CN115612099B - Low-expansion transparent copolyimide material and preparation method and application thereof - Google Patents
Low-expansion transparent copolyimide material and preparation method and application thereof Download PDFInfo
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses a low-expansion transparent copolyimide material, a preparation method and application thereof, wherein the polyimide is synthesized by condensation copolymerization of fluorine-containing diamine monomer, diamine monomer containing phenothiazine structure and amide bond and alicyclic dianhydride monomer; the fluorine-containing diamine monomer and the alicyclic dianhydride are polymerized, so that the polyimide chain segment has fluorine-containing groups and alicyclic structures, the conjugated structure and the regularity of a main chain are destroyed, the formation of intramolecular or intermolecular Charge Transfer Complexes (CTCs) is inhibited, and the optical performance of the polyimide film is improved; meanwhile, the heat resistance and the thermal expansion coefficient of the polyimide are regulated by copolymerization with diamine containing a phenothiazine structure and an amide bond, so that the problems that when the transparency of the polyimide is improved, the thermal performance is obviously reduced, the thermal expansion coefficient is improved, and a high polymer layer is warped or even peeled from an inorganic material under the action of thermal stress caused by expansion difference are solved.
Description
Technical Field
The invention relates to the technical field of synthesis of transparent polyimide materials, in particular to a low-expansion transparent copolymerized polyimide material, a preparation method and application thereof.
Background
With the development trend of wearable, ultrathin, light-weight and mass production of flexible display technology, polymer materials are receiving great attention because of flexibility, light weight and capability of realizing mass production in a roll-to-roll manner. The polymer substrate is used as a transmission path and medium of optical signals in a display device, and has certain requirements on optical transmittance. The conjugated units exist in the molecules of the traditional aromatic PI, so that a charge transfer complex (Charge transfer complex, CTC) is easy to generate, most of common polyimide films are brown yellow, the light transmittance in the visible light range is low, and the polyimide films are difficult to apply to flexible display devices with strict requirements on transparency.
In CN201710726438.1, a polyimide resin and a transparent polyimide film and a preparation method thereof are disclosed, wherein diamine monomer 2,2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether, 4' -diamino-2, 2' -bistrifluoromethyl biphenyl and dianhydride monomer triphenyldiether tetracarboxylic dianhydride, 4' - (hexafluoroisopropenyl) diphthalic anhydride are polymerized to obtain the polyimide film. In the polyimide structure, due to the introduction of fluorine-containing groups, the intermolecular arrangement is loose, the heat resistance is reduced, the linear thermal expansion coefficient of the film is higher, and the glass transition temperature of the polyimide is only 285-300 ℃. In electronic products, polyimide films are usually used together with inorganic materials such as copper and glass, and because the thermal expansion coefficient of the inorganic materials is far lower than that of the polymer materials, when the temperature changes, the polymer layers can warp or even peel from the inorganic materials under the effect of thermal stress caused by huge expansion difference. Thus, providing a highly transparent material with both low expansion and high heat resistance can promote the development of flexible materials.
Disclosure of Invention
The invention aims to solve the technical problems that the polyimide in the prior art has obviously reduced thermal performance and high thermal expansion coefficient when the transparency of the polyimide is improved, and provides a low-expansion transparent copolyimide material.
The invention aims to provide a preparation method of a low-expansion transparent copolyimide material.
The aim of the invention is realized by the following technical scheme:
a low-expansion transparent copolyimide material is synthesized by condensation copolymerization of fluorine-containing diamine monomer, diamine monomer containing phenothiazine structure and amide bond and alicyclic dianhydride monomer, and has the following structural general formula:
wherein m and n represent the number of repeating units, m and n are positive integers, m is 1-1000, and n is 1-1000;
y1 shown in the general structural formula is selected from one or more of the following structures:
the structure of Y2 shown is:
further, X in the general structural formula is selected from one or more of the following structures:
further, the molar ratio of the fluorine-containing diamine monomer to the diamine monomer containing the phenothiazine structure and the amide bond is 1:9-9:1.
Further, the preferred molar ratio of the fluorine-containing diamine monomer to the diamine monomer containing a phenothiazine structure and an amide bond is 4:6.
