CN111393645A - Preparation method of polyimide film containing benzimidazole structure - Google Patents

Preparation method of polyimide film containing benzimidazole structure Download PDF

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CN111393645A
CN111393645A CN202010267965.2A CN202010267965A CN111393645A CN 111393645 A CN111393645 A CN 111393645A CN 202010267965 A CN202010267965 A CN 202010267965A CN 111393645 A CN111393645 A CN 111393645A
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benzimidazole
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polyimide film
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CN111393645B (en
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张振宇
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Changzhou Huanfeng Electrical Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Abstract

The invention relates to a preparation method of polyimide film containing benzimidazole structure, the raw material comprises diamine monomer, the diamine monomer is benzimidazole diamine monomer, the general formula of the structure is:
Figure DDA0002442047210000011
wherein, X1、X2、Y1And Y2Is selected from-F, -H, -CH3、‑CH2CH3、‑CH2CH2CH3or-CH (CH)3)2One kind of (1). The preparation method of the polyimide film containing the benzimidazole structure is simple and easy to implement, has lower cost,can obviously improve the heat resistance and the solubility of the polyimide film and expand the application range of the polyimide film.

Description

Preparation method of polyimide film containing benzimidazole structure
Technical Field
The invention belongs to the technical field of polyimide preparation, and relates to a preparation method of a polyimide film containing a benzimidazole structure.
Background
In order to meet the requirements of high-temperature-resistant high-performance polymer materials in the current aerospace and electronic industry fields, organic polymer materials such as polyimide, polyamide, polyamideimide and polyurea are developed rapidly. Among them, diamine compounds are important raw materials for synthesizing such polymers. From the viewpoint of improving the heat resistance of the material, an aromatic heterocyclic group having good thermal stability is introduced into the polymer structure. The aromatic heterocyclic group is introduced into the main chain of the polymer to improve the heat resistance because the aromatic heterocyclic group has stronger rigidity and can also provide stronger acting force between molecular chains.
Patent CN101984157A discloses a polyimide fiber and a preparation method thereof, wherein 2- (4-aminophenyl) -5-aminobenzimidazole is introduced into a polymer structure as one of diamine monomers; patent CN102604091A discloses polyimide containing benzimidazole unit and a preparation method thereof, 6-aminophenyl-2-aminobenzimidazole is used as a diamine intermediate; patent CN102942310A discloses an organosilicon polyimide benzimidazole optical fiber coating and a preparation method thereof, wherein 2- (4-aminophenyl) -5-aminobenzimidazole is used as a diamine monomer; patent CN103422253A discloses a high strength polyimide porous membrane containing benzimidazole and benzene side groups and a preparation method thereof, wherein 2- (4-aminophenyl) -5-aminobenzimidazole is also used as a diamine monomer; patent CN105778130A discloses a high-strength high-heat-resistance polyimide microporous film and a preparation method thereof, wherein 2- (4-aminophenyl) -5-aminobenzimidazole is introduced into a heterocyclic structure; patent CN106928481A discloses an optimized preparation method of polyimide film, which uses a series of intermediates using 2- (4-aminophenyl) -5-aminobenzimidazole as main structure. Although the method disclosed in the above patent improves the heat resistance of polyimide to some extent, the glass transition temperature of the obtained polyimide is usually 400 ℃ or lower, and the strength and modulus are low.
Therefore, it is very important to research a preparation method of a high-strength and high-modulus polyimide film with good heat resistance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a polyimide film containing a benzimidazole structure.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the polyimide film containing the benzimidazole structure comprises the following steps of preparing a diamine monomer from a raw material, wherein the diamine monomer is a benzimidazole diamine monomer, and the structural general formula is as follows:
Figure BDA0002442047190000021
wherein, X1、X2、Y1And Y2Is selected from-F, -H, -CH3、-CH2CH3、-CH2CH2CH3or-CH (CH)3)2One kind of (1).
The diamine monomer in the raw materials is used for preparing the polyimide, and can obviously improve various properties of the polyimide material:
(1) because the diamine monomer has a rigid benzimidazole aromatic heterocyclic structure, stronger acting force can be given to molecular chains, so that the heat resistance of the polyimide can be obviously improved by introducing the structure into a side group of the molecular chain of the polyimide, and meanwhile, the large-volume rigid side group gives the high-strength high-modulus characteristic of the polyimide;
(2) the solubility of the polyimide film (the polyimide film can be dissolved in solvents such as tetrahydrofuran and the like at room temperature) is improved, because the side group of benzimidazole has larger volume, the hydrogen bond between molecules can be destroyed, and the solubility of polyimide is further improved, thus being beneficial to processing;
(3) the nitrogen atom in the triphenylamine structure has a hole transmission effect, so that electrochromism can be realized, and the structure is introduced into a polyimide molecular chain to provide potential value for the functionality of the polyimide material.
As a preferred technical scheme:
the preparation method of the polyimide film containing the benzimidazole structure comprises the following specific steps: firstly, dissolving a diamine monomer in an aprotic polar solvent (such as NMP, DMAC, DMF and the like) under a certain temperature condition, adding a dianhydride monomer in batches until the viscosity of the solution rises, adjusting the solid content of the solution to 5-20% to obtain a PAA solution, then coating the PAA solution on a substrate to form a uniform film, and finally, under the protection of nitrogen or inert gas, carrying out gradient heating until imidization is completed to obtain the polyimide film containing the benzimidazole structure, wherein 4,4' - (hexafluoro-isopropenyl) diphthalic anhydride and the dianhydride monomer are more than one of pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, monoether tetracarboxylic dianhydride and triphenyl diether tetracarboxylic dianhydride.
The preparation method of the polyimide film containing the benzimidazole structure has the following steps that the certain temperature is-10-40 ℃, the molar addition ratio of the diamine monomer to the dianhydride monomer is 1: 0.95-1.05, and the gradient temperature rise process is as follows: firstly, preserving heat for 1h under the condition of temperature of 60-80 ℃, then heating to 120-150 ℃, preserving heat for 1h, then heating to 200-220 ℃, preserving heat for 1h, and finally heating to 350-420 ℃, preserving heat for 10-30 min.
