection coefficient and the like, and has important application values in the following fields: (1) the Flexible Printed Circuit (FPC) substrate film is black, so that light can be effectively blocked, the circuit design is prevented from being cracked by competitors, and the black or simple color is more in line with the simple aesthetic requirement; (2) lithium battery: the lithium battery pack connecting sheet is insulated and protected, and black polyimide can shield light to prevent copper oxidation; (3) wireless charging: the wireless charging needs to use ultrathin black polyimide film glue as the insulation protection of the coil, but the current black polyimide can not meet the requirement, and the carbon black is coated on the common polyimide temporarily; (4) aerospace: the interference of various stray light to an imaging system and a sensor can be eliminated or avoided when the device is used for a satellite antenna; the light absorption film can be used for preparing light fixed attenuators and light terminals.
At present, the preparation method of the black PI film mainly has three modes: (1) graphene, perylene black and other organic and inorganic fillers are added; (2) the special monomer is used to increase the formation of charge transfer complex of polyimide molecular chain. Such as Liu et al (J Polym Res (2019)26:171) with an electron rich aromatic diamine monomer, 4,4' -diaminodiphenylamine (NDA) and PMDA, but the color of the used polymer did not turn black even with 100% NDA. Therefore, realization of black color of polyimide by conjugation is not completely realized black color, and use of a large amount of a special monomer causes increase in cost of the black polyimide film. In addition, the Chinese patent application with publication number CN109180936A adopts a copolymerization mode with commercial diamine, and prepares a series of intrinsic black polyimide by regulating and controlling the proportion of the two. The invention discloses a series of intrinsic black polyimides prepared by synthesizing a diamine monomer containing an isoindigo structure and homopolymerizing the diamine monomer and commercial dianhydride in Chinese invention patent application with publication number CN 111574426A.
However, the above-mentioned black polyimide preparation method has more or less the following disadvantages:
1. the preparation process is complex, and the filler needs to be modified in advance so as to be dispersed in the PI matrix more uniformly, so that the phenomenon of uneven mechanical properties and pinholes are avoided;
2. although the mechanical property and the thermal property of the PI film can be improved to a certain extent by introducing the inorganic filler, the insulativity and the breakdown strength of the PI film can be damaged, and the application of the PI film in the field of electronic industry is adversely affected.
3. Although the introduction of the organic pigment avoids influencing the electrical property of the PI film, the application of the PI film in the high-temperature field is hindered by the lower thermal decomposition temperature of the organic pigment, the PI film is easy to decompose under the influence of environmental factors, and the weather resistance is poor;
4. the existing intrinsic black polyimide still has defects on the index of optical transmittance, and cannot ensure that the optical transmittance is lower than 1 percent in all visible light bands.
For this reason, there is a continuing need in the art to develop a black intrinsic polyimide and a method for preparing the same.
Disclosure of Invention
The present application aims to provide a novel anthraquinone derivative monomer with a high molar extinction coefficient, wherein a plurality of auxochromic groups are introduced into an anthraquinone structure, so that the absorption wavelength of the monomer extends to a wide range, and the technical problem is solved.
The application also aims to provide a preparation method of the anthraquinone derivative tetramine monomer.
The invention also aims to provide black intrinsic polyimide synthesized by using the anthraquinone derivative tetramine monomer.
The present application also provides a method for preparing black intrinsic polyimide.
In order to solve the above technical problem, the present application provides the following technical solutions:
in a first aspect, the present application provides an anthraquinone derivative tetraamine monomer characterized by having a structure represented by the following general formula I:
in one embodiment, only two amine groups of the anthraquinone derivative tetraamine monomer can undergo polycondensation, thereby obtaining a linear polymer.
In a second aspect, the present application provides a process for the preparation of the anthraquinone derivative tetraamine monomer according to the first aspect, characterized in that the process comprises nitrating 1,8 dihydroxy-9, 10-anthraquinone to 1,8 dihydroxy-2, 4,5,7 tetranitro-9, 10-anthraquinone in the presence of concentrated sulphuric acid and concentrated nitric acid, followed by reduction of the nitro group to amino groups to give 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone.