Further, the molar ratio of the total molar amount of the fluorine-containing diamine monomer and the diamine monomer containing a phenothiazine structure and an amide bond to the alicyclic dianhydride monomer is 1:0.9-1.1.
Further, the preparation method of the low-expansion transparent copolyimide material comprises the following steps: dissolving fluorine-containing diamine monomer and diamine monomer containing phenothiazine structure and amide bond in polar aprotic solvent, adding alicyclic dianhydride under stirring action after diamine monomer is completely dissolved, stirring and reacting for 0.5-72 h at-10-40 ℃ to obtain homogeneous and viscous polyamic acid glue solution, and dehydrating and imidizing the polyamic acid glue solution to obtain the low-expansion transparent copolyimide material.
Further, the polar aprotic organic solvent is one or more of N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, 1, 4-dioxane, N-dimethylacetamide, N-dimethylformamide, m-cresol and tetrahydrofuran.
Further, the total mass of the fluorine-containing diamine monomer, the diamine monomer containing a phenothiazine structure and an amide bond and the alicyclic dianhydride accounts for 2-50% of the total mass of the glue solution.
Further, the imidization method of the polyamic acid glue solution is thermal imidization or chemical imidization.
Further, the temperature gradient control of the thermal imidization is as follows: the room temperature is heated to 100 ℃ and then kept at the constant temperature for 0.5-2 hours, the temperature is heated to 200 ℃ from 100 ℃ and then kept at the constant temperature for 0.8-2 hours, the temperature is heated to 300 ℃ from 200 ℃ and then kept at the constant temperature for 0.8-2 hours, the temperature is heated to 350-500 ℃ from 300 ℃ and then kept at the constant temperature for 0.5-2 hours, and the polyimide film material can be obtained after cooling.
Further, the specific operation of the chemical imidization is as follows: adding a dehydrating agent into the polyamic acid glue solution, stirring for 0.5-1 h at room temperature, then scraping the glue solution onto a glass plate, heating to remove the solvent, and completing imidization.
Further, the dehydrating agent is pyridine/acetic anhydride, or triethylamine/acetic anhydride, or sodium acetate/acetic anhydride, isoquinoline/acetic anhydride, and an aprotic solvent.
Further, the chemical imidization temperature is controlled to be constant temperature of room temperature to 80 ℃ for 1h, constant temperature of 80 ℃ to 150-200 ℃ for 1h, and then the mixture is transferred to a vacuum oven at 400 ℃ for 10min. After cooling, a polyimide film can be obtained.
Further, the low-expansion transparent copolyimide material is applied to a flexible photoelectric substrate.
Compared with the prior art, the beneficial effects are that:
the invention ensures that the polyimide has fluorine-containing groups and alicyclic structures in the molecular structure through the polymerization of the fluorine-containing diamine monomer and the alicyclic dianhydride, damages the conjugated structure and regularity of the main chain, inhibits the formation of Charge Transfer Complexes (CTCs) in molecules or among molecules, and improves the optical performance of the polyimide film. Meanwhile, the rigid planar structure and the amide bond are introduced by copolymerization with the diamine monomer containing the phenothiazine structure and the amide bond, so that the packing density of polymer molecular chains is improved, the thermal expansion coefficient is reduced, and the heat resistance is improved.
Drawings
FIG. 1 is an infrared spectrum of the polyimide obtained in examples 2, 7 and 8, in which:
a corresponds to example 2;
b corresponds to example 7;
c corresponds to example 8;
FIG. 2 is a dynamic thermo-mechanical analysis (DMA) graph of the examples and comparative examples;
fig. 3 is a graph of static thermo-mechanical analysis (TMA) for the examples and comparative examples.