According to the preparation method of the polyimide film containing the benzimidazole structure, the glass transition temperature of the polyimide film containing the benzimidazole structure is 410-450 ℃, the tensile strength is 290-380 MPa, and the elastic modulus is 6-12 GPa.
The preparation method of the polyimide film containing the benzimidazole structure, as described above, X1、X2、Y1And Y2Are all-H or are respectively-CH3、-H、-CH3and-H, or respectively-CH2CH3、-H、-CH3and-H, or respectively-CH2CH2CH3、-H、-CH3and-H, or respectively-CH (CH)3)2、-H、-CH3and-CH3Or are each-CH3、-CH3、-CH(CH3)2and-H, or-F, -H, -F and-H, respectively.
In the preparation method of the polyimide film containing the benzimidazole structure, the 5% thermal decomposition temperature of the diamine monomer of the benzimidazole is 500-550 ℃.
The preparation method of the benzimidazole-containing diamine monomer comprises the following steps: reducing a benzimidazole intermediate with a structural formula shown as a formula (III), mixing a reduction product of the benzimidazole intermediate with a compound with a structural formula shown as a formula (IV), and then sequentially carrying out substitution reaction and reduction reaction to obtain a diamine monomer of benzimidazole;
the benzimidazole intermediate with the structural formula shown in the formula (III) is prepared by carrying out partial reduction reaction on a compound with the structural formula shown in the formula (I), mixing a partial reduction product with a compound with the structural formula shown in the formula (II), and then sequentially carrying out substitution reaction and ring closure reaction;
by partial reduction is meant that only the nearest-NH-to-NO is reacted2Reduction to-NH2The reaction of (1);
the structural formulas of formula (I), formula (II), formula (III) and formula (IV) are respectively as follows:
Figure BDA0002442047190000031
the structural formula of the compound shown as the formula (I) is
Figure BDA0002442047190000032
Is prepared by one-step reaction of raw materials.
When the preparation method of the polyimide film containing the benzimidazole structure is used for synthesizing the compound with the structural formula shown in the formula (I),
Figure BDA0002442047190000033
the molar ratio of the solvent to the solvent is 1:1: 20-50, the temperature of the substitution reaction is 20-80 ℃, the time is 8-48 h, the reaction temperature and the reaction time are slightly adjusted according to different chemical structures of reactants, the reaction is monitored through thin-layer chromatography (T L C), and the time required by the reaction is judged according to the condition of the completion of the reaction.
In the preparation method of the polyimide film containing the benzimidazole structure, the preparation steps of the diamine monomer of the benzimidazole are as follows:
(1) mixing a compound with a structural formula shown as a formula (I), an organic solvent and a reducing agent, and then carrying out partial reduction reaction;
(2) mixing a partial reduction product of a compound with a structural formula shown as a formula (I), an organic solvent, a compound with a structural formula shown as a formula (II) and an acid-binding agent, then carrying out a substitution reaction, adding a catalyst into the mixture, and carrying out a ring-closing reaction to obtain a benzimidazole intermediate with a structural formula shown as a formula (III);
(3) mixing a benzimidazole intermediate with a structural formula shown as a formula (III), an organic solvent and a hydrogenation catalyst, and then carrying out reduction reaction;
(4) mixing a reduction product of a benzimidazole intermediate with a structural formula shown as a formula (III), an organic solvent, a compound with a structural formula shown as a formula (IV) and a catalyst, performing a substitution reaction, adding a hydrogenation catalyst, and performing a reduction reaction to obtain a diamine monomer of the benzimidazole.
In the preparation method of the polyimide film containing the benzimidazole structure, the organic solvent in the steps (1) and (2) is more than one of dichloroethane, dichloromethane, tetrahydrofuran, trichloromethane, chlorobenzene and toluene;
in the step (1), the reducing agent is more than one of sodium sulfide, sodium hydrosulfide, potassium sulfide, potassium hydrosulfide and cesium sulfide; the mol ratio of the compound with the structural formula shown as the formula (I), the organic solvent and the reducing agent is 1: 20-100: 1-20; the temperature of partial reduction reaction is 40-100 ℃, and the time is 8-48 h;
in the step (2), the acid-binding agent is more than one of triethylamine, diisopropylethylamine, pyridine, picoline, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the catalyst is more than one of potassium fluoride, sodium fluoride, calcium fluoride and cesium fluoride; the mol ratio of a partial reduction product of the compound with the structural formula shown in the formula (I), an organic solvent, the compound with the structural formula shown in the formula (II) and an acid-binding agent is 1: 20-100: 1-5: 5-20; the molar ratio of the catalyst to the substitution product in the step (2) is 1: 50-100; the more the compound with the structural formula shown as the formula (II) is used because the raw materials are relatively cheap, the increase of the use amount can increase the yield of the reaction of the compound with the structural formula shown as the formula (I), the increase of the use amount of the acid-binding agent is also used for increasing the yield of the reaction, the yield of the reaction of the compound I is reduced due to too low use, and the raw materials are wasted due to too much use; the temperature of the substitution reaction is 20-80 ℃, and the time is 8-48 h; the temperature of the ring closing reaction is 40-200 ℃, and the time is 8-48 h;
the organic solvent in the step (3) and the step (4) is more than one of tetrahydrofuran, dichloroethane, dichloromethane, trichloromethane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, benzene, toluene, chlorobenzene and xylene; the hydrogenation catalyst is more than one of palladium carbon, platinum carbon, rhodium carbon and active nickel;
in the step (3), the molar ratio of the benzimidazole intermediate with the structural formula shown as the formula (III), the organic solvent and the reducing agent is 1: 20-100: 0.01-0.05; the temperature of the reduction reaction is 0-100 ℃, the pressure is 0.1-5.0 MPa, and the time is 8-48 h;
in the step (4), the catalyst is glacial acetic acid, concentrated hydrochloric acid with the concentration of 6-12 mol/L or concentrated sulfuric acid with the concentration of 5-18.4 mol/L, the molar ratio of the reduction product of the benzimidazole intermediate with the structural formula (III), the organic solvent, the compound with the structural formula (IV) and the catalyst is 1: 20-100: 1-5: 0.02-0.1, the molar ratio of the hydrogenation catalytic reducing agent to the substitution product of the step (4) is 0.01-0.05: 1, the temperature of the substitution reaction is 20-80 ℃, the time is 8-48 hours, the temperature of the reduction reaction is 0-100 ℃, the pressure is 0.1-5.0 MPa, and the time is 8-48 hours;
the reduction reaction in the steps (3) and (4) is reduced by using hydrogen, and the reduction reaction can be fully reduced by carrying out the reduction reaction within a certain pressure range; the reaction temperature and time in the steps (1) - (4) are adjusted according to different activities of different reactants, the yield is influenced by overhigh or overlow temperature, the time is too short, the yield is overlow, the time is too long, and the efficiency is too low.
