CN112390950B - Polyimide, polyimide film and preparation method of polyimide film - Google Patents
Polyimide, polyimide film and preparation method of polyimide film Download PDFInfo
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Abstract
The invention discloses polyimide, a polyimide film and a preparation method of the polyimide film. The invention introduces a pyrimidinone structure into a polyimide molecular chain, provides a plurality of hydrogen bond binding sites, can form a large number of hydrogen bonds in molecules or among molecules, and ensures high light transmittance of the formed polyimide film and simultaneously has good mechanical property, heat resistance and bending resistance.
Description
Technical Field
The invention relates to the technical field of polyimide materials, in particular to polyimide, a polyimide film and a preparation method of the polyimide film.
Background
In recent years, flexible display technology has been developed more and more. The flexible substrate and the cover plate are important components in the flexible display device, play roles in structural support, protection and medium supply for optical signal transmission, and the functional characteristics of the flexible substrate and the cover plate determine the quality of the flexible device to a great extent.
Transparent polyimide films are one of the most desirable candidates for flexible display substrates and covers, which not only have high light transmittance, but also have good high temperature resistance and mechanical properties, and most importantly, flexibility is incomparable with glass (including ultra-thin flexible glass). The traditional transparent polyimide is designed to block the electron complexing transfer effect by introducing fluorine-containing groups, alicyclic groups and Gao Weizu groups into a molecular chain, increasing the asymmetry of the molecular chain and the like, so that the aim of improving the light transmittance is fulfilled, however, the mechanical property and the heat resistance of the material are inevitably reduced to a certain extent by the methods, and the application of the material in the flexible display field is limited. How to improve mechanical and thermal properties as much as possible while maintaining high light transmittance of polyimide is an important research topic to be solved in the flexible display field at present.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides polyimide which comprises a repeating unit shown in the following formula (1):
in the formula (1), X is tetravalent residue after removal of four carboxyl groups by a tetracarboxylic dianhydride monomer; y is a divalent residue of a diamine monomer containing a pyrimidinone structure after removal of two amino groups.
Preferably, in the formula (1), X is a tetravalent residue after removal of four carboxyl groups from an alicyclic tetracarboxylic dianhydride monomer or a fluorine-containing aromatic dianhydride monomer;
preferably, X is selected from one of the following groups:
preferably, in the formula (1), Y is selected from one of the following groups:
a polyimide film comprising the polyimide.
The preparation method of the polyimide film comprises the following steps: carrying out polycondensation reaction on diamine monomer containing pyrimidinone structure and tetracarboxylic dianhydride monomer to obtain polyamic acid, and carrying out imidization reaction on the polyamic acid to obtain polyimide; the polyimide film is obtained after the polyimide film is formed.
Preferably, the diamine monomer containing a pyrimidinone structure is 2, 5-diaminopyrimidin-4 (3H) -one, 2, 5-diureidopyrimidin-4 (3H) -one, or a combination thereof;
preferably, the tetracarboxylic dianhydride monomer comprises an alicyclic dianhydride, a fluorine-containing aromatic dianhydride, or a combination thereof; preferably, the tetracarboxylic dianhydride monomer comprises at least one of lipohydrogenated pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, 4' - (hexafluoroisopropenyl) diphthalic anhydride;
further, the molar ratio of the diamine monomer containing the pyrimidinone structure to the tetracarboxylic dianhydride monomer is 1: (0.995-1.005).
Preferably, the preparation method of the polyimide film comprises the following steps:
s1, adding diamine monomer containing pyrimidinone structure and tetracarboxylic dianhydride monomer into an organic solvent, and stirring for reaction to obtain polyamic acid solution;
s2, adding a dehydrating agent and a catalyst into the polyamic acid solution, and stirring for reaction to obtain a polyimide solution;
s3, coating the polyimide solution on a substrate, drying to obtain a gel film, and heating and orienting the gel film under the vacuumizing condition to obtain the polyimide film.
Preferably, the organic solvent is an aprotic polar solvent, preferably, the aprotic polar solvent is N, N-dimethylformamide, N-dimethylacetamide, or a combination thereof;
further, the solid content of the polyamic acid solution is 15 to 25 weight percent, and the viscosity is 300 to 1200 poise.