Detailed Description
The present invention is further illustrated and described below with reference to examples, which are not intended to be limiting in any way. Unless otherwise indicated, the methods and apparatus used in the examples were conventional in the art, the starting materials used were all conventional commercially available,
example 1
The present embodiment provides a method for preparing a diamine monomer containing a phenothiazine structure and an amide bond, the preparation steps comprising:
s1, synthesizing an intermediate 10H-phenothiazine-3,7-dicarbonitrile:
drying 0.01mol of 3, 7-dibromo-10H-phenohiazine, 0.05mol of cuprous cyanide and dehydrated N-methylpyridine50ml of pyrrolidone (NMP) was added to a three-necked flask, refluxed at 140℃for 24 hours, and then H was added 2 O(180mL),HCl(60mL)and FeCl 3 (25.8 mmol) was poured into the reaction and stirred for 1h, cooled to room temperature, filtered to give a brown precipitate, and washed with water, the resulting solid was redissolved in dichloromethane and washed with water, the solvent was removed under reduced pressure to give the crude product as a brown solid which was triturated with methanol to give intermediate 1. The structure of this intermediate 1 is as follows:
s2, synthesizing an intermediate 10H-phenothiazine-3,7-dicarboxylic acid:
adding 0.01mol of 10H-phenothiazine-3,7-dicarbonitrile, 20g of potassium hydroxide and 10ml of water into a three-necked flask, magnetically stirring, introducing argon, slowly heating until the reaction is finished to form brown potassium dicarboxylate, and diluting with distilled water; then acidifying with concentrated hydrochloric acid, separating out solid, washing with water, dissolving the crude product in hot ethanol, and recrystallizing to obtain intermediate 2. The structure of this intermediate 2 is as follows:
s3, synthesizing an intermediate 10H-phenothiazine-3,7-dicarbonyl dichloride:
0.05mol of 10H-phenothiazine-3,7-dicarboxylic acid is added into a three-neck flask, 100ml of dehydrated dichloromethane is added, 17.846g of thionyl chloride is slowly added dropwise under the ice bath condition, 3 to 4 drops of N, N-dimethylformamide are added dropwise as a catalyst, magnetic stirring is carried out, argon is introduced, and the temperature is raised to 75 ℃ for reaction reflux for 12 hours. The solvent and excess thionyl chloride were evaporated under reduced pressure to give intermediate 3. The intermediate 3 has the following structure:
s4, synthesizing an intermediate N 3 ,N 7 -bis(4-nitrophenyl)-10H-phenothiazine-3,7-dicarboxami-de：
0.1mol of 4-nitroaniline is dissolved in 150ml of a solution of N-methylpyrrolidone and pyridine in a ratio of 4:1, 0.02mol of 10H-phenohiazine-3, 7-dicarbonyl dichloride is slowly added, stirring is carried out for 2 hours at room temperature under argon environment, then the temperature is raised to 100 ℃ for reaction for 12 hours, the reaction solution is poured into methanol after cooling, the precipitate is filtered out, fully washed by methanol, recrystallized in N, N-dimethylformamide and water, and dried in a vacuum drying oven at 80 ℃ for 24 hours, thus obtaining the intermediate 4. The intermediate 4 has the following structure:
s5, synthesizing SNPDA:
0.01mol of N 3 ,N 7 Bis (4-nitrophenyl) -10H-phenothiazine-3,7-dicarboxa-mide is put into a three-mouth bottle, 450ml of absolute ethyl alcohol is added, magnetic stirring is carried out, argon is introduced, after oil bath is heated to 70 ℃, 10%wt of palladium carbon 0.1g is added, 10ml of hydrazine hydrate is gradually added dropwise, after reflux reaction is carried out for 24 hours, the reaction solution is filtered by a funnel, the filtrate is placed in a refrigerator for 24 hours for crystallization, off-white solid is collected after suction filtration, and the target product is obtained after drying in a vacuum drying oven at 80 ℃ for 24 hours. The structure of the target product is as follows:
example 2
The embodiment provides a preparation method of low-expansion transparent copolyimide, which comprises the following preparation steps:
s1, 0.002mol of SNPDA, 0.008mol of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFMB) and 13.4ml of N, N-dimethylformamide prepared in example 1 are taken and added into a three-neck flask, argon is introduced, stirring is carried out, after complete dissolution, 0.01mol of cyclobutane tetracarboxylic dianhydride (CBDA) is added, stirring reaction is continued for 12 hours, and a homogeneous transparent viscous polyamic acid solution is obtained.