In another embodiment, the present application provides a process for the preparation of an anthraquinone derivative tetraamine monomer according to the first aspect, characterized in that the process comprises nitrating 1,8 dihydroxy-4, 5 dinitro-9, 10-anthraquinone to 1,8 dihydroxy-2, 4,5,7 tetranitro-9, 10-anthraquinone in the presence of concentrated sulfuric acid and concentrated nitric acid, followed by reduction of the nitro group to an amino group to give 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone.
In a third aspect, the present application provides a black intrinsic polyimide, wherein the black intrinsic polyimide is formed by reacting the anthraquinone derivative tetraamine monomer according to the first aspect, a diamine monomer, and an anhydride monomer, wherein the anthraquinone derivative tetraamine monomer accounts for 4% to 100% of the total molar number of the anthraquinone derivative tetraamine monomer and the diamine monomer, on a weight percentage basis. In a preferred embodiment, the anthraquinone derivative quaternary amine monomer accounts for 4% -80% of the total molar number of the anthraquinone derivative quaternary amine monomer and the diamine monomer. In a preferred embodiment, the anthraquinone derivative quaternary amine monomer accounts for 4% -10% of the total molar number of the anthraquinone derivative quaternary amine monomer and the diamine monomer.
In one embodiment of the first aspect, the ratio of the total number of moles of amine groups reacted with the diamine monomer to the total number of moles of carboxylic anhydride groups reacted with the anhydride monomer is 1: 1. in this embodiment, the quaternary amine monomer of the anthraquinone derivative has a difference in the activity of the amine groups at the ortho-position due to the presence of intramolecular hydrogen bonds, and only two ortho-position amine groups can participate in the copolymerization reaction.
In one embodiment of the first aspect, the anhydride monomer is one or more of: 4,4' - (acetylene-1, 2, -diyl) diphthalic anhydride, pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 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 one or more of: m-phenylenediamine, p-phenylenediamine, 4' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4' -diaminobenzophenone, 4' -diaminodiphenylmethane, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 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-aminobenzazole) and 2,2' -p-phenyl-bis (6-aminobenzazole).
In a fourth aspect, the present application provides a method for preparing a black intrinsic polyimide as described in the third aspect, wherein the method comprises the steps of:
(1) under the anhydrous and anaerobic conditions, mixing anthraquinone derivative quaternary amine monomer and diamine monomer according to a preset weight ratio, stirring until the anthraquinone derivative quaternary amine monomer and the diamine monomer are dissolved to form a homogeneous solution, then adding an anhydride monomer, and stirring and reacting for a preset time period under a cold water bath to obtain a black polyamic acid solution;
(2) and carrying out imidization on the black polyamic acid solution to obtain black intrinsic polyimide.
In an embodiment of the fourth aspect, the imidizing the black polyamic acid solution includes defoaming the black polyamic acid solution, uniformly coating the defoamed black polyamic acid solution on a dry and clean glass plate through an automatic film coating machine, and performing imidization reaction by a thermal imidization method, wherein the temperature-rising curing procedure is as follows: 80 ℃/3h, 100 ℃/1h, 200 ℃/2h and 300 ℃/4 h.
Compared with the prior art, the black polyimide has the beneficial effects that the black polyimide has good shading performance, good mechanical property, thermal stability and dielectric property, and the optical transmittance of the whole waveband is less than 1%.
Drawings
Fig. 1 shows the ultraviolet absorption spectrum of the anthraquinone derivative quaternary amine monomer according to example 1.
Fig. 2 shows an infrared spectrum of a quaternary amine monomer of an anthraquinone derivative according to example 1.
Fig. 3 shows a nuclear magnetic hydrogen spectrum of the anthraquinone derivative tetraamine monomer according to example 1.
Fig. 4 shows an optical photograph of a polyimide according to example 3 on a white a4 paper sheet.
