CN111440318A - Preparation method of polyimide film containing benzimidazole structure - Google Patents

Preparation method of polyimide film containing benzimidazole structure Download PDF

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CN111440318A
CN111440318A CN202010268007.7A CN202010268007A CN111440318A CN 111440318 A CN111440318 A CN 111440318A CN 202010268007 A CN202010268007 A CN 202010268007A CN 111440318 A CN111440318 A CN 111440318A
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benzimidazole
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polyimide film
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张振宇
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Changzhou Huanfeng Electrical Materials Co ltd
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Abstract

The invention relates to a preparation method of a polyimide film containing a benzimidazole structure, which comprises the following steps of preparing a diamine monomer from raw materials, wherein the diamine monomer is a diamine monomer containing benzimidazole groups, and the structural general formula is as follows:
Figure DDA0002442059090000011
wherein Z is1And Z2Is 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 low cost, can obviously improve the heat resistance and the solubility of the polyimide film, and expands 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 polyimide obtained 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, wherein the diamine monomer is a diamine monomer containing benzimidazole groups, and the structural general formula is as follows:
Figure BDA0002442059070000021
wherein Z is1And Z2Is selected from-F, -H, -CH3、-CH2CH3、-CH2CH2CH3or-CH (CH)3)2One kind of (1). The diamine monomer containing the benzimidazole group can be used for preparing polyimide, and can obviously improve various properties of polyimide materials:
the diamine monomer has a rigid benzimidazole aromatic heterocyclic structure and can endow stronger acting force between 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 high-strength high-modulus characteristic of the polyimide is endowed by the large-volume rigid side group;
(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.
Monomers of the following structure exist in the prior art:
Figure BDA0002442059070000022
different from the diamine monomer of the invention, benzyl is connected to an N atom in a benzimidazole structure, and the connection between the benzyl and a main molecular structure is not firm and is easy to break, so that the thermal stability of polymers such as polyimide synthesized by using the benzyl as a monomer is poor; the benzene ring is directly connected with the N atom in the benzimidazole structure, so that the connection is firmer, and the thermal stability of materials such as polyimide and the like synthesized by taking the benzene ring as a raw material is greatly improved.
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, Z1And Z2Are all-H or are all-CH3Or are each-CH3and-H, or respectively-CH2CH3and-H, or respectively-CH2CH2CH3and-H, or respectively-CH (CH)3)2and-H, or-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 containing the benzimidazole group is 500-550 ℃.
The preparation method of the polyimide film containing the benzimidazole structure 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 containing a benzimidazole group;
the benzimidazole intermediate with the structural formula shown in the formula (III) is prepared by mixing a compound with the structural formula shown in the formula (I) and a compound with the structural formula shown in the formula (II) and then sequentially carrying out substitution reaction and ring closure reaction;
the structural formulas of formula (I), formula (II), formula (III) and formula (IV) are respectively as follows:
Figure BDA0002442059070000031
the structural formula of the compound shown as the formula (I) is
Figure BDA0002442059070000032
Is prepared by one-step reaction of raw materials.
The above-mentioned prior art diamine monomer is also prepared by a process which is completely different from the process of the present invention and which comprises the following steps:
Figure BDA0002442059070000041
the benzimidazole is synthesized firstly, and then benzyl benzene is linked to the nitrogen atom of the benzimidazole group through benzyl bromide, so that the benzene group cannot be directly linked to the nitrogen atom of the benzimidazole.
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 BDA0002442059070000042
Figure BDA0002442059070000043
the molar ratio of the solvent to the solvent is 1:1: 20-100, the temperature of one-step reaction is 20-80 ℃, and the time is 8-48 h.
The preparation method of the polyimide film containing the benzimidazole structure comprises the following steps of:
(1) mixing 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);
(2) 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;
(3) 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, then carrying out a substitution reaction, adding a hydrogenation catalyst, and then carrying out a reduction reaction to obtain a diamine monomer containing a benzimidazole group.