S2, removing bubbles from the polyamic acid solution, then scraping and coating the solution on a glass plate, placing the glass plate in a vacuum oven, vacuumizing, and carrying out gradient heating, wherein the heating is controlled as follows: the room temperature is heated to 100 ℃ and then kept for 1h, the temperature is heated to 200 ℃ and then kept for 1h, the temperature is heated to 300 ℃ and then kept for 1h, the temperature is heated to 400 ℃ and then kept for 1h, and the low-expansion transparent copolyimide film (SNPDA+TFMB/CBDA-20%) is obtained after cooling.
Examples 3 to 6
This example was prepared according to the method described in example 2, using different amounts of SNPDA, 2' -bis (trifluoromethyl) diaminobiphenyl (TFMB) and cyclobutane tetracarboxylic dianhydride (CBDA) to copolymerize to obtain a low-expansion transparent copolyimide film. The specific formulation is shown in table 1 below:
TABLE 1
| SNPDA | TFMB | CBDA | PI | |
| Example 3 | 0.004mol | 0.006mol | 0.01mol | SNPDA+TFMB/CBDA-40％ |
| Example 4 | 0.005mol | 0.005mol | 0.01mol | SNPDA+TFMB/CBDA-50％ |
| Example 5 | 0.006mol | 0.004mol | 0.01mol | SNPDA+TFMB/CBDA-60％ |
| Example 6 | 0.008mol | 0.002mol | 0.01mol | SNPDA+TFMB/CBDA-80％ |
Example 7
The embodiment provides a preparation method of low-expansion transparent copolyimide, which comprises the following preparation steps:
s1, 0.004mol of SNPDA, 0.006mol of 2, 2-bis (trifluoromethyl) -4, 4-diaminophenyl ether and 13.4ml of N, N-dimethylformamide prepared in example 1 are taken and added into a three-neck flask, argon is introduced, stirring is carried out, after complete dissolution, 0.01mol of cyclobutane tetracarboxylic dianhydride (CBDA) is added, stirring reaction is continued for 12 hours, and a homogeneous transparent viscous polyamic acid solution is obtained.
S2, removing bubbles from the polyamic acid solution, then scraping and coating the solution on a glass plate, placing the glass plate in a vacuum oven, vacuumizing, and carrying out gradient heating, wherein the heating is controlled as follows: heating the room temperature to 100 ℃ and then keeping the temperature for 1h, heating the room temperature to 200 ℃ and then keeping the temperature for 1h, heating the room temperature to 300 ℃ and then keeping the temperature for 1h, and cooling the room temperature to 400 ℃ to obtain the low-expansion transparent copolyimide film.
Example 8
The embodiment provides a preparation method of low-expansion transparent copolyimide, which comprises the following preparation steps:
s1, 0.004mol of SNPDA, 0.006mol of 2, 2-bis (4-aminophenyl) hexafluoropropane and 13.4ml of N, N-dimethylformamide prepared in example 1 are taken and added into a three-neck flask, argon is introduced, stirring is carried out, after complete dissolution, 0.01mol of cyclobutane tetracarboxylic dianhydride (CBDA) is added, stirring reaction is continued for 12 hours, and a homogeneous transparent viscous polyamic acid solution is obtained.
S2, removing bubbles from the polyamic acid solution, then scraping and coating the solution on a glass plate, placing the glass plate in a vacuum oven, vacuumizing, and carrying out gradient heating, wherein the heating is controlled as follows: heating the room temperature to 100 ℃ and then keeping the temperature for 1h, heating the room temperature to 200 ℃ and then keeping the temperature for 1h, heating the room temperature to 300 ℃ and then keeping the temperature for 1h, and cooling the room temperature to 400 ℃ to obtain the low-expansion transparent copolyimide film.
Comparative example 1
This comparative example was prepared by adding 0.01mol of SNPDA diamine monomer and 13.4ml of N, N-dimethylformamide in example 1 to a three-necked flask, introducing argon gas, stirring, completely dissolving, adding 0.01mol of cyclobutane tetracarboxylic dianhydride (CBDA), and stirring for reaction for 12 hours to obtain a homogeneous transparent viscous polyamic acid solution.