Has the advantages that:
(1) the preparation method of the polyimide film containing the benzimidazole structure is simple and easy to implement and low in cost;
(2) the preparation method of the polyimide film containing the benzimidazole structure can obviously improve the heat resistance and the solubility of the polyimide film and expand the application range of the polyimide film.
Drawings
FIG. 1 is a voltage curve of an electrochromic test conducted on a polyimide film obtained in example 25 of the present invention;
FIG. 2 is a nuclear magnetic spectrum of a diamine monomer of benzimidazole prepared in example 1;
FIG. 3 is a nuclear magnetic spectrum of a diamine monomer of benzimidazole prepared in example 2;
FIG. 4 is a nuclear magnetic spectrum of a diamine monomer of benzimidazole prepared in example 3;
FIG. 5 is a nuclear magnetic spectrum of a diamine monomer of benzimidazole obtained in example 4;
FIG. 6 is a nuclear magnetic spectrum of a diamine monomer of benzimidazole prepared in example 5;
FIG. 7 is a nuclear magnetic spectrum of a diamine monomer of benzimidazole obtained in example 6;
FIG. 8 is a nuclear magnetic spectrum of a diamine monomer of benzimidazole obtained in example 7.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Figure BDA0002442047190000051
Figure BDA0002442047190000061
Example 1
(X in the structural formula in this example)1、X2、Y1And Y2Are all-H)
The preparation method of the benzimidazole diamine monomer comprises the following basic steps:
(1) at a molar ratio of 1:1:20
Figure BDA0002442047190000062
Reacting with methanol in one step to obtain the compound with the structural formula shown in the specification(I) The reaction temperature is 20 ℃, and the reaction time is 48 hours;
(2) mixing a compound with a structural formula shown as a formula (I) and a molar ratio of 1:20:1, dichloroethane and sodium sulfide, and then carrying out partial reduction reaction (the partial reduction reaction refers to that only-NO closest to-NH-is subjected to partial reduction reaction2Reduction to-NH2The reaction) and the temperature of the partial reduction reaction is 40 ℃ and the time is 48 hours;
(3) mixing a partial reduction product of a compound with a structural formula shown in a formula (I) and a molar ratio of 1:20:1:5, dichloroethane, a compound with a structural formula shown in a formula (II) and triethylamine, performing a substitution reaction at 20 ℃ for 48 hours, adding potassium fluoride with a molar ratio of 1:50 to the substitution product, and performing a ring closing reaction at 40 ℃ for 48 hours to obtain a benzimidazole intermediate with a structural formula shown in a formula (III);
(4) mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:20:0.02, tetrahydrofuran and palladium-carbon in an autoclave, replacing three times with nitrogen, and then filling hydrogen to perform a reduction reaction at 50 ℃, under 0.8MPa for 48 hours;
(5) mixing a reduction product of a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:20:1:0.02, tetrahydrofuran, a compound with a structural formula shown as a formula (IV) and glacial acetic acid, then carrying out a substitution reaction at the temperature of 20 ℃ for 48h, adding the product into a high-pressure kettle, adding palladium-carbon with a molar ratio of 0.02:1 to the substitution product, then carrying out a reduction reaction to obtain a diamine monomer of the benzimidazole, replacing the diamine monomer with nitrogen for three times, then filling hydrogen to carry out the reduction reaction, wherein the temperature of the reduction reaction is 35 ℃, the pressure is 1.3MPa, and the time is 48 h.
The structural formula of the finally prepared diamine monomer of the benzimidazole is as follows:
Figure BDA0002442047190000063
the nuclear magnetic spectrum is shown in figure 2; the 5% thermal decomposition temperature of the diamine monomer of benzimidazoles was 500 ℃.
Example 2
(X in the structural formula in this example)1、X2、Y1And Y2Are respectively-CH3、-H、-CH3and-H)
The preparation method of the benzimidazole diamine monomer comprises the following basic steps:
(1) at a molar ratio of 1:1:30
Figure BDA0002442047190000071
Reacting with methanol at 40 deg.C for 25 hr to obtain compound of formula (I);
(2) mixing a compound with a structural formula shown as a formula (I) and a molar ratio of 1:40:5, dichloromethane and sodium hydrogen sulfide, and then carrying out partial reduction reaction (the partial reduction reaction refers to that only-NO closest to-NH-is subjected to partial reduction reaction2Reduction to-NH2The reaction) and the temperature of the partial reduction reaction is 60 ℃ and the time is 30 hours;
(3) mixing a partial reduction product of a compound with a structural formula shown in a formula (I) and a molar ratio of 1:40:2:8, dichloromethane, a compound with a structural formula shown in a formula (II) and diisopropylethylamine, then carrying out a substitution reaction at 50 ℃ for 15 hours, adding sodium fluoride into the mixture at a molar ratio of 1:60 to the substitution product, and then carrying out a ring closing reaction at 60 ℃ for 15 hours to obtain a benzimidazole intermediate with a structural formula shown in a formula (III);
(4) mixing a benzimidazole intermediate with a structural formula shown as a formula (III) in a molar ratio of 1:40:0.05, dichloroethane and platinum carbon in an autoclave, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at the temperature of 50 ℃ and under the pressure of 2.5MPa for 15 hours;
(5) mixing a reduction product of a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:40:2:0.05, dichloroethane, a compound with a structural formula shown as a formula (IV) and concentrated hydrochloric acid with a concentration of 6 mol/L, then carrying out a substitution reaction at 40 ℃ for 20h, adding the product into a high-pressure kettle, adding platinum carbon with a molar ratio of 0.03:1 to the substitution product, and then carrying out a reduction reaction to obtain a diamine monomer of the benzimidazole, wherein the temperature of the reduction reaction is 20 ℃, the pressure is 2.5MPa, and the time is 15 h.