Preferably, the dehydrating agent is acetic anhydride, and the molar ratio of the dehydrating agent to the diamine monomer containing the pyrimidinone structure is (2-4): 1, a step of;
preferably, the catalyst is pyridine, isoquinoline or a combination thereof, and the molar ratio of the catalyst to the diamine monomer containing the pyrimidinone structure is (0.3-0.5): 1.
preferably, the reaction in the step S1 is carried out in an inert atmosphere, the reaction temperature is 30-50 ℃, and the reaction time is 60-120 min.
Preferably, the reaction time of the step S2 is 30-60 min.
Preferably, in the step S3, the drying temperature is 60-180 ℃ and the drying time is 30-60 min; the temperature of the heating orientation is 280-350 ℃, the vacuum degree is minus 0.097-minus 0.090MPa, and the time is 30-60 min.
The beneficial effects of the invention are as follows:
1. the invention synthesizes polyimide by taking diamine monomer containing pyrimidinone structure, especially 2, 5-diamino pyrimidine-4 (3H) -ketone and 2, 5-biurea pyrimidine-4 (3H) -ketone as diamine monomer, can provide a plurality of hydrogen bond binding sites, and the polymer containing the structural unit can form a great amount of hydrogen bonds in molecules or among molecules, thereby effectively improving the mechanical property and heat resistance of the material. In addition, the formation and the damage of the hydrogen bond are reversible, so that the material has a certain self-repairing function, and the bending resistance of the material is greatly improved.
2. The invention adopts fluorine-containing aromatic dianhydride or alicyclic dianhydride as a repeating unit, can effectively reduce the electron complexation transfer effect between molecules and ensure that highly transparent polyimide can be obtained.
In summary, the invention introduces a pyrimidinone structure into a polyimide molecular chain, provides a plurality of hydrogen bond binding sites, and can form a large number of hydrogen bonds in molecules or among molecules, and the polyimide film formed by the method has good mechanical properties, heat resistance and bending resistance while ensuring high light transmittance.
Drawings
FIG. 1 is a schematic diagram of the structure of polyimide in example 2 of the present invention.
FIG. 2 is a nuclear magnetic spectrum of 2, 5-diureido pyrimidine-4 (3H) -one prepared by the invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
The preparation of 2, 5-diaminopyrimidin-4 (3H) -one used in the following examples was as follows:
60g (0.54 mol) of isocytosine is added into a 500ml three-neck round bottom flask, 360ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:1) is slowly added into the flask, and the adding time lasts for 1.5-2 h. After heating to 80 ℃, stirring and reacting for 2 hours, pouring the solution into 500ml of ice water, and regulating the solution to be slightly alkaline (pH is 8-10) by using 5mol/L NaOH solution, and carrying out ice bath for 3 hours. The resulting solid was filtered, washed 3 to 5 times with ice water and dried to give 75g of 2-amino-5-nitropyrimidin-4 (3H) -one in 89% yield.
The reaction equation is as follows:
25g (0.16 mol) of 2-amino-5-nitropyrimidin-4 (3H) -one was charged into a Parr apparatus, and 2g of a mixed solution of 10% palladium on carbon and 500ml of ethanol and water (volume ratio of ethanol to water: 1:9) was added thereto, and reacted for 5 hours under stirring at room temperature under a hydrogen atmosphere of 4 atmospheres, the obtained mixed liquid was suction-filtered with celite and washed 3 times with 100ml of hot water, and the filtrate was collected, and the solvent was distilled off in vacuo to obtain 19.2g of 2, 5-diaminopyrimidin-4 (3H) -one in a yield of 95%.
The reaction equation is as follows:
the preparation of 2, 5-Diureidopyrimidin-4 (3H) -one used in the following examples was as follows:
25.2g (0.2 mol) of 2, 5-diaminopyrimidin-4 (3H) -one was added to a 500ml three-necked round bottom flask, 200ml of 2mol/L hydrochloric acid solution was added and stirred to dissolve, 39g (0.48 mol) of potassium cyanate was added in portions under ice water bath treatment conditions, stirred for 30min, and stirred at room temperature for 4H after removal of the ice water bath, and white precipitate appeared. After 1H at low temperature of 0-5 ℃, filtration is carried out, 100ml ice water is used for washing 3 times, and white solid obtained by filtration is dried to obtain 39.9g of 2, 5-diureido pyrimidine-4 (3H) -ketone with the yield of 94%, and the nuclear magnetic spectrum is shown in figure 2. 1 H NMR(ppm，DMSO-d 6 ):8.0(s，1H)，6.1-5.9(s，2H)，6.1-5.9(s，4H)，5.1(s，1H)。
The reaction equation is as follows:
example 1
A polyimide comprising the following repeating units:
FT IR(cm -1 KBr): 3260. 3175 and 1445 (-NH), 1778, 1706 and 710 (C ═ O on the imide ring), 1664 (C ═ O on the pyrimidine ring), 1368 (C-N on the imide ring).
