CN108034049B - Polyimide resin and preparation method thereof - Google Patents

Polyimide resin and preparation method thereof Download PDF

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CN108034049B
CN108034049B CN201711373126.3A CN201711373126A CN108034049B CN 108034049 B CN108034049 B CN 108034049B CN 201711373126 A CN201711373126 A CN 201711373126A CN 108034049 B CN108034049 B CN 108034049B
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polyimide
polyimide resin
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cyclohexane
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CN108034049A (en
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陈国飞
唐咏梅
王玮
徐禄波
方省众
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract

The invention relates to a polyimide resin and a preparation method thereof, wherein the structural formula of the polyimide resin is shown as the following formula (I):
Figure DDA0001514118110000011
wherein n is an integer greater than 0; ar (Ar)1Is composed of
Figure DDA0001514118110000012
Any one of the structural formulas; ar (Ar)2Is any one of residues of aromatic diphenol monomers with a structural formula shown as a formula (II) or a formula (III),
Figure DDA0001514118110000013
R1，R2，R3，R4is any one of hydrogen atom, alkyl, phenyl or substituted phenyl, and the transverse lines attached to the benzene ring are Ar2A bond to an oxygen atom. The preparation method comprises the following steps: mixing an aromatic diphenol monomer with a structural formula shown as a formula (II) or a formula (III) and 1, 4-bis (4-fluoro-imide) cyclohexane in a solvent under a protective atmosphere, and carrying out heating reaction under an alkaline catalyst to obtain a polyimide solution; and mixing the polyimide solution with a precipitator, collecting the precipitate, and drying to obtain the polyimide resin with excellent heat resistance and optical transmittance.

Description

Polyimide resin and preparation method thereof
Technical Field
The invention relates to the field of polyimide and preparation thereof, in particular to polyimide resin and a preparation method thereof.
Background
In recent years, with the development of high and new technology industries, there is an increasing demand for highly heat-resistant and highly light-transmissive polyimides in the optical fields of optical guides, waveguides, liquid crystal displays, and the like. However, conventional polyimides generally exhibit a yellow color, which greatly limits the further use of polyimides in optoelectronic materials. Therefore, the development of a high-temperature-resistant and transparent polyimide resin material which can be used in the fields of flexible solar cell substrates, flexible display or illumination substrates and the like has very important application value.
At present, the most effective way to reduce the color is to obtain polyimide having aliphatic units using dianhydride or diamine monomers of a full-aliphatic structure, thereby fundamentally suppressing the formation of charge transfer complexes. However, (1) polyimide with high molecular weight cannot be obtained due to the reduction of the reactivity of the monomer of the aliphatic dianhydride, and for example, the synthesis of polyimide from the alicyclic dianhydride monomer is reported in the Chinese patent publications CN101084254A, CN101831074A and CN 1034707A; (2) diamine with an aliphatic structure, such as commonly-used 1, 4-cyclohexanediamine, is too basic, so that salt is easily precipitated in the preparation process, and the pH value needs to be regulated (Macromolecules, 2007, 40, 3527) or a temperature rise method (High Performance Polymers, 2001, 13, S93) is adopted, but polyamide acid is easily degraded due to the temperature rise, so that the preparation conditions are complicated and harsh. Meanwhile, the above method is suitable only for trans-form 1, 4-cyclohexanediamine, and a flexible film cannot be prepared for cis-trans mixed 1, 4-cyclohexanediamine. In contrast, chinese patent publication No. CN105754097A reports that easily soluble transparent polyimide is prepared from diphenol monomers of phenolphthalein series and phenolred series, but the high temperature resistance (glass transition temperature (Tg) and thermal stability (Td 5%) of the polyimide needs to be further improved, and particularly, due to the existence of ester bonds and sulfone groups, the thermal degradation temperature of the polymer is relatively low.
Disclosure of Invention
In view of the above, it is necessary to provide a polyimide having excellent heat resistance and optical transmittance, and a method for producing the same, which is easy to handle and control.