The structural formula of the finally prepared diamine monomer of the benzimidazole is as follows:
Figure BDA0002442047190000072
the nuclear magnetic spectrum is shown in figure 3; the 5% thermal decomposition temperature of the diamine monomer of the benzimidazole was 515 ℃.
Example 3
(X in the structural formula in this example)1、X2、Y1And Y2Are respectively-CH2CH3、-H、-CH3and-H)
The preparation method of the benzimidazole diamine monomer comprises the following basic steps:
(1) at a molar ratio of 1:1:45
Figure BDA0002442047190000081
Reacting with methanol at 80 deg.C for 8 hr to obtain compound of formula (I);
(2) mixing a compound with a structural formula shown as a formula (I) and a molar ratio of 1:80:10, tetrahydrofuran and potassium sulfide, and then carrying out partial reduction reaction (the partial reduction reaction refers to that only-NO closest to-NH-is subjected to partial reduction reaction2Reduction to-NH2The reaction) and the temperature of the partial reduction reaction is 70 ℃ and the time is 10 hours;
(3) mixing a partial reduction product of a compound with a structural formula shown as a formula (I) and a molar ratio of 1:60:4:10, tetrahydrofuran, a compound with a structural formula shown as a formula (II) and pyridine, then carrying out a substitution reaction at 60 ℃ for 20 hours, adding calcium fluoride into the mixture at a molar ratio of 1:85 to the substitution product, and then carrying out a ring closing reaction at 110 ℃ for 10 hours to obtain a benzimidazole intermediate with a structural formula shown as a formula (III);
(4) mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:78:0.03, dichloromethane and rhodium carbon in an autoclave, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at 70 ℃ under 4.2MPa for 12 hours;
(5) mixing a reduction product of a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:70:3:0.08, dichloromethane, a compound with a structural formula shown as a formula (IV) and concentrated hydrochloric acid with a concentration of 8 mol/L, then carrying out a substitution reaction at a temperature of 50 ℃ for 16h, adding the product into a high-pressure kettle, adding rhodium carbon with a molar ratio of 0.05:1 to the substitution product, then carrying out a reduction reaction to obtain a diamine monomer of the benzimidazole, wherein the temperature of the reduction reaction is 75 ℃, the pressure is 2.7MPa, and the time is 25 h.
The structural formula of the finally prepared diamine monomer of the benzimidazole is as follows:
Figure BDA0002442047190000082
the nuclear magnetic spectrum is shown in figure 4; the 5% thermal decomposition temperature of the diamine monomer of the benzimidazole was 520 ℃.
Example 4
(X in the structural formula in this example)1、X2、Y1And Y2Are respectively-CH2CH2CH3、-H、-CH3and-H)
The preparation method of the benzimidazole diamine monomer comprises the following basic steps:
(1) at a molar ratio of 1:1:50
Figure BDA0002442047190000091
Reacting with methanol at 80 deg.C for 8 hr to obtain compound of formula (I);
(2) mixing a compound with a structural formula shown as a formula (I) and a molar ratio of 1:100:2, trichloromethane and potassium hydrosulfide, and then carrying out partial reduction reaction (the partial reduction reaction refers to that only-NO closest to-NH-is subjected to partial reduction reaction2Reduction to-NH2The reaction) and the temperature of the partial reduction reaction is 60 ℃ and the time is 8 h;
(3) mixing a partial reduction product of a compound with a structural formula shown in a formula (I) and a molar ratio of 1:100:5:20, chloroform, a compound with a structural formula shown in a formula (II) and picoline, then carrying out a substitution reaction at 80 ℃ for 8 hours, adding cesium fluoride with the molar ratio of 1:100 into the mixture, and then carrying out a ring closing reaction at 200(80) ℃ for 8 hours to obtain a benzimidazole intermediate with a structural formula shown in a formula (III);
(4) mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:100:0.01, trichloromethane and active nickel in an autoclave, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at 80 ℃ under 5.0MPa for 8 hours;
(5) mixing a reduction product of a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:100:5:0.1, chloroform, a compound with a structural formula shown as a formula (IV) and concentrated hydrochloric acid with a concentration of 12 mol/L, then carrying out a substitution reaction at a temperature of 80 ℃ for 8 hours, adding the product into a high-pressure kettle, adding active nickel with a molar ratio of 0.05:1 to the substitution product, then carrying out a reduction reaction to obtain a diamine monomer of the benzimidazole, wherein the temperature of the reduction reaction is 100 ℃, the pressure is 5.0MPa, and the time is 8 hours.
The structural formula of the finally prepared diamine monomer of the benzimidazole is as follows:
Figure BDA0002442047190000092
the nuclear magnetic spectrum is shown in figure 5; the 5% thermal decomposition temperature of the diamine monomer of benzimidazole is 542 ℃; .
