CN111440318B - Preparation method of polyimide film containing benzimidazole structure - Google Patents

Preparation method of polyimide film containing benzimidazole structure Download PDF

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CN111440318B
CN111440318B CN202010268007.7A CN202010268007A CN111440318B CN 111440318 B CN111440318 B CN 111440318B CN 202010268007 A CN202010268007 A CN 202010268007A CN 111440318 B CN111440318 B CN 111440318B
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benzimidazole
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张振宇
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Jiangsu Huanfeng Electrical Material 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 is 1 And Z 2 Is selected from-F, -H, -CH 3 、‑CH 2 CH 3 、‑CH 2 CH 2 CH 3 or-CH (CH) 3 ) 2 One 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. In view 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, and 2- (4-aminophenyl) -5-aminobenzimidazole is also used as a diamine monomer; the patent CN105778130A discloses a high-strength high-heat-resistance polyimide microporous film and a preparation method thereof, and a heterocyclic structure is introduced by 2- (4-aminophenyl) -5-aminobenzimidazole; patent CN106928481A discloses an optimized preparation method of polyimide film, and a series of intermediates using 2- (4-aminophenyl) -5-aminobenzimidazole as a main structure are also used. 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 GDA0003789217350000021
wherein, Z 1 And Z 2 Is selected from-F, -H, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 or-CH (CH) 3 ) 2 To (3) is provided. The diamine monomer containing the benzimidazole group can be used for preparing polyimide, and can obviously improve various properties of polyimide materials:
(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.
Monomers of the following structure exist in the prior art:
Figure GDA0003789217350000022
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' - (hexafluoroisopropylene) diphthalic anhydride and the dianhydride monomer are more than one of pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, monoether tetracarboxylic dianhydride and triphenbisether 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 1.95-1.05, 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 ℃ and preserving heat for 1h, then heating to 200-220 ℃ and preserving heat for 1h, and finally heating to 350-420 ℃ and 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, Z 1 And Z 2 Are all-H or are all-CH 3 Or are each-CH 3 and-H or respectively-CH 2 CH 3 and-H, or respectively-CH 2 CH 2 CH 3 and-H, or respectively-CH (CH) 3 ) 2 and-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 in a formula (III), mixing a reduction product of the benzimidazole intermediate with a compound with a structural formula shown in a formula (IV), and then sequentially performing 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 GDA0003789217350000031
the structural formula of the compound shown as the formula (I) is
Figure GDA0003789217350000032
Is prepared by one-step reaction of raw materials.
The above-mentioned prior art diamine monomers are also prepared in a process which is completely different from the process of the present invention and which is prepared by the following steps:
Figure GDA0003789217350000041
the method firstly synthesizes benzimidazole, and then uses benzyl bromide to link benzyl benzene to nitrogen atom of benzimidazole group, so that the method can not directly link benzene group to nitrogen atom of benzimidazole.
The preparation method of the polyimide film containing the benzimidazole structure synthesizes the compound with the structural formula shown as the formula (I)When the material is used, the material is put into the container,
Figure GDA0003789217350000042
Figure GDA0003789217350000043
and the molar ratio of the solvent to the solvent is 1.
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 mol ratio of the compound with the structural formula shown as formula (I) to the organic solvent to the compound with the structural formula shown as formula (II) to the acid-binding agent is 1-5:5-20; the molar ratio of the catalyst to the substitution product in the step (1) is 1; 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 in the formula (III), the organic solvent and the hydrogenation catalyst is 1; 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 shown as the formula (III), the organic solvent, the compound with the structural formula shown as the formula (IV) and the catalyst is 1-20; the temperature of the substitution reaction is 20-80 ℃, and the time is 8-48 h; the temperature of the reduction reaction is 0-100 ℃, the pressure is 0.1-5.0 MPa, and the time is 8-48 h;
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 nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group prepared in example 1;
FIG. 2 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group prepared in example 2;
FIG. 3 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group prepared in example 3;
FIG. 4 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group prepared in example 4;
FIG. 5 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group prepared in example 5;
FIG. 6 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group prepared in example 6;
FIG. 7 is a nuclear magnetic spectrum of a diamine monomer containing a benzimidazole group obtained in example 7.