Detailed Description
The black polyimide has a wide potential application prospect, and has stimulated the interest of a plurality of research teams at home and abroad. For example, chinese patent publication No. CN105860112B discloses that by blending a polyamide acid (PAA) solution, which is a precursor of PI, with a polyacrylonitrile solution, a black film with excellent mechanical properties of PI and opacity after PAN pre-oxidation is obtained. Chinese patent publication No. CN105482115B reports a method of adding black filler such as carbon black or carbon fiber powder and coupling agent into polyamic acid solution, and then defoaming, casting and forming a film. The Chinese patent application with publication number CN108017910A reports a method for adding carbon black pigment into polyamic acid solution, filtering, adding an agglomeration agent, defoaming, casting and forming a film. Chinese patent application publication No. CN110387040A reports a method of adding conductive nanoparticles such as transition metal nitride, transition metal carbide, transition metal boride, noble metal, graphene, carbon-based nanomaterial, black pigment, black dye, etc. to a polyamic acid solution, defoaming, casting, and forming a film, so that the shielding property is significantly improved. Chinese patent application publication No. CN108976447A reports a method for preparing an ultrathin black polyimide film by adding carbon black with different particle sizes into a polyamic acid solution and defoaming and coating.
The intrinsic black polyimide has good light shielding performance, and can obtain better mechanical, thermal and electrical properties by adjusting the type and the dosage of the monomer. Therefore, the continuous development of new black intrinsic polyimide preparation methods is of great significance.
In one embodiment, the present application provides a novel anthraquinone derivative tetraamine monomer having a structure represented by the following general formula I:
in one embodiment, the present application provides a method of preparing an anthraquinone derivative tetraamine monomer as described above, said method comprising nitrating 1,8 dihydroxy-9, 10-anthraquinone to 1,8 dihydroxy-2, 4,5,7 tetranitro-9, 10-anthraquinone in the presence of concentrated sulfuric acid and concentrated nitric acid, followed by reduction of the nitro group to an amino group to give 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone.
In another embodiment, a method for preparing an anthraquinone derivative tetraamine monomer can include nitrating 1,8 dihydroxy-4, 5 dinitro-9, 10-anthraquinone to 1,8 dihydroxy-2, 4,5,7 tetranitro-9, 10-anthraquinone in the presence of concentrated sulfuric acid and concentrated nitric acid, and then reducing the nitro group to an amino group to provide 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone.
In one embodiment, the present application also provides a black intrinsic polyimide formed by the reaction of the anthraquinone derivative tetraamine monomer, the diamine monomer, and the anhydride monomer as described above. In this embodiment, the content of the anthraquinone derivative quaternary amine monomer is preferably 4% to 100% of the total molar number of all amine monomers. In the first aspect, when the content of the anthraquinone derivative tetraamine monomer is less than 4% of the total molar number of all the amine monomers, the polyimide prepared is yellow to blackish green, not pure black. In another aspect, when the content of the anthraquinone derivative tetraamine monomer is more than 10% of the total molar number of all the amine monomers, the LAB value of the resulting black intrinsic polyimide film does not change much. Therefore, in a preferred embodiment, the content of the anthraquinone derivative quaternary amine monomer is preferably 4% to 10% of the total moles of all amine monomers.
The present application also relates to a method for preparing the black intrinsic polyimide as described above, which comprises first reacting an anthraquinone derivative tetraamine monomer, a diamine monomer and an acid anhydride monomer to obtain a polyamic acid solution, and then imidizing the polyamic acid solution to obtain the black intrinsic polyimide.
Examples
The present application will now be described and illustrated in further detail with reference to the following examples. All chemical raw materials can be purchased from the market unless otherwise specified. Those skilled in the art will appreciate that the following embodiments are exemplary only.
In the examples described below, the characterization methods used are as follows.
Nuclear magnetic resonance hydrogen spectrum (1H NMR)：
Nuclear magnetic resonance spectrum of reaction product and intermediate (1H NMR) spectra were obtained on brueck AVANCE III HD 400/500, germany. The sample preparation method comprises the following steps: in a clean and dry glass magnetic tube, about 10mg of the sample was completely dissolved in about 0.5mL of deuterated reagent. The better soluble product was deuterated chloroform as solvent (CDCl)3) The product is dissolved at room temperature, the product with poor solubility takes deuterated dimethyl sulfoxide (DMSO-d6) as a solvent, DMSO-d6 is easy to solidify at low room temperature, and blowing is needed before loading. Tetramethylsilane (TMS) was used as an internal standard for the test at room temperature, and the chemical shift was 0 ppm.