Then the polyamic acid solution is scraped and coated on a glass plate after removing bubbles, and then the glass plate is placed in a vacuum oven, vacuumized, and subjected to gradient temperature rise, wherein the temperature rise is controlled as follows: heating the room temperature to 100 ℃ and then keeping the temperature for 1h, heating the room temperature to 200 ℃ and then keeping the temperature for 1h, heating the room temperature to 300 ℃ and then keeping the temperature for 1h, and cooling the room temperature to 400 ℃ to obtain the polyimide film.
Comparative example 2
This comparative example was prepared by adding 0.01mol of 2, 2-bis (trifluoromethyl) -4, 4-diaminophenyl ether and 13.4ml of N, N-dimethylformamide to a three-necked flask, introducing argon gas, stirring, completely dissolving, adding 0.01mol of cyclobutane tetracarboxylic dianhydride (CBDA), and stirring for reaction for 12 hours to obtain a homogeneous transparent viscous polyamic acid solution.
Then the polyamic acid solution is scraped and coated on a glass plate after removing bubbles, and then the glass plate is placed in a vacuum oven, vacuumized, and subjected to gradient temperature rise, wherein the temperature rise is controlled as follows: heating the room temperature to 100 ℃ and then keeping the temperature for 1h, heating the room temperature to 200 ℃ and then keeping the temperature for 1h, heating the room temperature to 300 ℃ and then keeping the temperature for 1h, and cooling the room temperature to 400 ℃ to obtain the polyimide film.
Comparative example 3
The comparative example adopts 0.01mol of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 13.2ml of N, N-dimethylformamide to be added into a three-neck flask, argon is introduced, stirring is carried out, after complete dissolution, 0.01mol of cyclobutane tetracarboxylic dianhydride (CBDA) is added, stirring reaction is carried out for 12 hours, and a homogeneous transparent viscous polyamic acid solution is obtained.
Then the polyamic acid solution is scraped and coated on a glass plate after removing bubbles, and then the glass plate is placed in a vacuum oven, vacuumized, and subjected to gradient temperature rise, wherein the temperature rise is controlled as follows: heating the room temperature to 100 ℃ and then keeping the temperature for 1h, heating the room temperature to 200 ℃ and then keeping the temperature for 1h, heating the room temperature to 300 ℃ and then keeping the temperature for 1h, and cooling the room temperature to 400 ℃ to obtain the polyimide film.
Comparative example 4
This comparative example was prepared by adding 0.01mol of 2, 2-bis (4-aminophenyl) hexafluoropropane and 13.4ml of N, N-dimethylformamide to a three-necked flask, introducing argon gas, stirring, completely dissolving, then adding 0.01mol of cyclobutane tetracarboxylic dianhydride (CBDA), and stirring for reaction for 12 hours to obtain a homogeneous transparent viscous polyamic acid solution.
Then the polyamic acid solution is scraped and coated on a glass plate after removing bubbles, and then the glass plate is placed in a vacuum oven, vacuumized, and subjected to gradient temperature rise, wherein the temperature rise is controlled as follows: heating the room temperature to 100 ℃ and then keeping the temperature for 1h, heating the room temperature to 200 ℃ and then keeping the temperature for 1h, heating the room temperature to 300 ℃ and then keeping the temperature for 1h, and cooling the room temperature to 400 ℃ to obtain the polyimide film.
1. Infrared spectroscopic detection
As can be seen from the infrared spectrum in FIG. 1, at 1720cm -1 And 1780cm -1 The characteristic peaks are symmetrical and asymmetrical stretching vibration of C=O bond in imide ring, 1610cm -1 A strong N-H bending vibration absorption peak appears nearby, 1364cm -1 Obvious C-N bond stretching vibration characteristic absorption peak appears at the position of 1080cm -1 The characteristic absorption peak of C-S-C appears nearby, but is between 3500 and 3300cm -1 No occurrence of-NH 2 These all demonstrate that examples 2, 7 and 8 have all successfully synthesized polyimides.