A transparent polyimide resin having a structural formula represented by the following formula (I):
Figure BDA0001514118100000021
wherein n is an integer greater than 0;
Ar1is composed of
Figure BDA0001514118100000022
Any one of the structural formulas;
Ar2is any one of residues of aromatic diphenol monomers with a structural formula shown as a formula (II) or a formula (III),
Figure BDA0001514118100000023
R1，R2，R3，R4is any one of hydrogen atom, alkyl, phenyl or substituted phenyl, and the transverse lines attached to the benzene ring are Ar2A bond to an oxygen atom.
The above structural formula
Figure BDA0001514118100000031
Represents a trans-cyclohexane group, structural formula
Figure BDA0001514118100000032
Represents a cis-cyclohexane group of the formula
Figure BDA0001514118100000033
Represents a trans cyclohexane group and a cis cyclohexane group which are mixed in any proportion.
The amide bond (-CO-NH-) or the carbon-carbon bond (-C-), which has better thermal stability, is introduced into the polyimide resin to replace the ester bond (-COO-) in the polyimide prepared by adopting diphenol monomers of phenolphthalein series and phenol red series in the prior art, so that the polyimide resin has higher thermal degradation temperature (Td 5%). Meanwhile, in the preparation method, the aromatic diphenol monomer is used as a raw material, and the aromatic diphenol monomer has larger rotation steric hindrance, so that the formation of a charge transfer complex in and among polyimide molecules can be inhibited, and the transparency and the glass transition temperature (Tg) of the polyimide can be improved. Specifically, the polyester imide resin is white, the glass transition temperature is 300-400 ℃, the 5% thermal weight loss temperature under a nitrogen environment is more than 400 ℃, and the light transmittance at 400nm is more than 80%. The polyimide resin can be further applied as a flexible substrate material, a flexible transparent conductive film substrate material, a liquid crystal display material and the like of a solar cell.
In one embodiment, the Ar1Is composed of
Figure BDA0001514118100000034
Any one of the structural formulas.
In one embodiment, the Ar2Is any one of residues of aromatic diphenol monomers shown in a structural formula as follows:
Figure BDA0001514118100000041
wherein, the horizontal lines attached to the benzene ring "-" all represent Ar2A bond to an oxygen atom.
The invention also provides a preparation method of the polyimide resin, which comprises the following steps:
mixing an aromatic diphenol monomer and 1, 4-bis (4-fluoro-imide) cyclohexane in a solvent under a protective atmosphere, and carrying out heating reaction under the action of an alkaline catalyst to obtain a polyimide solution;
and mixing the polyimide solution with a precipitator, collecting the precipitate, and drying to obtain the polyimide resin.
The preparation method of the polyimide resin adopts an aromatic nucleophilic substitution reaction method to replace the traditional dianhydride diamine polycondensation method, and overcomes the problem of salt precipitation caused by too strong alkalinity of 1, 4-cyclohexanediamine during the traditional dianhydride diamine polycondensation preparation. The preparation method also has the advantages of simple and convenient operation, easy control and the like.
In one embodiment, the structural formula of the diphenol monomer is shown as formula (IV) below or formula (V) below:
Figure BDA0001514118100000051
wherein R is1，R2，R3，R4Is any one of hydrogen atom, alkyl, phenyl or substituted phenyl.
Ar described above2In the aromatic diphenol monomer, the aromatic diphenol monomer with the structural formula shown in the formula (IV) is prepared by corresponding phenolphthalein and primary amine, and the aromatic diphenol monomer with the structural formula shown in the formula (V) can be directly purchased.
In one embodiment, the 1, 4-bis (4-fluoroamide) cyclohexane is one or both of 1, 4-bis (4-fluoroamide) cis-cyclohexane, 1, 4-bis (4-fluoroamide) trans-cyclohexane;
the structural formula of the 1, 4-bis (4-fluoro-imide) trans cyclohexane is as follows:
Figure BDA0001514118100000052
the structural formula of the 1, 4-bis (4-fluoro-imide) cis-cyclohexane is as follows:
Figure BDA0001514118100000053
the structural formula of the mixture of the 1, 4-bis (4-fluoro-imide) cis-cyclohexane and the 1, 4-bis (4-fluoro-imide) trans-cyclohexane is as follows:
Figure BDA0001514118100000061
in one embodiment, the molar ratio of the aromatic diol monomer to 1, 4-bis (4-fluoro imide) cyclohexane is 1: (0.95-1.05).