Fourier Infrared transform Spectroscopy (FT-IR):
in a dry environment, the test was performed using a Nicolet iS5(ThermoFisher Scientific, Inc., USA) Fourier transform Infrared Spectroscopy (FTIR) ATR mode, and the monomer (4NADA) was first placed in a vacuum oven at 80 ℃ for 2h to remove water before testing. The scanning range is set to 4000-650cm-1Resolution was set to 2cm-1The number of scans was set to 32, and the average value was automatically obtained.
Ultraviolet visible spectrum (UV-Vis):
intrinsic black polyimide filmThe optical transmittance of (A) was analyzed by Shimadzu UV-2600 spectrophotometer, and the scanning range was set to 360-800cm-1. The monomer UV absorbance was also analyzed by Shimadzu UV-2600 Spectrophotometer, and the absorbance in dilute solution was measured. The monomer concentration was 30. mu.M and the solvent chosen was N, N-dimethylformamide.
CIELAB color space:
the reflectivity of the prepared intrinsic black polyimide film is tested by adopting a Perkinelmer company LAMBDA 950UV/Vis/NIR spectrophotometer in America, and L is obtained by color gamut conversion calculation through a built-in conversion formula and combining the relative spectral function distribution of a used CIE standard illuminant D65 and a CIE1976 standard chromaticity observer*、a*、b*The parameter values. The light source was a standard light source D65, and the observation angle was 10 °.
Thermal performance analysis (TGA & DMA & TMA):
the thermal weight loss behavior of the intrinsic black polyimide film is carried out on a TA Discovery 550 thermogravimetric analyzer (TGA) under the protection of nitrogen, the gas flow is 50mL/min, the temperature is increased from room temperature to 120 ℃ at 20 ℃/min, the intrinsic black polyimide film stays for 15min, and then the temperature is increased from 50 ℃ to 800 ℃ at 10 ℃/min.
Glass transition temperature (T)g) The process was carried out on a TA Q800 dynamic thermomechanical analyzer (DMA) by cutting the intrinsically black polyimide film into rectangular strips of the same width (0.5cm), setting the loading frequency at 1Hz, increasing from 30 ℃ to 500 ℃ at a rate of 5 ℃/min, and protecting with nitrogen.
The thermal dimensional stability of the intrinsic black polyimide film was analyzed by a TA Q400 thermomechanical analyzer (TMA) in tensile mode to determine the change in the dimensions of the sample as the temperature increases. The intrinsic black polyimide film is prepared into a long and thin strip shape with uniform width (0.5cm), the static load is 0.05N, the heating rate is 10 ℃/min, the heating range is from room temperature to 400 ℃, and the nitrogen flow is 50 mL/min. The temperature programming step is divided into two parts, the temperature is raised at the same speed in the first step and then reduced to eliminate the residual internal stress of the film in the thermal imidization, and curve data of the second step of heating to 400 ℃ is recorded.
Mechanical property analysis:
the mechanical properties of the intrinsic black polyimide film were measured by a Sagitai SUST CMT1104 electronic universal tester, the test specimen was cut into a rectangular strip with a width of 1cm, the pulling rate was 5mm/min, and the average of the results of a number of effective tests was taken in accordance with ASTM D882-02 test standard.
And (3) dielectric property analysis:
the dielectric properties of the intrinsic black polyimide film were measured by a Keysight N5227B network Analyzer, Canada, and rectangular samples with side lengths greater than 3X 4mm were prepared for dielectric constant and dielectric loss testing. After drying at 80 ℃ for two hours, the test pieces were placed in a sensor and the test frequency was selected for the test. The test frequency was 24GHz, 40GHz and 60GHz, the sample thickness was 25 μm, and the medium was air.
