CN113277950B - Asymmetric aromatic diamine monomer and polyimide containing terphenyl macro-substituted side group - Google Patents

Asymmetric aromatic diamine monomer and polyimide containing terphenyl macro-substituted side group Download PDF

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CN113277950B
CN113277950B CN202110497984.9A CN202110497984A CN113277950B CN 113277950 B CN113277950 B CN 113277950B CN 202110497984 A CN202110497984 A CN 202110497984A CN 113277950 B CN113277950 B CN 113277950B
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汪称意
郑慧
陶正旺
赵晓燕
朱冠南
华广洲
李坚
任强
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Changzhou University
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Abstract

The invention belongs to the field of high polymer materials, and particularly relates to an asymmetric aromatic diamine monomer containing a terphenyl large substituent side group and polyimide. 2, 4-dinitrobromobenzene and 3, 5-diphenylphenylboronic acid are reacted according to the molar ratio under the alkaline condition to obtain an intermediate compound, and then the intermediate dinitro compound is reduced through a reduction reaction to obtain an asymmetric aromatic diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene containing a terphenyl large substituted structure. Adding diamine monomer and commercial aromatic dianhydride monomer with equal mass into organic solvent, stirring and reacting under the action of catalyst, settling, washing and drying to obtain fibrous asymmetric polyimide containing terphenyl large substituent lateral group. The solubility of the polyimide in a specific solvent can reach more than 30wt%, the polyimide has excellent film forming property, and the prepared polymer film has potential application value in the field of microelectronics.

Description

Asymmetric aromatic diamine monomer and polyimide containing terphenyl macro-substituted side group
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an asymmetric aromatic diamine monomer containing a terphenyl large substituent side group and polyimide.
Background
Polyimide (PI) is used as a high-performance polymer material with wide application, and has unique structural characteristics and excellent comprehensive performance. The functionalized PI film can be used in the high and new technical fields of gas separation films, flexible photoelectric device substrates, motor insulation, microelectronic manufacturing and packaging and the like. With the rapid development of the microelectronics industry, the density of the wires of the integrated circuit is continuously increased, which results in the problems of slow signal transmission speed, increased power loss and the like, and in order to solve the problems, the insulating layer material of the integrated circuit is required to have a lower dielectric constant k (1.6-2.8), but the dielectric constant k=3.6 of pure polyimide is not enough to meet the requirement of the modern microelectronics industry on low dielectric materials. Therefore, lowering the dielectric constant of PI has become a research hotspot for researchers, which is one of the keys for the further miniaturization of integrated circuits in the future. In addition, thermal properties play a very important role in many microelectronic manufacturing processes, PI has a rigid and conjugated backbone, and strong intermolecular and intramolecular interactions, so that it has superior high temperature resistance, but at the same time has problems in terms of refractory nature and the like.
Researchers develop researches on the structural modification of the bulk structure on the basis of the structural and composition design of the low-dielectric PI high polymer material: (1) Introducing fluorine-containing groups (-F), methylene groups (-CH) 2 (-), alicyclic groups (e.g., cyclohexyl, etc.), etc., are effective in lowering PI dielectric constants; (2) The introduction of functional groups with high molar volume, such as phenyl, naphthyl, fluorenyl, etc., can also be effective in lowering the dielectric constant of PI. PI containing cycloaliphatic substituents and fluorine-containing groups generally has both low molar polarizability and high molar volume characteristics, but its heat stability and mechanical properties are lost to some extent.
Disclosure of Invention
The invention aims to improve the dissolution film forming property of polyimide polymer and further improve the dielectric property of polymer film, and designs and prepares an asymmetric aromatic diamine monomer containing terphenyl large substituted side group and polyimide based on molecular design; by introducing nonpolar terphenyl with large free volume and an asymmetric structure into a polymer molecular main chain, the polymer has high solubility and excellent film forming property in a specific solvent, and can further effectively improve the dielectric property of polyimide film materials, and the polyimide polymer has important potential application value in the field of microelectronics.