In one embodiment, the basic catalyst is at least one of carbonate, bicarbonate, hydroxide and organic base, and the molar amount of the basic catalyst is 100 to 150 percent of the molar amount of the aromatic diphenol monomer. Among them, carbonates are more preferable because the carbonates are stable and the viscosity of the polymer to be produced is high.
In one embodiment, the temperature of the heating reaction is 180 ℃ to 230 ℃, and the solvent is a polar aprotic solvent.
In one embodiment, the polar aprotic solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
In one embodiment, the precipitating agent is selected from at least one of ethanol, methanol, acetone, and water.
In one embodiment, the temperature of the polyimide solution mixed with the precipitant is 70 ℃ to 90 ℃, preferably 80 ℃.
In one embodiment, the protective atmosphere is nitrogen or an inert gas, and the inert gas is an inert gas commonly used in the art, such as argon.
In one embodiment, the method further comprises, before the step of mixing the polyimide solution with the precipitant, the steps of: and (2) end-capping the polyimide in the polyimide solution by an end-capping agent, wherein the structure of the end-capping agent is shown as the following formula (VI):
Figure BDA0001514118100000071
in one embodiment, the molar amount of the end-capping agent is 1% to 5% of the molar amount of the diphenol monomer. When the end-capping agent is used, the thermal stability and processability of the resulting polyimide resin are further improved.
Compared with the prior art, the invention has the following beneficial effects:
the polyimide resin is white, the obtained polyimide film is transparent, the glass transition temperature is 300-400 ℃, the 5 percent thermal weight loss temperature under the nitrogen environment is more than 400 ℃, the light transmittance at 400nm is more than 80 percent, and the polyimide resin can have better application prospect in the related fields of flexible substrate materials of solar cells, flexible transparent conductive film substrate materials, liquid crystal display materials and the like.
The preparation method of the polyimide resin has the advantages of simple and convenient operation, easy control and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
in this example, the structural formula of the raw material aromatic diphenol monomer is as follows:
Figure BDA0001514118100000072
the polyimide resin obtained has the following structural formula:
Figure BDA0001514118100000081
the preparation method comprises the following steps: 2.0544(5.0mmol) of 1, 4-bis (4-fluoro-imide) trans-cyclohexane, 1.65684g (5.0mmol) of aromatic diphenol monomer, 0.7614g (5.5mmol) of potassium carbonate, 10 mL of N, N-dimethylacetamide and 15 mL of xylene (xylene is used as a water-carrying agent) are added into a 100mL reaction bottle under the protection of nitrogen, the temperature is increased to 180 ℃, stirring is carried out for 5 hours, then the temperature is gradually increased to 220 ℃, and reaction is carried out for 6 hours, so as to prepare viscous polyimide solution. Cooling the polyimide solution to 80 ℃, adding N, N-dimethylacetamide for dilution, then adding the diluted polyimide solution into ethanol for precipitation, filtering to obtain fibrous polyimide, and boiling, washing and drying to obtain polyimide powder. The glass transition temperature of the obtained polyimide powder was 316 ℃, and the 5% thermogravimetric temperature under a nitrogen atmosphere was 434 ℃.
Preparing the obtained polyimide powder into a solution with the weight percentage concentration of 10% by using N, N-dimethylacetamide, uniformly coating the solution on a clean glass plate by using a tape casting method, placing the glass plate in a drying oven at 80 ℃ overnight, and then heating according to the following procedures: 1 hour at 100 ℃; 1 hour at 150 ℃; 200 ℃ for 1 hour. And (3) taking out the glass plate after the temperature is reduced to room temperature, putting the glass plate into warm water for demoulding, and then putting the film into a drying oven at 100 ℃ for drying and dewatering to obtain the polyimide film with the thickness of 20 microns.
The detection data are as follows: FT-IR (film) 1776, 1710, 1373, 1238, 749cm-1(ii) a The transmission curve of the film prepared by the method is tested by an ultraviolet visible spectrometer, the ultraviolet absorption cut-off wavelength of the film is 350nm, and the light transmittance at 400nm is 83%.