Examples of monomer Synthesis
Example 1
1,8 dihydroxy-9, 10-anthraquinone (1.0mmol) was added to a three-necked flask, 5ml of concentrated sulfuric acid and 4ml of concentrated nitric acid were added at 0 ℃, after vigorous mechanical stirring for 4h, crushed ice was poured in, the solvent was removed by suction filtration, the solid material was washed with water/saturated sodium bicarbonate solution and dried under vacuum overnight to give crude product 1 in yellow.
The crude product 1 was purified by silica gel chromatography (short column) eluting with eluent (methanol) to give the yellow product 1,8 dihydroxy-2, 4,5,7 tetranitro-9, 10-anthraquinone.
The yellow product (1mmol) was weighed, dissolved in ethanol in a flask, and Na was weighed2S·9H2O (8mmol) was dissolved in distilled water to saturation, and the solution was charged into a flask. The mixture is refluxed and reacted for 12 hours; after cooling to room temperature, the mixture was poured into a prepared ice-water mixture and stirred continuously. After filtration, washing with water and vacuum drying overnight, the black target product 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone was obtained.
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 has strong absorption in the visible light band of 400-700nm, and the half-peak width reaches nearly 150nm, so that the monomer is black due to the self-plane conjugated structure and the influence of intramolecular hydrogen bonds. As shown in fig. 2, located at 3500-1Infrared ray of (2)The absorption peaks can be sequentially assigned to ortho-amino and para-amino, and the shift and the broadening of the peaks can indicate that the latter has intramolecular hydrogen bonds, i.e. the two amino groups have reaction activity difference. At the same time, appear at 1567cm-1The carbonyl peak also indicates that various hydrogen bonds exist in the molecule, i.e., the carbonyl forms an intramolecular hydrogen bond with both the hydroxyl and the para-amino. This unusual hydrogen bonding is common at 1700cm-1The carbonyl peak at the left and the right is reduced to 1567cm-1To (3).
This difference in activity between the amino groups is also demonstrated in FIG. 3, i.e.the nuclear magnetic peak of the ortho amino hydrogen occurs at a higher field position.
The molar absorption coefficient of 1, 8-dihydroxy-2, 4,5, 7-tetraamino-9, 10-anthraquinone according to example 1 was also determined.
Molar absorptivity calculation methods are as follows:
the molar absorptivity is the absorptivity at a concentration of 1 mol/liter and is represented by ε. The calculation formula is as follows:
A＝εbc；
wherein A is ultraviolet absorbance, and the value is obtained by measuring an ultraviolet spectrophotometer, wherein epsilon is a molar absorption coefficient, b is the thickness of the absorption cell, and c is the molar concentration of the liquid to be measured.
Thus, in combination with the UV absorption spectrum of 1, 8-dihydroxy-2, 4,5, 7-tetraamino-9, 10-anthraquinone, the molar absorption coefficient at the maximum absorption wavelength λ max is about 105L/(mol cm), wherein the molar concentration of the liquid to be measured is 30 MuM, the thickness of the absorption cell is 1cm, and the absorbance at the maximum absorption wavelength is 0.296, at the moment, the diluted solution still presents black blue, and the molar absorption coefficient is sufficiently strong.
Example 2
1,8 dihydroxy-4, 5 dinitro-9, 10-anthraquinone (1.0mmol) is added to a three-necked flask, 3ml of concentrated sulfuric acid and 2ml of concentrated nitric acid are added at 0 ℃, after 4 hours of vigorous mechanical stirring, crushed ice is poured in, the solvent is removed by suction filtration, the solid material is washed with water/saturated sodium bicarbonate solution and dried under vacuum overnight to give a yellow crude product 1.
Dissolving the crude product 1 by using methanol, adding cyclohexane, and recrystallizing to obtain a yellow product 1, 8-dihydroxy-2, 4,5, 7-tetranitro-9, 10-anthraquinone.