Detailed Description
The present invention will be further described with reference to the following 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 GDA0003789217350000061
Example 1
(Z in the structural formula in this example) 1 And Z 2 Are all-H)
The preparation method of diamine monomer containing benzimidazole group comprises the following basic steps:
(1) Mixing a mixture of 1
Figure GDA0003789217350000062
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 as a formula (I) and dichloroethane in a molar ratio of 1;
(3) Mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1.02 to 1:0.02 in a high-pressure reaction kettle, then replacing the mixture with nitrogen for three times, and then filling hydrogen to perform a reduction reaction at 50 ℃ under 0.8MPa for 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.
The structural formula of the finally prepared diamine monomer containing the benzimidazole group is as follows:
Figure GDA0003789217350000071
the nuclear magnetic spectrum is shown in figure 1; 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) 1 And Z 2 Are all-CH 3 )
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) 1
Figure GDA0003789217350000072
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 as a formula (I) and a structural formula shown as a formula (II) in a molar ratio of 1;
(3) Mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1.05, 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 50 ℃ under 2.5MPa for 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.
The structural formula of the finally prepared diamine monomer containing the benzimidazole group is as follows:
Figure GDA0003789217350000081
the nuclear magnetic spectrum is shown in figure 2; 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) 1 And Z 2 Are each-CH 3 and-H)
The preparation method of diamine monomer containing benzimidazole group comprises the following basic steps:
(1) Mixing a mixture of 1
Figure GDA0003789217350000082
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, a compound with a structural formula shown as a formula (II) and pyridine in a molar ratio of 1;
(3) Mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1.03, 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, wherein the temperature of the reduction reaction is 70 ℃, the pressure is 4.2MPa, and the time is 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.
The structural formula of the finally prepared diamine monomer containing the benzimidazole group is as follows:
Figure GDA0003789217350000091
the nuclear magnetic spectrum is shown in figure 3; 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) 1 And Z 2 Are respectively-CH 2 CH 3 and-H)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) Mixing the molar ratio of 1
Figure GDA0003789217350000092
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;
(3) Mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1.02, 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, 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.
The structural formula of the finally prepared diamine monomer containing the benzimidazole group is as follows:
Figure GDA0003789217350000093
the nuclear magnetic spectrum is shown in figure 4; 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) 1 And Z 2 Are respectively-CH 2 CH 2 CH 3 and-H)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) Mixing the molar ratio of 1
Figure GDA0003789217350000101
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;
(3) Mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1.100, 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 100 ℃ under the pressure of 5.0MPa for 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.
The structural formula of the finally prepared diamine monomer containing the benzimidazole group is as follows:
Figure GDA0003789217350000102
the nuclear magnetic spectrum is shown in figure 5; 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) 1 And Z 2 Are respectively-CH (CH) 3 ) 2 and-H)
The preparation method of the diamine monomer containing the benzimidazole group comprises the following basic steps:
(1) Mixing a raw material with a molar ratio of 1
Figure GDA0003789217350000111
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;
(3) Mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1.20, N-methyl pyrrolidone and palladium carbon in a high-pressure reaction kettle, and then carrying out a reduction reaction at 70 ℃ under a 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.
The structural formula of the finally prepared diamine monomer containing the benzimidazole group is as follows:
Figure GDA0003789217350000112
the nuclear magnetic spectrum is shown in figure 6; the 5% thermal decomposition temperature of the benzimidazole group-containing diamine monomer was 529 ℃.
Example 7
(Z in the structural formula in this example) 1 And Z 2 Are respectively-F and-H)
The preparation method of diamine monomer containing benzimidazole group comprises the following basic steps:
(1) Mixing a raw material with a molar ratio of 1
Figure GDA0003789217350000113
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;
(3) Mixing a benzimidazole intermediate with a structural formula shown as a formula (III) and a molar ratio of 1.02, N-methyl pyrrolidone 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 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.