Example 5
(X in the structural formula in this example)1、X2、Y1And Y2Are respectively-CH (CH)3)2、-H、-CH3and-CH3)
The preparation method of the benzimidazole diamine monomer comprises the following basic steps:
(1) will rubIn a molar ratio of 1:1:50
Figure BDA0002442047190000101
Reacting with ethanol at 80 deg.C for 8 hr to obtain compound of formula (I);
(2) mixing a compound with a structural formula shown as a formula (I) and a molar ratio of 1:100:20, chlorobenzene and cesium sulfide, and then carrying out partial reduction reaction (the partial reduction reaction refers to that only-NO closest to-NH-is subjected to partial reduction reaction2Reduction to-NH2The reaction) and the temperature of the partial reduction reaction is 100 ℃ and the time is 8 hours;
(3) mixing a partial reduction product of a compound with a structural formula shown in a formula (I) and a molar ratio of 1:50:2:15, chlorobenzene, a compound with a structural formula shown in a formula (II) and sodium carbonate, then carrying out a substitution reaction at 80 ℃ for 8 hours, adding a mixture of potassium fluoride and sodium fluoride (the molar ratio of the potassium fluoride to the sodium fluoride is 1: 100) with the substitution product, and then carrying out a ring closing reaction to obtain a benzimidazole intermediate with a structural formula shown in a formula (III), wherein the temperature of the ring closing reaction is 200 ℃ and the time is 8 hours;
(4) mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:100:0.01, dimethylformamide and a mixture of palladium carbon and platinum carbon (the molar ratio of the two is 2:1) in an autoclave, replacing the mixture with nitrogen for three times, and then filling hydrogen for reduction reaction at the temperature of 100 ℃, the pressure of 5.0MPa and the time of 8 hours;
(5) mixing a reduction product of a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:100:5:0.1, dimethylformamide, a compound with a structural formula shown as a formula (IV) and concentrated sulfuric acid with a concentration of 5 mol/L, then carrying out a substitution reaction at a temperature of 80 ℃ for 8 hours, adding the product into a high-pressure kettle, adding active nickel with a molar ratio of 0.01:1 to the substitution product, then carrying out a reduction reaction to obtain a diamine monomer of the benzimidazole, wherein the temperature of the reduction reaction is 100 ℃, the pressure is 5.0MPa, and the time is 8 hours.
The structural formula of the finally prepared diamine monomer of the benzimidazole is as follows:
Figure BDA0002442047190000102
the nuclear magnetic spectrum is shown in figure 6; the 5% thermal decomposition temperature of the diamine monomer of benzimidazoles was 550 ℃.
Example 6
(X in the structural formula in this example)1、X2、Y1And Y2Are respectively-CH3、-CH3、-CH(CH3)2and-H)
The preparation method of the benzimidazole diamine monomer comprises the following basic steps:
(1) at a molar ratio of 1:1:50
Figure BDA0002442047190000111
Reacting with ethanol at 50 deg.C for 18h to obtain compound of formula (I);
(2) mixing a compound with a structural formula shown as a formula (I) and a molar ratio of 1:50:12, toluene, sodium sulfide and sodium hydrosulfide in a molar ratio of 1:1, and then carrying out partial reduction reaction (the partial reduction reaction refers to that only-NO closest to-NH-is subjected to partial reduction reaction2Reduction to-NH2The reaction) and the temperature of the partial reduction reaction is 100 ℃ and the time is 8 hours;
(3) mixing a partial reduction product of a compound with a structural formula shown in a formula (I) and a molar ratio of 1:100:3:15, toluene, a compound with a structural formula shown in a formula (II) and sodium bicarbonate, then carrying out a substitution reaction at 80 ℃ for 8 hours, adding potassium fluoride into the mixture at a molar ratio of 1:100 to the substitution product, and then carrying out a ring closing reaction to obtain a benzimidazole intermediate with a structural formula shown in a formula (III), wherein the ring closing reaction is carried out at 200 ℃ for 8 hours;
(4) mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:20:0.02, N-methyl pyrrolidone and palladium carbon in an autoclave, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at the temperature of 70 ℃, the pressure of 5.0MPa and the time of 20 hours;
(5) mixing a reduction product of a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:100:1:0.02, dimethylacetamide, a compound with a structural formula shown as a formula (IV) and concentrated sulfuric acid with a concentration of 13.5 mol/L, then carrying out a substitution reaction at 80 ℃ for 15h, adding the product into a high-pressure kettle, adding active nickel with a molar ratio of 0.02:1 to the substitution product, and then carrying out a reduction reaction to obtain a diamine monomer of the benzimidazole, wherein the reduction reaction temperature is 100 ℃, the pressure is 5.0MPa, and the time is 8 h.
The structural formula of the finally prepared diamine monomer of the benzimidazole is as follows:
Figure BDA0002442047190000112
the nuclear magnetic spectrum is shown in figure 7; the 5% thermal decomposition temperature of the diamine monomer of benzimidazoles was 529 ℃.
Example 7
(X in the structural formula in this example)1、X2、Y1And Y2Are respectively-F, -H, -F and-H)
The preparation method of the benzimidazole diamine monomer comprises the following basic steps:
(1) at a molar ratio of 1:1:50
Figure BDA0002442047190000121
Reacting with methanol at 80 deg.C for 8 hr to obtain compound of formula (I);
(2) mixing a compound with a structural formula shown as a formula (I) and a molar ratio of 1:55:10, toluene and cesium sulfide, and then carrying out partial reduction reaction (the partial reduction reaction refers to that only-NO closest to-NH-is subjected to partial reduction reaction2Reduction to-NH2The reaction) and the temperature of the partial reduction reaction is 100 ℃ and the time is 8 hours;
(3) mixing a partial reduction product of a compound with a structural formula shown as a formula (I) and a molar ratio of 1:100:5:15, toluene, a compound with a structural formula shown as a formula (II) and potassium carbonate, then carrying out a substitution reaction at 80 ℃ for 8 hours, adding calcium fluoride into the mixture at a molar ratio of 1:100 to the substitution product, and then carrying out a ring closing reaction to obtain a benzimidazole intermediate with a structural formula shown as a formula (III), wherein the temperature of the ring closing reaction is 180 ℃ and the time is 8 hours;
(4) mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:100:0.03, N-methyl pyrrolidone and active nickel in an autoclave, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at the temperature of 80 ℃ and under the pressure of 4.0MPa for 12 hours;
(5) mixing a reduction product of a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:100:5:0.1, N-methyl pyrrolidone, a compound with a structural formula shown as a formula (IV) and concentrated sulfuric acid with a concentration of 18.4 mol/L, then carrying out a substitution reaction at 80 ℃ for 8h, adding the product into a high-pressure kettle, adding palladium carbon with a molar ratio of 0.02:1 to the substitution product, and then carrying out a reduction reaction to obtain a diamine monomer of the benzimidazole, wherein the temperature of the reduction reaction is 100 ℃, the pressure is 5.0MPa, and the time is 8 h.
The structural formula of the finally prepared diamine monomer of the benzimidazole is as follows:
Figure BDA0002442047190000122
the nuclear magnetic spectrum is shown in figure 8; the 5% thermal decomposition temperature of the diamine monomer of the benzimidazole was 528 ℃.