The polyimide film containing the polyimide comprises the following preparation method:
s1, dissolving 12.6g (0.1 mol) of 2, 5-diaminopyrimidine-4 (3H) -ketone in 182.5g of N, N-dimethylformamide in a reaction kettle at 30 ℃, adding 19.502g (0.0995 mol) of cyclobutane tetracarboxylic dianhydride, and stirring and reacting for 120min under nitrogen atmosphere to obtain a polyamide acid solution with 15% of solid content and 300 poise of viscosity;
s2, adding 20.4g of acetic anhydride and 2.79g of pyridine into the polyamic acid solution, and stirring and reacting for 30min to obtain polyimide solution;
s3, coating the polyimide solution on a glass plate after vacuum defoamation treatment, and putting the glass plate into a blast drying box for drying treatment to obtain a gel film, wherein the concrete process of the drying treatment is as follows: firstly, treating at 60 ℃ for 30min, then at 120 ℃ for 20min, and finally at 150 ℃ for 10min; stripping the gel film from the glass plate, fixing on a metal frame, placing into a vacuum drying oven, and heating and orienting for 60min under the conditions of vacuum degree of-0.090 MPa and temperature of 280 ℃ to obtain the polyimide film.
Example 2
A polyimide comprising the following repeating units:
FT IR(cm -1 KBr): 3258. 3170 and 1445 (NH in pyrimidine ring and amide group), 1777, 1712 and 716 (C ═ O on imide ring), 1665 and 1643 (pyrimidine ring and amide group)C ═ O) 1368 (C-N on the imide ring).
The polyimide film containing the polyimide comprises the following preparation method:
s1, dissolving 21.2g (0.1 mol) of 2, 5-diureidopyrimidine-4 (3H) -ketone into 231.2g of N, N-dimethylacetamide in a reaction kettle at 30 ℃, adding 19.6g (0.1 mol) of cyclobutane tetracarboxylic dianhydride, and stirring under nitrogen atmosphere to react for 120min to obtain a polyamide acid solution with the solid content of 15% and the viscosity of 330 poise;
s2, adding 20.4g of acetic anhydride and 2.79g of pyridine into the polyamic acid solution, and stirring and reacting for 30min to obtain polyimide solution;
s3, coating the polyimide solution on a glass plate after vacuum defoamation treatment, and putting the glass plate into a blast drying box for drying treatment to obtain a gel film, wherein the concrete process of the drying treatment is as follows: firstly, treating at 60 ℃ for 30min, then at 120 ℃ for 20min, and finally at 150 ℃ for 10min; stripping the gel film from the glass plate, fixing on a metal frame, placing into a vacuum drying oven, and heating and orienting for 60min under the conditions of vacuum degree of-0.090 MPa and temperature of 280 ℃ to obtain the polyimide film.
Example 3
A polyimide comprising the following repeating units:
FT IR(cm -1 KBr): 3264. 3176 and 1445 (-NH), 1780, 1717 and 724 (C ═ O on the imide ring), 1670 (C ═ O on the pyrimidine ring), 1366 (C-N on the imide ring).
The polyimide film containing the polyimide comprises the following preparation method:
s1, dissolving 12.6g (0.1 mol) of 2, 5-diaminopyrimidine-4 (3H) -ketone in 140g of N, N-dimethylformamide in a reaction kettle at 40 ℃, adding 22.4g (0.1 mol) of hydrogenated pyromellitic dianhydride, and stirring under nitrogen atmosphere for reaction for 90min to obtain a polyamide acid solution with 20% of solid content and 500 poise of viscosity;
s2, adding 30.6g of acetic anhydride and 3.7g of pyridine into the polyamic acid solution, and stirring and reacting for 45min to obtain polyimide solution;
s3, coating the polyimide solution on a glass plate after vacuum defoamation treatment, and putting the glass plate into a blast drying box for drying treatment to obtain a gel film, wherein the concrete process of the drying treatment is as follows: firstly, treating for 30min at 120 ℃ and then treating for 15min at 150 ℃; stripping the gel film from the glass plate, fixing on a metal frame, placing into a vacuum drying oven, and heating and orienting for 45min under the conditions of vacuum degree of-0.094 MPa and temperature of 320 ℃ to obtain the polyimide film.