The structural formula of the finally prepared diamine monomer containing the benzimidazole group is as follows:
Figure GDA0003789217350000121
the nuclear magnetic spectrum is shown in figure 7; the 5% thermal decomposition temperature of the diamine monomer containing a benzimidazole group was 528 ℃.
Example 8
The procedure for preparing 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 obtained benzimidazole group-containing diamine monomer was the same as in example 7.
Examples 9 to 15
The procedure of preparation of the diamine monomer containing benzimidazole group 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 prepared diamine monomer containing benzimidazole group was the same as in example 7.
Examples 16 to 21
The preparation method of the diamine monomer containing the benzimidazole group is basically the same as that of the embodiment 7, except that the N-methyl pyrrolidone in the step (4) is replaced by 1,4-dioxane, benzene, toluene, chlorobenzene, xylene and a mixture of chlorobenzene and xylene with the mass ratio of 1:1, and the structural formula of the finally prepared diamine monomer containing the benzimidazole group is the same as that of the embodiment 7.
Examples 22 to 24
The preparation method of the diamine monomer containing the benzimidazole group is basically the same as that in the 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, and the structural formula of the finally prepared diamine monomer containing the benzimidazole group is the same as that in the 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'- (hexafluoroisopropylene) 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, raising the temperature 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 4,4' - (hexafluoroisopropylene) diphthalic anhydride is 1: 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 15min;
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 7Gpa; 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 26
Dissolving the diamine monomer prepared in the example 2 in an aprotic polar solvent (NMP) at a 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 temperature rise 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: 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 30min;
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 8GPa; 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
A preparation method of polyimide film containing benzimidazole structure comprises the steps of dissolving diamine monomer prepared in example 3 in aprotic polar solvent (DMAC) at the temperature of 0 ℃, adding biphenyl tetracarboxylic dianhydride in batches until the viscosity of the solution rises, adjusting the solid content of the solution to 8% to obtain 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 argon 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 biphenyl tetracarboxylic dianhydride is 1:1, and the gradient heating 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 26min;
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 9GPa; 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 polyimide film containing benzimidazole structure, under the temperature condition of 15 ℃, dissolving the diamine monomer prepared in the above example 4 in aprotic polar solvent (DMAC), adding monoether tetracarboxylic dianhydride in batches until the solution viscosity rises, adjusting the solid content of the solution to 15% to obtain PAA solution, then coating the PAA solution on a substrate to form a uniform film, and finally, under the protection of nitrogen, gradient heating until imidization is completed to obtain polyimide film containing benzimidazole structure, wherein the molar addition ratio of the diamine monomer to the monoether tetracarboxylic dianhydride is 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 22min;
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 9GPa; 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 triphendiether 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 temperature rise 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 triphendiether tetracarboxylic dianhydride is 1: firstly, preserving heat for 1h at the temperature of 77 ℃, then heating to 140 ℃, preserving heat for 1h, then heating to 213 ℃, preserving heat for 1h, and finally heating to 400 ℃, preserving heat for 18min;
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 12GPa; 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
A preparation method of polyimide film containing benzimidazole structure, under the temperature condition of 35 ℃, dissolving the diamine monomer prepared in the above example 6 in an aprotic polar solvent (DMF), adding a dianhydride monomer (specifically, a mixture of pyromellitic dianhydride and biphenyltetracarboxylic dianhydride in a mass ratio of 1:1) in batches until the solution viscosity rises, adjusting the solid content of the solution to 14% to obtain a PAA solution, then coating the PAA solution on a substrate to form a uniform film, and finally, under the protection of argon, performing gradient heating until imidization is completed to obtain the polyimide film containing benzimidazole structure, wherein the molar addition ratio of the diamine monomer to the dianhydride monomer is 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 15min;
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 6GPa; 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 above example 7 in 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 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 polyimide film containing benzimidazole structure, wherein the molar addition ratio of the diamine monomer to the biphenyl tetracarboxylic dianhydride is 1.05: 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 10min;
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 10GPa; 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 polyimide film containing 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 8-24, and the properties of the finally prepared polyimide film containing benzimidazole structure are shown in table 1; and 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 GDA0003789217350000151
Figure GDA0003789217350000161

Claims (7)

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 FDA0003758640700000011
wherein Z is 1 And Z 2 Are all-CH 3 Or are each-CH 3 and-H, or respectively-CH 2 CH 3 and-H, or respectively-CH 2 CH 2 CH 3 and-H, or respectively-CH (CH) 3 ) 2 and-H, or-F and-H, respectively;
the 5 percent thermal decomposition temperature of the diamine monomer containing benzimidazole group is 515 to 550 ℃;
the polyimide film containing benzimidazole structure has glass transition temperature of 410-450 deg.c, tensile strength of 290-380 MPa and elastic modulus of 6-12 GPa.