2. Performance detection
The polyimide films of examples 2 to 8 and comparative examples 1 to 4 were each tested for thermal expansion coefficient, light transmittance, thermal properties, and the like, and the results of the test data are shown in table 2 below:
TABLE 2
| Coefficient of thermal expansion (ppm/K) | Transmittance (500 nm) (%) | Glass transition temperature (. Degree. C.) | |
| Example 2 | 53.2 | 92.2 | 288.2 |
| Example 3 | 36.8 | 90.3 | 332.5 |
| Example 4 | 29.4 | 89.1 | 342.6 |
| Example 5 | 25.3 | 87.9 | 353.2 |
| Example 6 | 17.3 | 85.8 | 373.4 |
| Example 7 | 42.6 | 91.2 | 324.2 |
| Example 8 | 38.4 | 90.8 | 327.6 |
| Comparative example 1 | 16.4 | 70.2 | 396.2 |
| Comparative example 2 | 78.6 | 98.3 | 253.2 |
| Comparative example 3 | 70.4 | 96.4 | 262.4 |
| Comparative example 4 | 74.3 | 97.2 | 256.7 |
As can be seen from Table 2 and the accompanying figures 2-3, the prepared copolyimide has good light transmittance, can reach more than 85%, has low thermal expansion rate and high heat resistance, wherein the thermal expansion coefficient can be as low as 16.4, is close to that of metal, has a glass transition temperature as high as 373.4 ℃, and can meet the heat resistance requirement in a flexible substrate.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. The low-expansion transparent copolymerized polyimide material is characterized by being prepared by condensation copolymerization of a fluorine-containing diamine monomer, a diamine monomer containing a phenothiazine structure and an amide bond and a cycloaliphatic dianhydride monomer, and has the following structural general formula:
wherein m and n represent the number of repeating units, m and n are positive integers, m is 1-1000, and n is 1-1000;
y1 shown in the general structural formula is selected from one or more of the following structures:
the structure of Y2 shown is:
x in the general structural formula is selected from one or more of the following structures:
2. the low expansion transparent copolyimide material according to claim 1, wherein the molar ratio of the fluorine-containing diamine monomer to the diamine monomer containing phenothiazine structure and amide bond is 1:9 to 9:1.
3. The low expansion transparent copolyimide material according to claim 1, wherein the preferred molar ratio of the fluorine-containing diamine monomer and the diamine monomer containing phenothiazine structure and amide bond is 4:6.
4. The low expansion transparent copolymerized polyimide material according to claim 1, wherein the molar ratio of the total molar amount of the fluorine-containing diamine monomer and the diamine monomer having a phenothiazine structure and an amide bond to the alicyclic dianhydride monomer is 1:0.9 to 1.1.
5. The method for preparing a low expansion transparent copolyimide material according to claim 1, wherein the preparing step comprises: dissolving a fluorine-containing diamine monomer and a diamine monomer containing a phenothiazine structure and an amide bond in a polar aprotic solvent, adding alicyclic dianhydride under the stirring action after the diamine monomer is completely dissolved, stirring and reacting for 0.5-72 h at the temperature of minus 10-40 ℃ to obtain a homogeneous and viscous polyamic acid glue solution, and dehydrating and imidizing the polyamic acid glue solution to obtain the low-expansion transparent copolyimide material.
6. The method for preparing a low expansion transparent copolymerized polyimide material according to claim 5, wherein the polar aprotic organic solvent is one or more of N-methylpyrrolidone, dimethylsulfoxide, dimethylsulfone, sulfolane, 1, 4-dioxane, N-dimethylacetamide, N-dimethylformamide, m-cresol, and tetrahydrofuran.
7. The method for preparing a low expansion transparent copolyimide according to claim 5, wherein the total mass of the fluorine-containing diamine monomer, the diamine monomer containing phenothiazine structure and amide bond, and the alicyclic dianhydride is 2 to 50% of the total mass of the glue solution.
8. The method for preparing a low expansion transparent copolyimide according to claim 5, wherein the method for dehydrating imidization of the polyamic acid solution is thermal imidization or chemical imidization.
9. Use of the low expansion transparent copolyimide material according to claim 1 in flexible photovoltaic substrates.
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