Example 4
A polyimide comprising the following repeating units:
FT IR(cm -1 KBr): 3254. 3165 and 1450 (NH in pyrimidine ring and amide group), 1773, 1716 and 709 (C ═ O on imide ring), 1671 and 1647 (C ═ O on pyrimidine ring and in amide group), 1367 (C-N on imide ring).
The polyimide film containing the polyimide comprises the following preparation method:
s1, dissolving 21.2g (0.1 mol) of 2, 5-diureido pyrimidine-4 (3H) -ketone in 174.4g of N, N-dimethylacetamide in a reaction kettle at 40 ℃, adding 22.4g (0.1 mol) of hydrogenated pyromellitic dianhydride, and stirring under nitrogen atmosphere for reaction for 90min to obtain a polyamide acid solution with 20% of solid content and 570 poise of viscosity;
s2, adding 30.6g of acetic anhydride and 5.2g of isoquinoline into the polyamic acid solution, and stirring and reacting for 45min to obtain polyimide solution;
s3, coating the polyimide solution on a glass plate after vacuum defoamation treatment, and putting the glass plate into a blast drying box for drying treatment to obtain a gel film, wherein the concrete process of the drying treatment is as follows: firstly, treating for 30min at 120 ℃ and then treating for 15min at 150 ℃; stripping the gel film from the glass plate, fixing on a metal frame, placing into a vacuum drying oven, and heating and orienting for 45min under the conditions of vacuum degree of-0.094 MPa and temperature of 320 ℃ to obtain the polyimide film.
Example 5
A polyimide comprising the following repeating units:
FT IR(cm -1 KBr): 3265. 3174 and 1444 (-NH), 1774, 1708 and 719 (C ═ O on imide ring), 1667 (C ═ O on pyrimidine ring), 1369 (C-N on imide ring), 1332 and 734 (C-F).
The polyimide film containing the polyimide comprises the following preparation method:
s1, in a reaction kettle at 50 ℃, firstly dissolving 12.6g (0.1 mol) of 2, 5-diaminopyrimidine-4 (3H) -ketone into 171g of N, N-dimethylformamide, then adding 44.4g (0.1 mol) of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride, and stirring and reacting for 60min under nitrogen atmosphere to obtain a polyamide acid solution with 25% of solid content and 1050 poise of viscosity;
s2, adding 40.8g of acetic anhydride and 6.45g of isoquinoline into the polyamic acid solution, and stirring and reacting for 60min to obtain polyimide solution;
s3, coating the polyimide solution on a glass plate after vacuum defoamation treatment, and putting the glass plate into a blast drying box for drying treatment to obtain a gel film, wherein the concrete process of the drying treatment is as follows: firstly, treating for 10min at 120 ℃, then treating for 10min at 150 ℃, and finally treating for 10min at 180 ℃; stripping the gel film from the glass plate, fixing on a metal frame, placing into a vacuum drying oven, and heating and orienting for 30min under the conditions of vacuum degree of-0.097 MPa and temperature of 350 ℃ to obtain the polyimide film.
Example 6
A polyimide comprising the following repeating units:
FT IR(cm -1 KBr): 3257. 3168 and 1454 (NH in pyrimidine ring and amide group), 1770, 1716 and 711 (C ═ O on imide ring), 1672 and 1650 (C ═ O on pyrimidine ring and in amide group), 1368 (C-N on imide ring), 1330 and 733 (C-F).
The polyimide film containing the polyimide comprises the following preparation method:
s1, 21.2g (0.1 mol) of 2, 5-diureidopyrimidine-4 (3H) -ketone is dissolved in 196.8g of N, N-dimethylacetamide in a reaction kettle at 50 ℃, 44.622g (0.1005 mol) of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride is added, and the mixture is stirred and reacted for 60min under a nitrogen atmosphere to obtain a polyamide acid solution with 25% of solid content and 1200 poise of viscosity;
s2, adding 40.8g of acetic anhydride and 6.45g of isoquinoline into the polyamic acid solution, and stirring and reacting for 60min to obtain polyimide solution;
s3, coating the polyimide solution on a glass plate after vacuum defoamation treatment, and putting the glass plate into a blast drying box for drying treatment to obtain a gel film, wherein the concrete process of the drying treatment is as follows: firstly, treating for 10min at 120 ℃, then treating for 10min at 150 ℃, and finally treating for 10min at 180 ℃; stripping the gel film from the glass plate, fixing on a metal frame, placing into a vacuum drying oven, and heating and orienting for 30min under the conditions of vacuum degree of-0.097 MPa and temperature of 350 ℃ to obtain the polyimide film.