Example 8
The procedure of the preparation of the benzimidazole diamine monomer is substantially the same as that of example 7, except that the toluene in the steps (2) and (3) is replaced by a mixture of tetrahydrofuran and chlorobenzene in a mass ratio of 1:1, and the structural formula of the finally prepared benzimidazole diamine monomer is the same as that of example 7.
Examples 9 to 15
The preparation method of the benzimidazole diamine monomer is basically the same as that in the example 7, except that the N-methylpyrrolidone in the step (4) is replaced by dimethylacetamide, 1, 4-dioxane, benzene, toluene, chlorobenzene, xylene and a mixture of benzene and xylene in a mass ratio of 1:1, and the structural formula of the finally prepared benzimidazole diamine monomer is the same as that in the example 7.
Examples 16 to 21
The preparation method of the benzimidazole diamine monomer is basically the same as that in example 7, except that the N-methylpyrrolidone in the step (5) is replaced by 1, 4-dioxane, benzene, toluene, chlorobenzene, xylene and a mixture of chlorobenzene and xylene in a mass ratio of 1:1, and the structural formula of the finally prepared benzimidazole diamine monomer is the same as that in example 7.
Examples 22 to 24
The preparation method of the benzimidazole diamine monomer is basically the same as that in example 7, except that potassium carbonate in the step (3) is replaced by a mixture of sodium bicarbonate, potassium bicarbonate and triethylamine and diisopropylethylamine in a mass ratio of 1:1, and the structural formula of the finally prepared benzimidazole diamine monomer is the same as that in example 7.
Example 25
A preparation method of a polyimide film containing a benzimidazole structure comprises the steps of dissolving a diamine monomer prepared in example 1 in an aprotic polar solvent (NMP) at the temperature of 20 ℃, adding 4,4'- (hexafluoro-isopropyl) diphthalic anhydride in batches until the viscosity of the solution rises, adjusting the solid content of the solution to 10% to obtain a PAA solution, coating the PAA solution on a substrate to form a uniform film, and finally, heating in a gradient manner under the protection of nitrogen until imidization is completed to obtain the polyimide film containing the benzimidazole structure, wherein the molar addition ratio of the diamine monomer to the 4,4' - (hexafluoro-isopropyl) diphthalic anhydride is 1:1.02, and the gradient heating process is as follows: firstly, preserving heat for 1h at the temperature of 65 ℃, then heating to 135 ℃ and preserving heat for 1h, then heating to 212 ℃ and preserving heat for 1h, and finally heating to 365 ℃ and preserving heat for 15 min;
the prepared polyimide film containing the benzimidazole structure has the glass transition temperature of 430 ℃, the tensile strength of 300MPa and the elastic modulus of 10 Gpa; the polyimide film was soluble in tetrahydrofuran at room temperature, and as shown in fig. 1, when a voltage was applied to the film, the polymer film changed from pale yellow to green with an increase in voltage.
Example 26
Dissolving the diamine monomer prepared in the example 2 in an aprotic polar solvent (NMP) at the temperature of-10 ℃, adding pyromellitic dianhydride in batches until the viscosity of the solution rises, adjusting the solid content of the solution to 5% to obtain a PAA solution, then coating the PAA solution on a substrate to form a uniform film, and finally performing gradient heating under the protection of helium until imidization is completed to obtain the polyimide film containing the benzimidazole structure, wherein the molar addition ratio of the diamine monomer to the pyromellitic dianhydride is 1:0.95, and the gradient heating process is as follows: firstly, preserving heat for 1h at the temperature of 60 ℃, then heating to 120 ℃ and preserving heat for 1h, then heating to 200 ℃ and preserving heat for 1h, and finally heating to 350 ℃ and preserving heat for 30 min;
the prepared polyimide film containing the benzimidazole structure has the glass transition temperature of 410 ℃, the tensile strength of 290MPa and the elastic modulus of 12 Gpa; the polyimide film is soluble in tetrahydrofuran at room temperature, and when a voltage is applied to the film, the polymer film changes from pale yellow to green with an increase in voltage.
Example 27
Dissolving the diamine monomer prepared in the example 3 in an aprotic polar solvent (DMAC) at the temperature of 0 ℃, adding the biphenyl tetracarboxylic dianhydride in batches until the viscosity of the solution rises, adjusting the solid content of the solution to 8% to obtain a PAA solution, then coating the PAA solution on a substrate to form a uniform film, and finally performing gradient temperature rise under the protection of argon until imidization is completed to obtain the polyimide film containing the benzimidazole structure, wherein the molar addition ratio of the diamine monomer to the biphenyl tetracarboxylic dianhydride is 1:1.03, and the gradient temperature rise process is as follows: firstly, preserving heat for 1h at the temperature of 75 ℃, then heating to 125 ℃ and preserving heat for 1h, then heating to 210 ℃ and preserving heat for 1h, and finally heating to 370 ℃ and preserving heat for 26 min;
the prepared polyimide film containing the benzimidazole structure has the glass transition temperature of 418 ℃, the tensile strength of 310MPa and the elastic modulus of 6 GPa; the polyimide film is soluble in tetrahydrofuran at room temperature, and when a voltage is applied to the film, the polymer film changes from pale yellow to green with an increase in voltage.
Example 28
A preparation method of a polyimide film containing a benzimidazole structure comprises the steps of dissolving a diamine monomer prepared in the embodiment 4 in an aprotic polar solvent (DMAC) at the temperature of 15 ℃, adding monoether tetracarboxylic dianhydride in batches until the viscosity of the solution rises, adjusting the solid content of the solution to 15% to obtain a PAA solution, coating the PAA solution on a substrate to form a uniform film, and finally performing gradient heating under the protection of nitrogen until imidization is completed to obtain the polyimide film containing the benzimidazole structure, wherein the molar adding amount ratio of the diamine monomer to the monoether tetracarboxylic dianhydride is 1:1.05, and the gradient heating process is as follows: firstly, preserving heat for 1h at the temperature of 70 ℃, then heating to 138 ℃, preserving heat for 1h, then heating to 215 ℃, preserving heat for 1h, and finally heating to 390 ℃, preserving heat for 22 min;
the prepared polyimide film containing the benzimidazole structure has the glass transition temperature of 427 ℃, the tensile strength of 330MPa and the elastic modulus of 7 GPa; the polyimide film is soluble in tetrahydrofuran at room temperature, and when a voltage is applied to the film, the polymer film changes from pale yellow to green with an increase in voltage.