The invention adopts 2, 4-dinitrobromobenzene and 3, 5-diphenyl phenylboronic acid as initial raw materials, successfully prepares an asymmetric aromatic diamine monomer containing a terphenyl large substituted side group structure through Suzuki coupling and redox two-step reaction, and successfully introduces the terphenyl large side group and the asymmetric structure onto a polyimide main chain by utilizing the prepared aromatic diamine monomer containing the diphenyl substituted asymmetric structure and dianhydride monomer through one-step solution polycondensation, thereby increasing the space free volume by interfering the close packing of polymer molecular chains, simultaneously maintaining the inherent rigid structure, and effectively avoiding the thermal and mechanical property loss of PI caused by introducing fat or fluorine-containing groups. And the nonpolar terphenyl bulky side group structure increases free volume, reduces the density of polarizable groups, and reduces hygroscopicity. Therefore, the polyimide has higher solubility, lower dielectric constant and hygroscopicity, so that the polyimide has potential application value in the field of microelectronics industry.
The invention provides an asymmetric aromatic diamine monomer containing a terphenyl large substituent group, which has the structural formula:
Figure BDA0003055217590000021
the preparation method of the asymmetric aromatic diamine monomer containing the terphenyl macro-substituted side group comprises the following steps:
(1) Under the protection of nitrogen, adding 2, 4-dinitrobromobenzene and 3, 5-diphenyl phenylboric acid with a certain molar ratio into a three-neck flask with mechanical stirring, further respectively adding a proper amount of organic solvent, sodium carbonate aqueous solution and catalyst, stirring at room temperature for half an hour, heating to 60-120 ℃ for reaction for 6-12 hours, ending the reaction, and obtaining a white intermediate dinitro compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene after sedimentation, filtration, drying and recrystallization.
(2) Adding an intermediate dinitro compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene into a three-neck flask with mechanical stirring, further adding a proper amount of an organic solvent, a reducing agent and a catalyst respectively, reacting for 4-12 hours under reflux, ending the reaction, pouring the solution into a beaker, standing, filtering after the product is separated out, washing with ethanol, and vacuum drying to obtain the monomer 3,5- (diphenyl) phenyl-2, 4-diamine benzene.
The invention also provides a highly soluble polyimide containing a terphenyl macro-substituted side group and having an asymmetric structure, and the structural formula is as follows:
Figure BDA0003055217590000031
wherein ,
Figure BDA0003055217590000032
can be +.>
Figure BDA0003055217590000033
In (2) repeating units n=40 to 100.
The preparation method of the highly soluble polyimide polymer containing the terphenyl macro-substituted side group asymmetric structure comprises the following specific steps:
adding an equal amount of asymmetric aromatic diamine monomer containing a terphenyl large substituent group and an aromatic dianhydride monomer into an organic solvent under the protection of nitrogen, adding a catalyst, stirring at 80-100 ℃ for half an hour, continuously heating to 180-200 ℃ for reaction for 6-10 hours after the monomer is completely dissolved, obtaining a viscous polymer solution, ending the reaction, pouring the polymer solution into ethanol for sedimentation, and further filtering, washing and drying to obtain fibrous high-solubility polyimide containing the terphenyl large substituent group asymmetric structure.
The asymmetric aromatic diamine monomer containing the terphenyl macro-substituted side group is 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, and the dianhydride monomer is one of diphenyl ether tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.
The organic solvent is m-cresol or N-methyl pyrrolidone, and the dosage of the organic solvent is 7-15 times of the total mass of diamine and dianhydride monomers; the catalyst is isoquinoline, and the dosage of the catalyst is 1-3% of the mass of diamine.