In the preparation method of the polyimide film containing the benzimidazole structure, in the step (1), the organic solvent is more than one of dichloroethane, dichloromethane, tetrahydrofuran, trichloromethane, chlorobenzene and toluene; the acid-binding agent is more than one of triethylamine, diisopropylethylamine, pyridine, picoline, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; the catalyst is more than one of potassium fluoride, sodium fluoride, calcium fluoride and cesium fluoride; the compound with the structural formula shown as the formula (I), the organic solvent, the compound with the structural formula shown as the formula (II) and the acid-binding agent are in a molar ratio of 1: 10-100: 1-5: 5-20; the molar ratio of the catalyst to the substitution product in the step (1) 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 (2) and the step (3) is more than one of tetrahydrofuran, dichloroethane, dichloromethane, trichloromethane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, benzene, toluene, chlorobenzene and xylene, and the hydrogenation catalyst is more than one of palladium carbon, platinum carbon, rhodium carbon and active nickel;
in the step (2), the molar ratio of the benzimidazole intermediate with the structural formula shown as the formula (III), the organic solvent and the hydrogenation catalyst 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 (3), 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 catalyst and the substitution product of the step (3) 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 (2) and (3) 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) - (3) 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 containing a benzimidazole group prepared in example 1;
FIG. 3 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group prepared in example 2;
FIG. 4 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group prepared in example 3;
FIG. 5 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group obtained in example 4;
FIG. 6 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group prepared in example 5;
FIG. 7 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group obtained in example 6;
FIG. 8 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group 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 BDA0002442059070000061
Example 1
(Z in the structural formula in this example)1And Z2Are all-H)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) at a molar ratio of 1:1:20
Figure BDA0002442059070000062
The compound with the structural formula shown in the formula (I) is prepared from methanol through a one-step reaction at the temperature of 20 ℃ for 48 hours;
(2) mixing a compound with a structural formula shown in a formula (I), dichloroethane, a compound with a structural formula shown in a formula (II) and triethylamine in a molar ratio of 1:10:1:5, performing a substitution reaction at 20 ℃ for 48 hours, adding potassium fluoride in a molar ratio of 1:50 to a 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);
(3) 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 a high-pressure reaction kettle, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at the temperature of 50 ℃, the pressure of 0.8MPa and the time of 48 hours;
(4) 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, and then carrying out a reduction reaction at the temperature of 60 ℃, under the pressure of 2.0MPa for 48h to obtain a diamine monomer containing a benzimidazole group.
The structural formula of the finally prepared diamine monomer containing the benzimidazole group is as follows:
Figure BDA0002442059070000071
the nuclear magnetic spectrum is shown in figure 2; the 5% thermal decomposition temperature of the diamine monomer containing a benzimidazole group was 500 ℃.
Example 2
(Z in the structural formula in this example)1And Z2Are all-CH3)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) at a molar ratio of 1:1:30
Figure BDA0002442059070000072
Reacting with ethanol at 40 deg.C for 25 hr to obtain compound of formula (I);
(2) mixing a compound with a structural formula shown in a formula (I) and a dichloromethane in a molar ratio of 1:40:2:8, a compound with a structural formula shown in a formula (II) and diisopropylethylamine, then carrying out a substitution reaction at 50 ℃ for 15h, adding sodium fluoride in a molar ratio of 1:60 to a 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 60 ℃ for 15 h;
(3) 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 a high-pressure reaction kettle, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at the temperature of 50 ℃, the pressure of 2.5MPa and the time of 15 hours;
(4) 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 containing a benzimidazole group, 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 containing the benzimidazole group is as follows:
Figure BDA0002442059070000081
the nuclear magnetic spectrum is shown in figure 3; the 5% thermal decomposition temperature of the diamine monomer containing a benzimidazole group was 515 ℃.