The yellow product (1mmol) was weighed, dissolved in N, N-dimethylformamide in a flask, and 0.01g of palladium on carbon was weighed and added to the flask. The mixture is refluxed and reacted for 12 hours under the atmosphere of standard atmosphere and hydrogen; after cooling to room temperature, pour into the preparation water and stir continuously. After filtration, washing with water and vacuum drying overnight, the black target product 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone was obtained.
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 above-mentioned purification and reduction means can be used interchangeably with the purification and reduction means in example 1
Example for preparation of Black intrinsic polyimide
Example 3
This example relates to the synthesis of black intrinsic polyimide PI-1.
A black polyimide film was prepared with a solid content of 15.3% by mixing 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone and ODA (4,4' -diaminodiphenyl ether) with PMDA (pyromellitic dianhydride) in a molar ratio of 4: 96. The ratio of the total moles of the amine groups reacted with the anthraquinone derivative quaternary amine monomer to the total moles of the carboxylic anhydride groups reacted with the anhydride monomer is 1: 1.
under the conditions of sufficient water removal, oxygen removal and nitrogen protection, 0.36mmol of target monomer, 5.64mmol of ODA and 10mL of DMAc are added into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath and stirred until the target monomer, the ODA and the DMAc are dissolved to form a homogeneous solution; adding 6mmol PMDA in total into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a black polyamide acid solution with certain viscosity.
The polyamic acid solution is defoamed, uniformly coated on a dry and clean glass plate through an automatic coating machine, and imidized by a thermal imidization method. The temperature-rising curing procedure is as follows: 80 ℃/3h, 100 ℃/1h, 200 ℃/2h and 300 ℃/4 h.
Example 4
This example relates to the synthesis of black intrinsic polyimide PI-2.
A black polyimide film was prepared with a solid content of 15.3% by mixing 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone and ODA (4,4' -diaminodiphenyl ether) with PMDA (pyromellitic dianhydride) in a molar ratio of 6: 94. The ratio of the total moles of the amine groups reacted with the anthraquinone derivative quaternary amine monomer to the total moles of the carboxylic anhydride groups reacted with the anhydride monomer is 1: 1.
under the conditions of sufficient water removal, oxygen removal and nitrogen protection, 0.36mmol of target monomer, 5.64mmol of ODA and 10mL of DMAc are added into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath and stirred until the target monomer, the ODA and the DMAc are dissolved to form a homogeneous solution; adding 6mmol PMDA in total into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a black polyamide acid solution with certain viscosity.
The polyamic acid solution is defoamed, uniformly coated on a dry and clean glass plate through an automatic coating machine, and imidized by a thermal imidization method. The temperature-rising curing procedure is as follows: 80 ℃/3h, 100 ℃/1h, 200 ℃/2h and 300 ℃/4 h.
Example 5
This example relates to the synthesis of black intrinsic polyimide PI-3.
A black polyimide film was prepared with a solid content of 15.3% by mixing 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone and ODA (4,4' -diaminodiphenyl ether) with PMDA (pyromellitic dianhydride) in a molar ratio of 8: 92. The ratio of the total moles of the amine groups reacted with the anthraquinone derivative quaternary amine monomer to the total moles of the carboxylic anhydride groups reacted with the anhydride monomer is 1: 1.
under the conditions of sufficient water removal, oxygen removal and nitrogen protection, 0.36mmol of target monomer, 5.64mmol of ODA and 10mL of DMAc are added into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath and stirred until the target monomer, the ODA and the DMAc are dissolved to form a homogeneous solution; adding 6mmol PMDA in total into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a black polyamide acid solution with certain viscosity.
The polyamic acid solution is defoamed, uniformly coated on a dry and clean glass plate through an automatic coating machine, and imidized by a thermal imidization method. The temperature-rising curing procedure is as follows: 80 ℃/3h, 100 ℃/1h, 200 ℃/2h and 300 ℃/4 h.
Example 6
This example relates to the synthesis of black intrinsic polyimide PI-4.