The specific synthetic route of the asymmetric aromatic diamine monomer and polyimide polymer containing the terphenyl macro-substituted side group is as follows:
(1) Synthesis of an asymmetric aromatic diamine monomer containing a terphenyl macro-substituted side group:
Figure BDA0003055217590000041
(2) Synthesis of polyimide polymer containing terphenyl macro-substituted side group asymmetric structure:
Figure BDA0003055217590000042
the polyimide polymer film containing the terphenyl large-substituted side group asymmetric structure has important potential application value in the field of microelectronics.
The beneficial effects of the invention are as follows:
(1) The asymmetric aromatic diamine monomer containing the terphenyl macro-substituted side group prepared by the invention has the advantages that the used initial raw materials are easy to obtain, the adopted synthetic route is relatively simple and convenient, and the product is easy to purify and separate, has high yield and is stable at normal temperature;
(2) The polyimide film material prepared by the invention can directly obtain polyimide polymer by one-step solution polycondensation, and is not required to be converted into polyimide by polyamide acid, so that the synthesis preparation process is simple and easy to industrialize;
(3) The polyimide film material prepared by the invention has good dissolving film forming property, heat resistance and dielectric property due to the introduction of large-volume terphenyl large-substituted side group and asymmetric structure in the molecular structure of the polymer, and the prepared film has potential application value in the field of microelectronics.
Drawings
FIG. 1 is a schematic illustration of an intermediate dinitro compound and the diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene in an embodiment of the present invention 1 H NMR spectrum.
FIG. 2 is a diagram of polyimide PI a prepared from diamine monomers 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and diphenyl ether tetracarboxylic dianhydride in example 1 1 H NMR spectrum.
FIG. 3 is an infrared spectrum of the intermediate dinitro compound, diamine monomer and polyimide PI a in example 1.
FIG. 4 is a DSC graph of 3 kinds of polyimides PI a to C prepared from diamine monomers 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively, in examples.
FIG. 5 shows the respective N-type polyimide PIb prepared from diamine monomers 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and biphenyl tetracarboxylic dianhydride 2 And thermal weight loss under air.
FIG. 6 is a graph showing the UV-visible spectra of 3 polyimide PI a-c films prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively, in the example.
FIG. 7 is a graph showing the relationship between the dielectric constants of 3 kinds of polyimide PI a to c and standard Kapton thin films prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively, and the changes in the electric field frequencies in examples.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below in connection with specific examples.
The following raw materials and medicines used in the examples were:
2, 4-dinitrobromobenzene: the purity of the Wuhan growth chemical industry Co., ltd is 98%.
3, 5-diphenylphenylboronic acid: suzhou Su Kailu chemical technology Co., ltd., purity 98%.
Tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ): palladium content from Shaanxi, chemical Co., ltd.): more than or equal to 9.20 percent.
Pd/C catalyst: palladium content from Shaanxi, chemical Co., ltd.): 5.0%.
3,5- (diphenyl) phenyl-2, 4-diaminobenzene: the laboratory is self-made, and the purity is 99%.
Diphenyl ether tetracarboxylic dianhydride: the Shanghai institute of synthetic resins had a purity of 99%.
Biphenyltetracarboxylic dianhydride: the Shanghai institute of synthetic resins had a purity of 99%.
Benzophenone tetracarboxylic dianhydride: the Shanghai institute of synthetic resins had a purity of 99%.
Toluene: the purity of the chemical reagent of the national medicine group is 99 percent.
Ethylene glycol dimethyl ether: alfa company, 99% purity.
Hydrazine hydrate: the purity of the chemical reagent of the national medicine group is more than or equal to 50 percent.
M-cresol: ara Ding Shiji Co., ltd., purity 99%.
Isoquinoline: alfa company, 99% purity.
N-methylpyrrolidone, N-dimethylacetamide: the Jiangsu Seu Strong functional chemical Co., ltd., purity was 99%.