Example 3
(Z in the structural formula in this example)1And Z2Are respectively-CH3and-H)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) at a molar ratio of 1:1:45
Figure BDA0002442059070000082
Reacting with methanol at 20 deg.C for 48h to obtain compound of formula (I);
(2) mixing a compound with a structural formula shown as a formula (I) and tetrahydrofuran in a molar ratio of 1:60:4:10, a compound with a structural formula shown as a formula (II) and pyridine, then carrying out a substitution reaction at the temperature of 60 ℃ for 20 hours, adding calcium fluoride in a molar ratio of 1:85 to a 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 110 ℃ for 10 hours;
(3) 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 a high-pressure reaction kettle, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at the temperature of 70 ℃, under the pressure of 4.2MPa for 12 hours;
(4) 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 containing a benzimidazole group, 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 containing the benzimidazole group is as follows:
Figure BDA0002442059070000091
the nuclear magnetic spectrum is shown in figure 4; the 5% thermal decomposition temperature of the diamine monomer containing a benzimidazole group was 520 ℃.
Example 4
(Z in the structural formula in this example)1And Z2Are respectively-CH2CH3and-H)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) at a molar ratio of 1:1:50
Figure BDA0002442059070000092
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 trichloromethane, a compound with a structural formula shown as a formula (II) and picoline in a molar ratio of 1:100:5:20, then carrying out a substitution reaction at 80 ℃ for 8 hours, adding cesium fluoride in a molar ratio of 1:100 to a substitution product, and carrying out a ring closing reaction to obtain a benzimidazole intermediate with a structural formula shown as a formula (III), wherein the ring closing reaction is carried out at 200 ℃ for 8 hours;
(3) mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:100:0.02, trichloromethane and active nickel in a high-pressure reaction kettle, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at the temperature of 100 ℃, the pressure of 5.0MPa and the time of 8 hours;
(4) 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 0.02:1 to the substitution product, then carrying out a reduction reaction to obtain a diamine monomer containing a benzimidazole group, 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 containing the benzimidazole group is as follows:
Figure BDA0002442059070000093
the nuclear magnetic spectrum is shown in figure 5; the 5% thermal decomposition temperature of the diamine monomer containing a benzimidazole group was 542 ℃.
Example 5
(Z in the structural formula in this example)1And Z2Are respectively-CH2CH2CH3and-H)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) at a molar ratio of 1:1:50
Figure BDA0002442059070000101
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 in a formula (I) and a chlorobenzene with a molar ratio of 1:100:5:5, 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 with a molar ratio of 1:100 to a substitution product (the molar ratio of the two is 1:1), 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;
(3) mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1:100:0.02, dimethylformamide and a mixture of palladium carbon and platinum carbon (the molar ratio of the two is 2:1) in a high-pressure reaction kettle, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction, wherein the temperature of the reduction reaction is 100 ℃, the pressure is 5.0MPa, and the time is 8 hours;
(4) 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 0.05:1 to the substitution product, then carrying out a reduction reaction to obtain a diamine monomer containing a benzimidazole group, 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 containing the benzimidazole group is as follows:
Figure BDA0002442059070000102
the nuclear magnetic spectrum is shown in figure 6; the 5% thermal decomposition temperature of the diamine monomer containing a benzimidazole group was 550 ℃.