Example 2:
in this example, the structural formula of the raw material aromatic diphenol monomer is as follows:
Figure BDA0001514118100000091
the polyimide resin obtained has the following structural formula:
Figure BDA0001514118100000092
the preparation method comprises the following steps: 4.1004(10.0mmol) of 1, 4-bis (4-fluoro-imide) trans-cyclohexane, 3.5947g (10.0mmol) of aromatic diphenol monomer, 1.5230g (11.0mmol) of potassium carbonate, 40 mL of N, N-dimethylacetamide and 30 mL of xylene are added into a 150mL reaction bottle under the protection of nitrogen, the temperature is increased to 190 ℃, the mixture is stirred for 5 hours, and then the temperature is gradually increased to 210 ℃ for reaction for 8 hours, so that viscous polyimide solution is prepared. Cooling the polyimide solution to 80 ℃, adding N, N-dimethylacetamide for dilution, then adding the diluted polyimide solution into ethanol for precipitation, filtering to obtain fibrous polyimide, and boiling, washing and drying to obtain polyimide powder. The glass transition temperature of the obtained polyimide powder was 306 ℃, and the 5% thermogravimetric temperature under a nitrogen atmosphere was 421 ℃.
Preparing the obtained polyimide powder into a solution with the weight percentage concentration of 10% by using N, N-dimethylacetamide, uniformly coating the solution on a clean glass plate by using a tape casting method, placing the glass plate in a drying oven at 80 ℃ overnight, and then heating according to the following procedures: 1 hour at 100 ℃; 1 hour at 150 ℃; 200 ℃ for 1 hour. And (3) taking out the glass plate after the temperature is reduced to room temperature, putting the glass plate into warm water for demoulding, and then putting the film into a drying oven at 100 ℃ for drying and dewatering to obtain the polyimide film with the thickness of 20 microns.
The detection data are as follows: FT-IR (film) 1771, 1706, 1369, 1238, 749cm-1(ii) a The transmission curve of the film prepared by the method is tested by an ultraviolet visible spectrometer, the ultraviolet absorption cut-off wavelength of the film is 345nm, and the light transmittance at 400nm is 87%.
Example 3:
in this example, the structural formula of the raw material aromatic diphenol monomer is as follows:
Figure BDA0001514118100000101
the polyimide resin obtained has the following structural formula:
Figure BDA0001514118100000102
the preparation method comprises the following steps: 2.0515(5.0mmol) of 1, 4-bis (4-fluoro-imide) trans-cyclohexane, 1.8923g (5.0mmol) of aromatic diphenol monomer, 0.7612g (5.5mmol) of potassium carbonate, 10 mL of N, N-dimethylacetamide and 15 mL of xylene are added into a 100mL reaction bottle under the protection of nitrogen, and the temperature is increased to 200 ℃ for reaction for 8 hours, so that viscous polyimide solution is prepared. Cooling the polyimide solution to 80 ℃, adding N, N-dimethylacetamide for dilution, then adding the diluted polyimide solution into ethanol for precipitation, filtering to obtain fibrous polyimide, and boiling, washing and drying to obtain polyimide powder. The glass transition temperature of the obtained polyimide powder was 310 ℃, and the 5% thermogravimetric temperature under a nitrogen atmosphere was 432 ℃.
Preparing the obtained polyimide powder into a solution with the weight percentage concentration of 10% by using N, N-dimethylacetamide, uniformly coating the solution on a clean glass plate by using a tape casting method, placing the glass plate in a drying oven at 80 ℃ overnight, and then heating according to the following procedures: 1 hour at 100 ℃; 1 hour at 150 ℃; 200 ℃ for 1 hour. And (3) taking out the glass plate after the temperature is reduced to room temperature, putting the glass plate into warm water for demoulding, and then putting the film into a drying oven at 100 ℃ for drying and dewatering to obtain the polyimide film with the thickness of 20 microns.
The transmission curve of the film prepared by the method is tested by an ultraviolet visible spectrometer, the ultraviolet absorption cut-off wavelength of the film is 347nm, and the light transmittance at 400nm is 80%.