Example 1
(1) Preparation of asymmetric aromatic diamine monomer containing terphenyl macro-substituted side group
(a) 19.76g (8 mmol) of 2, 4-dinitrobromobenzene, 24.12g (88 mmol) of 3, 5-diphenylphenylboronic acid and 1.85g (0.16 mmol) of tetrakis (triphenylphosphine) palladium are added into a 500mL three-necked flask under the protection of nitrogen, 150mL of a mixed solvent of toluene and ethylene glycol dimethyl ether with a volume ratio of 2:1 and 120mL of 1mol/L of sodium carbonate solution are respectively added, the mixture is stirred at room temperature for half an hour and then heated to 100 ℃ for reaction for 8 hours, after the reaction is finished, the intermediate compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene is obtained through suction filtration, drying and further recrystallization, and the yield is 91% (the yield is obtained from the ratio of the mass of the intermediate compound obtained in practice to the mass of the intermediate compound obtained in theory).
(b) Into a three-necked flask equipped with a stirrer, 18.82g (0.05 mol) of 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene as an intermediate compound, 12.01g (0.23 mol) of hydrazine hydrate reducing agent and 0.95g of ethanol were charged, respectivelyAfter the reaction, pouring the solution into a beaker, standing, filtering after the product is separated out, washing with ethanol, and vacuum drying to obtain yellow crystalline 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, wherein the yield is 85% (the yield is obtained by the ratio of the mass of the actually obtained diamine monomer to the mass of the theoretically obtained diamine monomer) 1 H NMR(DMSO-d 6 400 MHz) is shown in fig. 1; FT-IR (KBr) is shown in FIG. 3.
(2) Preparation of polyimide containing terphenyl large-substituted side group asymmetric structure
1.3457g (4 mmol) of diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, 1.2408g (4 mmol) of diphenyl ether tetracarboxylic dianhydride and then 14mL of m-cresol (the solid content of the system is 5-20%) and 0.08mmol of isoquinoline are sequentially added into a 100mL dry three-neck flask with nitrogen protection and a condenser tube, stirring is carried out at 80 ℃ for half an hour until the monomers are completely dissolved, then the temperature is continuously increased to 180 ℃ for reaction for 10 hours, a viscous polymer solution is obtained, the reaction is ended, the polymer solution is poured into ethanol for sedimentation, and further filtration, washing and drying are carried out, thus obtaining the fibrous polyimide polymer (PI a) with the terphenyl large substituent side group asymmetric structure. Yield 99%; 1 H NMR(DMSO-d 6 400 MHz) is shown in fig. 2; FT-IR (KBr) is shown in FIG. 3.
Example 2
(1) Preparation of aromatic diamine monomer containing terphenyl macro-substituted side group asymmetric structure
(a) 19.76g (8 mmol) of 2, 4-dinitrobromobenzene, 24.12g (88 mmol) of 3, 5-diphenylphenylboronic acid and 2.10g (0.18 mmol) of tetrakis (triphenylphosphine) palladium are added into a 1000mL three-necked flask under the protection of nitrogen, 320mL of a mixed solvent of toluene and ethylene glycol dimethyl ether with a volume ratio of 4:1 and 240mL of a sodium carbonate solution are respectively added, the mixture is stirred at room temperature for half an hour and then heated to 110 ℃ for reaction for 7 hours, after the reaction is finished, the intermediate compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene is obtained through suction filtration, drying and further recrystallization, and the yield is 88% (the yield is obtained by the ratio of the mass of the intermediate compound obtained in practice to the mass of the intermediate compound obtained in theory).
(b) Into a three-necked flask equipped with a stirrer, 18.82g (0.05 mol) of 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene as an intermediate compound, 250mL of ethanol, 15.01g (0.3 mol) of hydrazine hydrate reducing agent and 1.80g of Pd/C catalyst with a solid content of 10% were added, respectively, and reacted at 95℃under reflux for 10 hours, after the completion of the reaction, the solution was poured into a beaker, left to stand, and after the precipitation of the product, suction filtration and washing with ethanol, yellow crystalline 3,5- (diphenyl) phenyl-2, 4-diaminobenzene was obtained after vacuum drying, and the yield was 81% (where the yield was obtained from the ratio of the mass of the diamine monomer actually obtained to the mass of the diamine monomer theoretically obtained).