Example 29
Dissolving the diamine monomer prepared in the example 5 in an aprotic polar solvent (DMF) at a temperature of 25 ℃, adding the triphenyldiether tetracarboxylic dianhydride in batches until the viscosity of the solution rises, adjusting the solid content of the solution to 12% to obtain a PAA solution, then coating the PAA solution on a substrate to form a uniform film, and finally performing gradient heating under the protection of helium until imidization is completed to obtain the polyimide film containing the benzimidazole structure, wherein the molar addition ratio of the diamine monomer to the triphenyldiether tetracarboxylic dianhydride is 1:0.98, and the gradient heating process is as follows: firstly, preserving heat for 1h at the temperature of 77 ℃, then heating to 140 ℃ and preserving heat for 1h, then heating to 213 ℃ and preserving heat for 1h, and finally heating to 400 ℃ and preserving heat for 18 min;
the prepared polyimide film containing the benzimidazole structure has the glass transition temperature of 435 ℃, the tensile strength of 350MPa and the elastic modulus of 9 GPa; the polyimide film is soluble in tetrahydrofuran at room temperature, and when a voltage is applied to the film, the polymer film changes from pale yellow to green with an increase in voltage.
Example 30
Dissolving the diamine monomer prepared in the example 6 in an aprotic polar solvent (DMF) at a temperature of 35 ℃, adding a dianhydride monomer (specifically, a mixture of pyromellitic dianhydride and biphenyltetracarboxylic dianhydride in a mass ratio of 1:1) in batches until the viscosity of the solution rises, adjusting the solid content of the solution to 14% to obtain a PAA solution, coating the PAA solution on a substrate to form a uniform film, and finally performing gradient heating under the protection of argon until imidization is completed to obtain the polyimide film containing the benzimidazole structure, wherein the molar addition ratio of the diamine monomer to the dianhydride monomer is 1:0.97, and the gradient heating process is as follows: firstly, preserving heat for 1h at the temperature of 80 ℃, then heating to 145 ℃ and preserving heat for 1h, then heating to 218 ℃ and preserving heat for 1h, and finally heating to 415 ℃ and preserving heat for 15 min;
the prepared polyimide film containing the benzimidazole structure has the glass transition temperature of 440 ℃, the tensile strength of 370MPa and the elastic modulus of 10 GPa; the polyimide film is soluble in tetrahydrofuran at room temperature, and when a voltage is applied to the film, the polymer film changes from pale yellow to green with an increase in voltage.
Example 31
A preparation method of polyimide film containing benzimidazole structure, under the temperature condition of 40 ℃, dissolving the diamine monomer prepared in the embodiment 7 in an aprotic polar solvent (DMF), adding biphenyl tetracarboxylic dianhydride in batches until the solution viscosity rises, adjusting the solid content of the solution to 20% to obtain a PAA solution, then coating the PAA solution on a substrate to form a uniform film, and finally performing gradient temperature rise under the protection of nitrogen until imidization is completed to obtain the polyimide film containing benzimidazole structure, wherein the molar adding amount ratio of the diamine monomer to the biphenyl tetracarboxylic dianhydride is 1:1, and the gradient temperature rise process is as follows: firstly, preserving heat for 1h at the temperature of 68 ℃, then heating to 150 ℃ and preserving heat for 1h, then heating to 220 ℃ and preserving heat for 1h, and finally heating to 420 ℃ and preserving heat for 10 min;
the prepared polyimide film containing the benzimidazole structure has the glass transition temperature of 450 ℃, the tensile strength of 380MPa and the elastic modulus of 11 GPa; the polyimide film is soluble in tetrahydrofuran at room temperature, and when a voltage is applied to the film, the polymer film changes from pale yellow to green with an increase in voltage.
Examples 32 to 48
The preparation method of the polyimide film containing the benzimidazole structure is basically the same as that in example 25, except that the diamine monomers used are the diamine monomers prepared in the above examples 8 to 24, and the performances of the finally prepared polyimide film containing the benzimidazole structure are shown in table 1; furthermore, the polyimide films prepared in examples 32 to 48 were soluble in tetrahydrofuran at room temperature, and when a voltage was applied to the films, the polymer films changed from pale yellow to green with increasing voltage.
TABLE 1
Figure BDA0002442047190000161

Claims (10)

1. The preparation method of the polyimide film containing the benzimidazole structure comprises the following steps of preparing a diamine monomer from the raw materials, wherein the preparation method comprises the following steps: the diamine monomer is a diamine monomer of benzimidazole, and the structural general formula is as follows:
Figure FDA0002442047180000011
wherein, X1、X2、Y1And Y2Is selected from-F, -H, -CH3、-CH2CH3、-CH2CH2CH3or-CH (CH)3)2One kind of (1).
2. The preparation method of the polyimide film containing the benzimidazole structure according to claim 1, wherein the specific process comprises: firstly, dissolving a diamine monomer in an aprotic polar solvent under a certain temperature condition, adding a dianhydride monomer in batches until the viscosity of the solution rises, adjusting the solid content of the solution to 5-20% to obtain a PAA solution, then coating the PAA solution on a substrate to form a uniform film, and finally, heating in a gradient manner under the protection of nitrogen or inert gas until imidization is completed to obtain the polyimide film containing the benzimidazole structure.
3. The preparation method of the polyimide film containing the benzimidazole structure according to claim 2, wherein the certain temperature is-10 to 40 ℃, the molar addition ratio of the diamine monomer to the dianhydride monomer is 1:0.95 to 1.05, and the gradient temperature rise process comprises: firstly, preserving heat for 1h under the condition of temperature of 60-80 ℃, then heating to 120-150 ℃, preserving heat for 1h, then heating to 200-220 ℃, preserving heat for 1h, and finally heating to 350-420 ℃, preserving heat for 10-30 min.