A black polyimide film was prepared with a solid content of 15.3% by mixing 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone and ODA (4,4' -diaminodiphenyl ether) with PMDA (pyromellitic dianhydride) in a molar ratio of 10: 90. The ratio of the total moles of the amine groups reacted with the anthraquinone derivative quaternary amine monomer to the total moles of the carboxylic anhydride groups reacted with the anhydride monomer is 1: 1.
under the conditions of sufficient water removal, oxygen removal and nitrogen protection, 0.36mmol of target monomer, 5.64mmol of ODA and 10mL of DMAc are added into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath and stirred until the target monomer, the ODA and the DMAc are dissolved to form a homogeneous solution; adding 6mmol PMDA in total into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a black polyamide acid solution with certain viscosity.
The polyamic acid solution is defoamed, uniformly coated on a dry and clean glass plate through an automatic coating machine, and imidized by a thermal imidization method. The temperature-rising curing procedure is as follows: 80 ℃/3h, 100 ℃/1h, 200 ℃/2h and 300 ℃/4 h.
Example 7
A black polyimide film was prepared with a solid content of 15.3% by mixing 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone and ODA (4,4' -diaminodiphenyl ether) with PMDA (pyromellitic dianhydride) in a molar ratio of 80: 20. The ratio of the total number of moles of amine groups reacted with the diamine monomer to the total number of moles of carboxylic anhydride groups reacted with the anhydride monomer is 1: 1.
under the conditions of sufficient water removal, oxygen removal and nitrogen protection, 0.36mmol of target monomer, 5.64mmol of ODA and 10mL of DMAc are added into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath and stirred until the target monomer, the ODA and the DMAc are dissolved to form a homogeneous solution; adding 6mmol PMDA in total into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a black polyamide acid solution with certain viscosity.
The polyamic acid solution is defoamed, uniformly coated on a dry and clean glass plate through an automatic coating machine, and imidized by a thermal imidization method. The temperature-rising curing procedure is as follows: 80 ℃/3h, 100 ℃/1h, 200 ℃/2h and 300 ℃/4 h.
The black intrinsic polyimide of example 7 has lower optical properties, improved modulus, reduced elongation at break and tensile strength, and almost unchanged dielectric properties, compared to the black intrinsic polyimide of example 6.
Comparative example 1
This example relates to the synthesis of PMDA-ODA type PI membranes.
Mixing a mixture of 1: 1 ODA (4,4' -diaminodiphenyl ether) and PMDA (pyromellitic dianhydride) to prepare a Kapton-type polyimide film with a solid content of 15.1%. The ratio of the total number of moles of amine groups of the diamine monomer to the total number of moles of carboxylic anhydride groups of the anhydride monomer is 1: 1.
under the conditions of sufficient water removal, oxygen removal and nitrogen protection, 6mmol ODA and 10mL DMAc are added into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath, and are stirred until the materials are dissolved to form a homogeneous solution; adding 6mmol PMDA in total into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a light yellow polyamide acid solution with certain viscosity.
The polyamic acid solution is defoamed, uniformly coated on a dry and clean glass plate through an automatic coating machine, and imidized by a thermal imidization method. The temperature-rising curing procedure is as follows: 80 ℃/3h, 100 ℃/1h, 200 ℃/2h and 300 ℃/4 h.
Comparative example 2
Comparative example 2 is a clear-side black-doped film purchased from Ningbo Jinshan under the designation BY112
Comparative example 3
Comparative example 3 is a sub-photo-doped black film purchased from Ningbo Jinshan under the designation BY122
Performance characterization
The polyimides according to examples 3 to 6 and comparative examples 1 to 3 were measured for ultraviolet absorption spectrum and LAB value, dielectric properties, thermal properties and mechanical properties, and the results of the tests are shown in tables 1 to 4 below.
TABLE 1 600nm transmittance T of polyimides of examples 3 to 6 and comparative examples 1 to 3600(%) and LAB values.
Table 2 thermal and mechanical property data for the polyimides of examples 3-6 and comparative examples 1-3.
Table 3 mechanical property data for the polyimides of examples 3-6 and comparative examples 1-3.
Table 4 dielectric property data for the polyimides of examples 3-6 and comparative examples 1-3.