Example 6
(Z in the structural formula in this example)1And Z2Are respectively-CH (CH)3)2and-H)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) at a molar ratio of 1:1:100
Figure BDA0002442059070000111
Reacting with methanol 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 structural formula shown as a formula (II) in a molar ratio of 1:100:3:15, toluene, and sodium bicarbonate, then carrying out a substitution reaction at 80 ℃ for 8 hours, adding potassium fluoride with a molar ratio of 1:100 to a 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 ring closing reaction is carried out at 200 ℃ for 8 hours;
(3) mixing a benzimidazole intermediate with a structural formula shown in a formula (III), N-methyl pyrrolidone and palladium carbon in a molar ratio of 1:20:0.02 in a high-pressure reaction kettle, and then carrying out reduction reaction at the temperature of 70 ℃, under the pressure of 5.0MPa for 20 hours;
(4) 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, replacing three times with nitrogen, then filling hydrogen for reduction reaction at a temperature of 80 ℃ for 15h, adding the product into an autoclave, adding active nickel with a molar ratio of 0.02:1 to the substitution product, and then carrying out reduction reaction to obtain a diamine monomer containing benzimidazole groups, 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 containing the benzimidazole group is as follows:
Figure BDA0002442059070000112
the nuclear magnetic spectrum is shown in figure 7; the 5% thermal decomposition temperature of the diamine monomer containing a benzimidazole group was 529 ℃.
Example 7
(Z in the structural formula in this example)1And Z2Are respectively-F and-H)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) at a molar ratio of 1:1:80
Figure BDA0002442059070000113
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 structural formula shown as a formula (II) in a molar ratio of 1:10:5:15, toluene, and potassium carbonate, then carrying out a substitution reaction at 80 ℃ for 8 hours, adding calcium fluoride into the mixture in a molar ratio of 1:100 to a 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 ring closing reaction is carried out at 180 ℃ for 8 hours;
(3) mixing a benzimidazole intermediate with a structural formula shown as a formula (III), N-methyl pyrrolidone and active nickel in a molar ratio of 1:100:0.02 in a high-pressure reaction kettle, replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at the temperature of 80 ℃ and the pressure of 4.0MPa for 12 hours;
(4) 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 0.03:1 to the substitution product, and then carrying out a reduction reaction to obtain a diamine monomer containing a benzimidazole group, 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 containing the benzimidazole group is as follows:
Figure BDA0002442059070000121
the nuclear magnetic spectrum is shown in figure 8; the 5% thermal decomposition temperature of the diamine monomer containing a benzimidazole group was 528 ℃.
Example 8
The procedure for producing a benzimidazole group-containing diamine monomer was substantially the same as in example 7, except that toluene in the step (3) was replaced with a mixture of tetrahydrofuran and chlorobenzene in a mass ratio of 1:1, and the structural formula of the finally produced benzimidazole group-containing diamine monomer was the same as in example 7.
Examples 9 to 15
The procedure for preparing a benzimidazole group-containing diamine monomer was substantially the same as in example 7, except that N-methylpyrrolidone in the step (3) was replaced with dimethylacetamide, 1, 4-dioxane, benzene, toluene, chlorobenzene, xylene, and a mixture of benzene and xylene in a mass ratio of 1:1, respectively, and the structural formula of the finally obtained benzimidazole group-containing diamine monomer was the same as in example 7.
Examples 16 to 21
The procedure for preparing a benzimidazole group-containing diamine monomer was substantially the same as in example 7, except that N-methylpyrrolidone in the step (4) was replaced with 1, 4-dioxane, benzene, toluene, chlorobenzene, xylene, and a mixture of chlorobenzene and xylene in a mass ratio of 1:1, respectively, and the structural formula of the finally obtained benzimidazole group-containing diamine monomer was the same as in example 7.
Examples 22 to 24
The preparation method of the diamine monomer containing the benzimidazole group is basically the same as that in example 7, except that potassium carbonate in the step (2) is replaced by a mixture of sodium bicarbonate, potassium bicarbonate and triethylamine and diisopropylethylamine in a mass ratio of 1:1, respectively, and the structural formula of the finally prepared diamine monomer containing the benzimidazole group is the same as that in example 7.
Example 25
Dissolving a diamine monomer prepared in example 1 in an aprotic polar solvent (NMP) at the temperature of 20 ℃, adding 4,4'- (hexafluoroisopropylidene) 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, 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 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' - (hexafluoroisopropylidene) diphthalic anhydride is 1:0.98, 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 423 ℃, the tensile strength of 375MPa and the elastic modulus of 7 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 pale blue with increasing 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 1:0.96, 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 448 ℃, the tensile strength of 290MPa and the elastic modulus of 8 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 pale blue as the voltage increases.