4. The method for preparing the polyimide film containing the benzimidazole structure according to claim 3, wherein the polyimide film containing the benzimidazole structure has a glass transition temperature of 410-450 ℃, a tensile strength of 290-380 MPa, and an elastic modulus of 6-12 GPa.
5. The method for preparing polyimide film containing benzimidazole structure according to claim 1, wherein X is1、X2、Y1And Y2Are all-H or are respectively-CH3、-H、-CH3and-H, or respectively-CH2CH3、-H、-CH3and-H, or respectively-CH2CH2CH3、-H、-CH3and-H, or respectively-CH (CH)3)2、-H、-CH3and-CH3Or are each-CH3、-CH3、-CH(CH3)2and-H, or-F, -H, -F and-H, respectively.
6. The method for preparing the polyimide film containing the benzimidazole structure according to claim 5, wherein the 5% thermal decomposition temperature of the diamine monomer of the benzimidazole is 500-550 ℃.
7. The method for preparing the polyimide film containing the benzimidazole structure according to claim 6, wherein the benzimidazole diamine monomer is prepared by: reducing a benzimidazole intermediate with a structural formula shown as a formula (III), mixing a reduction product of the benzimidazole intermediate with a compound with a structural formula shown as a formula (IV), and then sequentially carrying out substitution reaction and reduction reaction to obtain a diamine monomer of benzimidazole;
the benzimidazole intermediate with the structural formula shown in the formula (III) is prepared by carrying out partial reduction reaction on a compound with the structural formula shown in the formula (I), mixing a partial reduction product with a compound with the structural formula shown in the formula (II), and then sequentially carrying out substitution reaction and ring closure reaction;
by partial reduction is meant that only the nearest-NH-to-NO is reacted2Reduction to-NH2The reaction of (1);
the structural formulas of formula (I), formula (II), formula (III) and formula (IV) are respectively as follows:
Figure FDA0002442047180000021
the structural formula of the compound shown as the formula (I) is
Figure FDA0002442047180000022
Is prepared by one-step reaction of raw materials.
8. The method for preparing polyimide film containing benzimidazole structure according to claim 7, wherein the compound having formula (I) is synthesized,
Figure FDA0002442047180000023
and a solvent in a molar ratio of 1:1: 20-50, and carrying out substitution reactionThe temperature is 20-80 ℃, and the time is 8-48 h.
9. The method for preparing the polyimide film containing the benzimidazole structure according to claim 8, wherein the benzimidazole diamine monomer is prepared by the following steps:
(1) mixing a compound with a structural formula shown as a formula (I), an organic solvent and a reducing agent, and then carrying out partial reduction reaction;
(2) mixing a partial reduction product of a compound with a structural formula shown as a formula (I), an organic solvent, a compound with a structural formula shown as a formula (II) and an acid-binding agent, then carrying out a substitution reaction, adding a catalyst into the mixture, and carrying out a ring-closing reaction to obtain a benzimidazole intermediate with a structural formula shown as a formula (III);
(3) mixing a benzimidazole intermediate with a structural formula shown as a formula (III), an organic solvent and a hydrogenation catalyst, and then carrying out reduction reaction;
(4) mixing a reduction product of a benzimidazole intermediate with a structural formula shown as a formula (III), an organic solvent, a compound with a structural formula shown as a formula (IV) and a catalyst, performing a substitution reaction, adding a hydrogenation catalyst, and performing a reduction reaction to obtain a diamine monomer of the benzimidazole.
10. The method for preparing a polyimide film containing a benzimidazole structure according to claim 9, wherein the organic solvent used in the steps (1) and (2) is one or more of dichloroethane, dichloromethane, tetrahydrofuran, chloroform, chlorobenzene, and toluene;
in the step (1), the reducing agent is more than one of sodium sulfide, sodium hydrosulfide, potassium sulfide, potassium hydrosulfide and cesium sulfide; the mol ratio of the compound with the structural formula shown as the formula (I), the organic solvent and the reducing agent is 1: 20-100: 1-20; the temperature of partial reduction reaction is 40-100 ℃, and the time is 8-48 h;
in the step (2), the acid-binding agent is more than one of triethylamine, diisopropylethylamine, pyridine, picoline, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the catalyst is more than one of potassium fluoride, sodium fluoride, calcium fluoride and cesium fluoride; the mol ratio of a partial reduction product of the compound with the structural formula shown in the formula (I), an organic solvent, the compound with the structural formula shown in the formula (II) and an acid-binding agent is 1: 20-100: 1-5: 5-20; the molar ratio of the catalyst to the substitution product in the step (2) is 1: 50-100; the temperature of the substitution reaction is 20-80 ℃, and the time is 8-48 h; the temperature of the ring closing reaction is 40-200 ℃, and the time is 8-48 h;
the organic solvent in the step (3) and the step (4) is more than one of tetrahydrofuran, dichloroethane, dichloromethane, trichloromethane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, benzene, toluene, chlorobenzene and xylene; the hydrogenation catalyst is more than one of palladium carbon, platinum carbon, rhodium carbon and active nickel;
in the step (3), the molar ratio of the benzimidazole intermediate with the structural formula shown as the formula (III), the organic solvent and the reducing agent is 1: 20-100: 0.01-0.05; the temperature of the reduction reaction is 0-100 ℃, the pressure is 0.1-5.0 MPa, and the time is 8-48 h;
in the step (4), the catalyst is glacial acetic acid, concentrated hydrochloric acid with the concentration of 6-12 mol/L or concentrated sulfuric acid with the concentration of 5-18.4 mol/L, the molar ratio of the reduction product of the benzimidazole intermediate with the structural formula (III), the organic solvent, the compound with the structural formula (IV) and the catalyst is 1: 20-100: 1-5: 0.02-0.1, the molar ratio of the hydrogenation catalytic reducing agent to the substitution product of the step (4) is 0.01-0.05: 1, the temperature of the substitution reaction is 20-80 ℃, the time is 8-48 hours, the temperature of the reduction reaction is 0-100 ℃, the pressure is 0.1-5.0 MPa, and the time is 8-48 hours.
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