Example 4:
in this example, the structural formula of the raw material aromatic diphenol monomer is as follows:
Figure BDA0001514118100000111
the obtained polyimide resin material has the following structural formula:
Figure BDA0001514118100000112
the preparation method comprises the following steps: 2.0515(5.0mmol) of 1, 4-bis (4-fluoro-imide) trans-cyclohexane, 2.0326g (5.0mmol) of aromatic diphenol monomer, 0.7612g (5.5mmol) of potassium carbonate, 10 mL of N, N-dimethylacetamide and 15 mL of xylene are added into a 100mL reaction bottle under the protection of nitrogen, and the temperature is increased to 200 ℃ for reaction for 8 hours, so that viscous polyimide solution is prepared. Cooling the polyimide solution to 80 ℃, adding N, N-dimethylacetamide for dilution, then adding the diluted polyimide solution into ethanol for precipitation, filtering to obtain fibrous polyimide, and boiling, washing and drying to obtain polyimide powder. The glass transition temperature of the obtained polyimide powder was 360 ℃, and the 5% thermogravimetric temperature under a nitrogen atmosphere was 431 ℃.
Preparing the obtained polyimide powder into a solution with the weight percentage concentration of 10% by using N, N-dimethylacetamide, uniformly coating the solution on a clean glass plate by using a tape casting method, placing the glass plate in a drying oven at 80 ℃ overnight, and then heating according to the following procedures: 1 hour at 100 ℃; 1 hour at 150 ℃; 200 ℃ for 1 hour. And (3) taking out the glass plate after the temperature is reduced to room temperature, putting the glass plate into warm water for demoulding, and then putting the film into a drying oven at 100 ℃ for drying and dewatering to obtain the polyimide film with the thickness of 20 microns.
The transmission curve of the film prepared by the method is tested by an ultraviolet visible spectrometer, the ultraviolet absorption cut-off wavelength of the film is 323nm, and the light transmittance at 400nm is 86%.
Example 5:
in this example, the structural formula of the raw material aromatic diphenol monomer is as follows:
Figure BDA0001514118100000121
the obtained polyimide resin material has the following structural formula:
Figure BDA0001514118100000122
wherein the cyclohexane structure is trans/cis-5/1
The preparation method comprises the following steps: 2.0515(5.0mmol) of a mixture of 1, 4-bis (4-fluoroamide) cis-cyclohexane and 1, 4-bis (4-fluoroamide) trans-cyclohexane, 2.0326g (5.0mmol) of aromatic diphenol monomer, 0.7612g (5.5mmol) of potassium carbonate, 10 mL of N, N-dimethylacetamide and 15 mL of xylene are added into a 100mL reaction flask under the protection of nitrogen, and the mixture is heated to 200 ℃ to react for 8 hours to prepare a viscous polyimide solution. Cooling the polyimide solution to 80 ℃, adding N, N-dimethylacetamide for dilution, then adding the diluted polyimide solution into ethanol for precipitation, filtering to obtain fibrous polyimide, and boiling, washing and drying to obtain polyimide powder. The glass transition temperature of the obtained polyimide powder was 344 ℃, and the 5% thermogravimetric temperature under a nitrogen atmosphere was 426 ℃.
Preparing the obtained polyimide powder into a solution with the weight percentage concentration of 10% by using N, N-dimethylacetamide, uniformly coating the solution on a clean glass plate by using a tape casting method, placing the glass plate in a drying oven at 80 ℃ overnight, and then heating according to the following procedures: 1 hour at 100 ℃; 1 hour at 150 ℃; 200 ℃ for 1 hour. And (3) taking out the glass plate after the temperature is reduced to room temperature, putting the glass plate into warm water for demoulding, and then putting the film into a drying oven at 100 ℃ for drying and dewatering to obtain the polyimide film with the thickness of 18 mu m.
The transmission curve of the film prepared by the method is tested by an ultraviolet visible spectrometer, the ultraviolet absorption cut-off wavelength of the film is 345nm, and the light transmittance at 400nm is 83%.