From the data, when the mole number of the anthraquinone derivative quaternary amine monomer in all the amine monomers is greater than or equal to 4%, the prepared black polyimide has good light shielding performance, good mechanical property, thermal stability and dielectric property, and the optical transmittance of the full-wave band is less than 1%.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (10)
1. An anthraquinone derivative tetraamine monomer, characterized in that it has a structure represented by the following general formula I:
2. a method for preparing an anthraquinone derivative tetraamine monomer according to claim 1, which comprises nitrating 1,8 dihydroxy-9, 10-anthraquinone to 1,8 dihydroxy-2, 4,5,7 tetranitro-9, 10-anthraquinone in the presence of concentrated sulfuric acid and concentrated nitric acid, and then reducing the nitro group to an amino group to give 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone.
3. A method for preparing an anthraquinone derivative tetraamine monomer according to claim 1, which comprises nitrating 1,8 dihydroxy-4, 5 dinitro-9, 10-anthraquinone to 1,8 dihydroxy-2, 4,5,7 tetranitro-9, 10-anthraquinone in the presence of concentrated sulfuric acid and concentrated nitric acid, and then reducing the nitro group to an amino group to give 1,8 dihydroxy-2, 4,5,7 tetraamino-9, 10-anthraquinone.
4. A black intrinsic polyimide formed by reacting the anthraquinone derivative tetraamine monomer of claim 1, a diamine monomer, and an anhydride monomer, wherein the anthraquinone derivative tetraamine monomer comprises from 4% to 100% by weight of the total moles of the anthraquinone derivative tetraamine monomer and the diamine monomer.
5. The black intrinsic polyimide of claim 4, wherein said anthraquinone derivative tetraamine monomer comprises from 4% to 10% of the total moles of said anthraquinone derivative tetraamine monomer and said diamine monomer.
6. The black intrinsic polyimide according to claim 4, wherein the ratio of the total moles of amine groups reacted with the anthraquinone derivative tetraamine monomer and the diamine monomer to the total moles of carboxylic anhydride groups reacted with the anhydride monomer is from 1: 1.
7. the black intrinsic polyimide according to claim 4, wherein the acid anhydride monomer is one or more of: 4,4' - (acetylene-1, 2, -diyl) diphthalic anhydride, pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 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.
8. The black intrinsic polyimide of claim 4, wherein said diamine monomer is one or more of: m-phenylenediamine, p-phenylenediamine, 4' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4' -diaminobenzophenone, 4' -diaminodiphenylmethane, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 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-aminobenzazole) and 2,2' -p-phenyl-bis (6-aminobenzazole).
9. A method of preparing the black intrinsic polyimide according to claim 4, comprising the steps of:
(1) mixing anthraquinone derivative quaternary amine monomer and diamine monomer according to a predetermined weight ratio in the absence of water and oxygen according to claim 1, stirring until the monomers are dissolved to form a homogeneous solution, then adding anhydride monomer, stirring and reacting for a predetermined period of time in a cold water bath to obtain a black polyamic acid solution;
(2) and carrying out imidization on the black polyamic acid solution to obtain black intrinsic polyimide.
10. The method of claim 9, wherein the imidizing of the black polyamic acid solution comprises defoaming the black polyamic acid solution, uniformly coating the black polyamic acid solution on a dry and clean glass plate by an automatic film coating machine, and performing imidization by a thermal imidization method, wherein the temperature-rising curing procedure is as follows: 80 ℃/3h, 100 ℃/1h, 200 ℃/2h and 300 ℃/4 h.
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| CN115232303A (en) * | 2022-04-19 | 2022-10-25 | 上海交通大学 | Polymer for black matrix, preparation method and application thereof |
| CN115368255A (en) * | 2022-05-31 | 2022-11-22 | 上海交通大学 | Anthraquinone-based diamine monomer, cyan intrinsic polyimide derived from anthraquinone-based diamine monomer and preparation method of cyan intrinsic polyimide |
| CN117534836A (en) * | 2023-12-18 | 2024-02-09 | 上海交通大学 | Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition |
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