(2) Preparation of high-solubility polyimide containing terphenyl large-substituted side group asymmetric structure
1.3457g (4 mmol) of diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, 1.1769g (4 mmol) of biphenyl tetracarboxylic dianhydride and then 13mL of N-methylpyrrolidone (the solid content of the system is 5-20%) and 0.12mmol of isoquinoline are sequentially added into a 100mL dry three-neck flask with nitrogen protection and a condenser tube, stirring is carried out at 100 ℃ for half an hour, after the monomer is completely dissolved, the temperature is continuously increased to 200 ℃ for 6 hours, the reaction is ended, the polymer solution is poured into ethanol for sedimentation, and further filtration, washing and drying are carried out, thus obtaining the fibrous polyimide polymer (PI b) containing the terphenyl macro-substituted side group asymmetric structure. The yield was 98%.
Example 3
(1) Preparation of aromatic diamine monomer containing terphenyl macro-substituted side group asymmetric structure
(a) 14.82g (6 mmol) of 2, 4-dinitrobromobenzene, 18.09g (66 mmol) of 3, 5-diphenylphenylboronic acid and 1.39g (0.13 mmol) of tetrakis (triphenylphosphine) palladium are added into a 500mL three-necked flask under the protection of nitrogen, 250mL of a mixed solvent of toluene and ethylene glycol dimethyl ether with a volume ratio of 3:1 and 150mL of a sodium carbonate solution are respectively added, the mixture is stirred at room temperature for half an hour and then heated to 100 ℃ for reaction for 10 hours, after the reaction is finished, the intermediate compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene is obtained through suction filtration, drying and further recrystallization, and the yield is 89% (the yield is obtained from the ratio of the mass of the intermediate compound obtained in practice to the mass of the intermediate compound obtained in theory).
(b) 10.16g (0.03 mol) of 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene as an intermediate compound, 9.72g (0.2 mol) of ethanol, and 0.51g of a Pd/C catalyst having a solid content of 10% were added to a three-necked flask equipped with a stirrer, and reacted at 90℃for 9 hours, after the completion of the reaction, the solution was poured into a beaker, left standing, suction-filtered after the precipitation of the product and washing with ethanol, and vacuum-dried to obtain 3,5- (diphenyl) phenyl-2, 4-diaminobenzene as yellow crystals in a yield of 84% (the yield here being obtained from the ratio of the mass of the diamine monomer actually obtained to the mass of the diamine monomer theoretically obtained).
(2) Preparation of high-solubility polyimide containing terphenyl large-substituted side group asymmetric structure
1.3457g (4 mmol) of diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, 1.2890g (4 mmol) of benzophenone tetracarboxylic dianhydride and then 16mL of m-cresol (the solid content of the system is 5-20%) and 0.06mmol of isoquinoline are sequentially added into a 100mL dry three-neck flask with nitrogen protection and a condenser tube, stirring is carried out at 90 ℃ for half an hour until the monomers are completely dissolved, then the temperature is continuously increased to 200 ℃ for reaction for 8 hours, the reaction is ended, the polymer solution is poured into ethanol for sedimentation, and further filtration, washing and drying are carried out, thus obtaining the fibrous polyimide polymer (PI c) with the terphenyl large substituent side group asymmetric structure. The yield thereof was found to be 99%.
TABLE 1 intrinsic viscosity and molecular weight of polyimide
Figure BDA0003055217590000101
a Using polystyrene as a standard,DMF was used as an eluent.
Table 1 shows intrinsic viscosities of 3 kinds of polyimides PI a to C prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, respectively, in DMAc and M of polyimide PI a to c dissolved in DMF w 、M n Values and polydispersity index (PDI).