Example 6:
in this example, the structural formula of the raw material aromatic diphenol monomer is as follows:
Figure BDA0001514118100000131
the structural formula of the blocking agent is as follows:
Figure BDA0001514118100000132
the obtained polyimide resin material has the following structural formula:
Figure BDA0001514118100000133
wherein the cyclohexane structure is trans/cis-5/1
The preparation method comprises the following steps: 2.0515(5.0mmol) of a mixture of 1, 4-bis (4-fluoroamide) cis-cyclohexane and 1, 4-bis (4-fluoroamide) trans-cyclohexane, 2.0326g (5.0mmol) of aromatic diphenol monomer, 0.7612g (5.5mmol) of potassium carbonate, 10 mL of N, N-dimethylacetamide and 15 mL of xylene are added into a 100mL reaction flask under the protection of nitrogen, the temperature is raised to 230 ℃ for reaction for 8 hours, and then 0.1mmol of an end-capping reagent is added to prepare a viscous polyimide solution. Cooling the polyimide solution to 80 ℃, adding N, N-dimethylacetamide for dilution, then adding the diluted polyimide solution into ethanol for precipitation, filtering to obtain fibrous polyimide, and boiling, washing and drying to obtain polyimide powder. The glass transition temperature of the obtained polyimide powder was 347 ℃, and the 5% thermogravimetric temperature under a nitrogen atmosphere was 436 ℃.
Preparing the obtained polyimide powder into a solution with the weight percentage concentration of 10% by using N, N-dimethylacetamide, uniformly coating the solution on a clean glass plate by using a tape casting method, placing the glass plate in a drying oven at 80 ℃ overnight, and then heating according to the following procedures: 1 hour at 100 ℃; 1 hour at 150 ℃; 200 ℃ for 1 hour. And (3) taking out the glass plate after the temperature is reduced to room temperature, putting the glass plate into warm water for demoulding, and then putting the film into a drying oven at 100 ℃ for drying and dewatering to obtain the polyimide film with the thickness of 18 mu m.
The transmission curve of the film prepared by the method is tested by an ultraviolet visible spectrometer, the ultraviolet absorption cut-off wavelength of the film is 345nm, and the light transmittance at 400nm is 85%.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (6)

1. A polyimide resin, wherein the structural formula of the polyimide resin is shown as the following formula (I):
Figure FDA0002591378870000011
wherein n is an integer greater than 0;
Ar1is composed of
Figure FDA0002591378870000012
Ar2Is composed of
Figure FDA0002591378870000013
The transverse lines attached to the benzene rings "-" all represent Ar2A bond to an oxygen atom.
2. A method for preparing the polyimide resin according to claim 1, comprising the steps of:
mixing an aromatic diphenol monomer and 1, 4-bis (4-fluoro-imide) cyclohexane in a solvent under a protective atmosphere, and carrying out heating reaction under the action of an alkaline catalyst to obtain a polyimide solution;
mixing the polyimide solution with a precipitator, collecting the precipitate, and drying to obtain polyimide resin;
wherein the 1, 4-bis (4-fluoro-imide) cyclohexane is 1, 4-bis (4-fluoro-imide) trans cyclohexane;
the structural formula of the aromatic diphenol monomer is shown as the following formula (V):
Figure FDA0002591378870000021
wherein R is3，R4Is methyl.
3. The method of claim 2, wherein the basic catalyst is at least one of carbonate, bicarbonate, hydroxide, and organic base, and the molar amount of the basic catalyst is 100 to 150% of the molar amount of the aromatic diphenol monomer.
4. The method for preparing a polyimide resin according to claim 2, wherein the temperature of the heating reaction is 180 ℃ to 230 ℃, and the solvent is a polar aprotic solvent.
5. The method of preparing a polyimide resin according to claim 2, further comprising, before the step of mixing the polyimide solution with the precipitant, the steps of: and (2) end-capping the polyimide in the polyimide solution by an end-capping agent, wherein the structure of the end-capping agent is shown as the following formula (VI):
Figure FDA0002591378870000022
6. the method of claim 5, wherein the molar amount of the end-capping agent is 1 to 5% of the molar amount of the aromatic diphenol monomer.
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