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, 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 410 ℃, 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 pale blue as the voltage increases.
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 1:1.02, 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 415 ℃, the tensile strength of 380MPa 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 pale blue as the voltage increases.
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 1:0.95, 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 418 ℃, the tensile strength of 328MPa 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 pale blue as the voltage increases.
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 1:1.01, 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 422 ℃, the tensile strength of 316MPa 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 pale blue as the voltage increases.
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 1:1.05, 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 315MPa 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 pale blue as the voltage increases.
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; 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 pale blue with increasing voltage.
TABLE 1
Figure BDA0002442059070000151
Figure BDA0002442059070000161

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 containing a benzimidazole group and has the following structural general formula:
Figure FDA0002442059060000011
wherein Z is1And Z2Is 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 a polyimide film containing a benzimidazole structure according to claim 1, wherein Z is1And Z2Are all-H or are all-CH3Or are each-CH3and-H, or respectively-CH2CH3and-H, or respectively-CH2CH2CH3and-H, or respectively-CH (CH)3)2and-H, or-F and-H, respectively.
6. The method for preparing the polyimide film containing a benzimidazole structure according to claim 5, wherein the 5% thermal decomposition temperature of the diamine monomer containing a benzimidazole group is 500 to 550 ℃.
7. The method for preparing the polyimide film containing the benzimidazole structure according to claim 6, wherein the method for preparing the diamine monomer containing the benzimidazole group comprises: 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 containing a benzimidazole group;
the benzimidazole intermediate with the structural formula shown in the formula (III) is prepared by mixing a compound with the structural formula shown in the formula (I) and a compound with the structural formula shown in the formula (II) and then sequentially carrying out substitution reaction and ring closure reaction;
the structural formulas of formula (I), formula (II), formula (III) and formula (IV) are respectively as follows:
Figure FDA0002442059060000021
the structural formula of the compound shown as the formula (I) is
Figure FDA0002442059060000022
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 FDA0002442059060000023
the molar ratio of the solvent to the solvent is 1:1: 20-100, the temperature of one-step reaction is 20-80 ℃, and the time is 8-48 h.
9. The method for preparing the polyimide film containing a benzimidazole structure according to claim 8, wherein the diamine monomer containing a benzimidazole group is prepared by the following steps:
(1) mixing 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);
(2) 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;
(3) 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, then carrying out a substitution reaction, adding a hydrogenation catalyst, and then carrying out a reduction reaction to obtain a diamine monomer containing a benzimidazole group.
10. The method for preparing a polyimide film containing a benzimidazole structure according to claim 9, wherein the organic solvent in step (1) is at least one of dichloroethane, dichloromethane, tetrahydrofuran, chloroform, chlorobenzene, and toluene; the acid-binding agent is more than one of triethylamine, diisopropylethylamine, pyridine, picoline, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; the catalyst is more than one of potassium fluoride, sodium fluoride, calcium fluoride and cesium fluoride; the compound with the structural formula shown as the formula (I), the organic solvent, the compound with the structural formula shown as the formula (II) and the acid-binding agent are in a molar ratio of 1: 10-100: 1-5: 5-20; the molar ratio of the catalyst to the substitution product in the step (1) 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 (2) and the step (3) is more than one of tetrahydrofuran, dichloroethane, dichloromethane, trichloromethane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, benzene, toluene, chlorobenzene and xylene, and the hydrogenation catalyst is more than one of palladium carbon, platinum carbon, rhodium carbon and active nickel;
in the step (2), the molar ratio of the benzimidazole intermediate with the structural formula shown as the formula (III), the organic solvent and the hydrogenation catalyst 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 (3), 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 catalyst and the substitution product of the step (3) 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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