TABLE 2 dissolution Properties of polyimide
Figure BDA0003055217590000102
Note that: ++,0.1g sample dissolved in 1mL solvent (10 wt%); ++, soluble at 5wt%; ++, soluble at 1wt%; s, swelling; -, insolated.
Table 2 shows the solubility properties of 3 polyimides PI a to PI c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively.
TABLE 3 thermal Properties of polyimide
Figure BDA0003055217590000103
a. 10％weight loss temperature in TGA；
b .Residual weight retention at 800℃in nitrogen.
Table 3 shows the thermal properties of 3 polyimides PI a-c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively.
TABLE 4 mechanical and optical Properties of polyimides
Figure BDA0003055217590000104
a. Transmittance(％)at 450nm(T 450 )；
Table 4 shows the mechanical and optical properties of 3 polyimides PI a-c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively.
TABLE 5 dielectric Properties, contact Angle and Water absorption of polyimides
Figure BDA0003055217590000111
Table 5 shows the dielectric properties and water absorption of 3 polyimides PI a-c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, diphenyl ether tetracarboxylic dianhydride, diphenyl tetramic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively.

Claims (3)

1. A polyimide containing terphenyl large substituted side group asymmetric structure for microelectronics field is characterized in that: the polyimide has the structural formula:
Figure FDA0004049284420000011
wherein ,
Figure FDA0004049284420000012
is->
Figure FDA0004049284420000013
Repeating unit n=40 to 100;
the preparation method of the polyimide containing the terphenyl macro-substituted side group asymmetric structure comprises the following steps: adding an equal amount of aromatic diamine monomer containing a terphenyl large substituent group and an aromatic dianhydride monomer into an organic solvent under the protection of nitrogen, adding a catalyst, stirring for half an hour at 80-100 ℃, continuously heating to 180-200 ℃ for reaction for 6-10 hours after the monomer is completely dissolved, obtaining a viscous polymer solution, ending the reaction, pouring the polymer solution into ethanol for sedimentation, and further filtering, washing and drying to obtain a fibrous polyimide polymer;
the aromatic diamine monomer is 3,5- (diphenyl) phenyl-2, 4-diamine benzene, and the structural formula is as follows:
Figure FDA0004049284420000014
the dianhydride monomer is one of diphenyl ether tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride; the preparation method of the asymmetric aromatic diamine monomer containing the terphenyl macro-substituted side group comprises the following steps:
(1) Under the protection of nitrogen, adding 2, 4-dinitrobromobenzene and 3, 5-diphenyl phenylboric acid into a three-neck flask with mechanical stirring, further respectively adding an organic solvent, a sodium carbonate aqueous solution and a catalyst, stirring at room temperature for half an hour, heating to 60-120 ℃ for reaction for 6-12 hours, ending the reaction, and obtaining a white intermediate dinitro compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene after sedimentation, filtration, drying and recrystallization;
(2) Adding an intermediate dinitro compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene into a three-neck flask with mechanical stirring, further adding an organic solvent, a reducing agent and a catalyst respectively, reacting for 4-12 hours under reflux, ending the reaction, pouring the solution into the beaker, standing, leaching and washing with ethanol after the product is separated out, and vacuum drying to obtain a monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene;
the polyimide application method comprises the following steps: adding polyimide polymer into organic solvent to prepare 5-10wt% solution, filtering, coating, and vacuum drying at 60-100deg.C for 12-24 h to obtain polyimide film material with asymmetric structure of terphenyl large substituted side group.
2. The polyimide with an asymmetric structure of a terphenyl macro-substituted side group according to claim 1, wherein: the organic solvent is m-cresol or N-methyl pyrrolidone, and the dosage of the organic solvent is 7-15 times of the total mass of diamine and dianhydride monomers.
3. The polyimide with an asymmetric structure of a terphenyl macro-substituted side group according to claim 1, wherein: the catalyst is isoquinoline, and the dosage of the catalyst is 1-3% of the mass of diamine.
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