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 1.95 to 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 ℃ and preserving heat for 1h, then heating to 200-220 ℃ and preserving heat for 1h, and finally heating to 350-420 ℃ and preserving heat for 10-30 min.
4. The method for preparing the polyimide film containing the benzimidazole structure according to claim 1, 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 FDA0003758640700000021
the structural formula of the compound shown as the formula (I) is
Figure FDA0003758640700000022
Is prepared by one-step reaction of raw materials.
5. The method for preparing polyimide film containing benzimidazole structure according to claim 4, wherein the compound having formula (I) is synthesized,
Figure FDA0003758640700000023
and the molar ratio of the solvent to the solvent is 1.
6. The method for preparing polyimide film containing benzimidazole structure according to claim 5, wherein the preparation of the diamine monomer containing benzimidazole group comprises 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 a 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.
7. The method for preparing a polyimide film containing a benzimidazole structure according to claim 6, 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 mol ratio of the compound with the structural formula shown as formula (I) to the organic solvent to the compound with the structural formula shown as formula (II) to the acid-binding agent is 1-5:5-20; the molar ratio of the catalyst to the substitution product in the step (1) is 1; 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 in the formula (III), the organic solvent and the hydrogenation catalyst is 1; 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 shown as the formula (III), the organic solvent, the compound with the structural formula shown as the formula (IV) and the catalyst is 1-20; the temperature of the substitution reaction is 20-80 ℃, and the time is 8-48 h; the temperature of the reduction reaction is 0-100 ℃, the pressure is 0.1-5.0 MPa, and the time is 8-48 h.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109400536A (en) * 2018-12-21 2019-03-01 东华大学 A kind of N substituted benzimidazole diamines and preparation method thereof
CN110204719A (en) * 2019-06-25 2019-09-06 东华大学 A kind of polyimides that benzimidazole replaces and the Kapton that preparation method, benzimidazole replace and preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109400536A (en) * 2018-12-21 2019-03-01 东华大学 A kind of N substituted benzimidazole diamines and preparation method thereof
CN110204719A (en) * 2019-06-25 2019-09-06 东华大学 A kind of polyimides that benzimidazole replaces and the Kapton that preparation method, benzimidazole replace and preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Cai wan an 等.Synthesis and Electrochromic Properties of Polyimides with Pendent Benzimidazole and Triphenylamine Units.《Chinese Journal of Polymer Science》.2016,第34卷(第9期), *
Nucleophilic Aromatic Substitution Reactions in Water Enabled by Micellar Catalysis;Nicholas A. Isley;《Org. Lett.》;20150914;第17卷;4734-4737页 *
Synthesis and Electrochromic Properties of Polyimides with Pendent Benzimidazole and Triphenylamine Units;Cai wan an 等;《Chinese Journal of Polymer Science》;20160728;第34卷(第9期);第1091-1102页 *

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