Comparative example 1
Comparative example 1 is a control of example 1, and is specifically as follows:
s1, dissolving 20g (0.1 mol) of 4,4' -diaminodiphenyl ether in 224.4g of N, N-dimethylformamide in a reaction kettle at 30 ℃, adding 19.502g (0.0995 mol) of cyclobutane tetracarboxylic dianhydride, and stirring and reacting for 120min under a nitrogen atmosphere to obtain a polyamide acid solution with the solid content of 15% and the viscosity of 650 poise;
s2, adding 20.4g of acetic anhydride and 2.79g of pyridine into the polyamic acid solution, and stirring and reacting for 30min to obtain polyimide solution;
s3, coating the polyimide solution on a glass plate after vacuum defoamation treatment, and putting the glass plate into a blast drying box for drying treatment to obtain a gel film, wherein the concrete process of the drying treatment is as follows: firstly, treating at 60 ℃ for 30min, then at 120 ℃ for 20min, and finally at 150 ℃ for 10min; stripping the gel film from the glass plate, fixing on a metal frame, placing into a vacuum drying oven, and heating and orienting for 60min under the conditions of vacuum degree of-0.090 MPa and temperature of 280 ℃ to obtain the polyimide film.
Comparative example 2
Comparative example 2 is a control of example 4, and is specifically as follows:
s1, dissolving 10.8g (0.1 mol) of p-phenylenediamine in 132.8g of N, N-dimethylacetamide in a reaction kettle at 40 ℃, adding 22.4g (0.1 mol) of hydrogenated pyromellitic dianhydride, and stirring and reacting for 90min under a nitrogen atmosphere to obtain a polyamide acid solution with the solid content of 20% and the viscosity of 880 poise;
s2, adding 30.6g of acetic anhydride and 5.2g of isoquinoline into the polyamic acid solution, and stirring and reacting for 45min to obtain polyimide solution;
s3, coating the polyimide solution on a glass plate after vacuum defoamation treatment, and putting the glass plate into a blast drying box for drying treatment to obtain a gel film, wherein the concrete process of the drying treatment is as follows: firstly, treating for 30min at 120 ℃ and then treating for 15min at 150 ℃; stripping the gel film from the glass plate, fixing on a metal frame, placing into a vacuum drying oven, and heating and orienting for 45min under the conditions of vacuum degree of-0.094 MPa and temperature of 320 ℃ to obtain the polyimide film.
Comparative example 3
Comparative example 2 is a control of example 6, and is specifically as follows:
s1, dissolving 20g (0.1 mol) of 4,4 '-diaminodiphenyl ether in 193.2g of N, N-dimethylacetamide in a reaction kettle at 50 ℃, adding 44.622g (0.1 mol) of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride, and stirring and reacting for 60min under nitrogen atmosphere to obtain a polyamide acid solution with 25% of solid content and 1450 poise of viscosity;
s2, adding 40.8g of acetic anhydride and 6.45g of isoquinoline into the polyamic acid solution, and stirring and reacting for 60min to obtain polyimide solution;
s3, coating the polyimide solution on a glass plate after vacuum defoamation treatment, and putting the glass plate into a blast drying box for drying treatment to obtain a gel film, wherein the concrete process of the drying treatment is as follows: firstly, treating for 10min at 120 ℃, then treating for 10min at 150 ℃, and finally treating for 10min at 180 ℃; stripping the gel film from the glass plate, fixing on a metal frame, placing into a vacuum drying oven, and heating and orienting for 30min under the conditions of vacuum degree of-0.097 MPa and temperature of 350 ℃ to obtain the polyimide film.
The polyimide films prepared in the examples and comparative examples were subjected to performance test, and the results are shown in table 1.
TABLE 1 polyimide film Performance test results
As can be seen from table 1, under the same process conditions, the transparent polyimide film prepared by polymerizing the diamine monomer containing the pyrimidinone structure and the common diamine monomer has higher light transmittance, better mechanical property, heat resistance and bending resistance than the transparent polyimide film prepared by polymerizing the diamine monomer containing the pyrimidinone structure and the common diamine monomer, and has the potential of being used as a substrate and a cover plate material of a flexible organic light emitting diode display screen.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. A polyimide comprising a repeating unit represented by the following formula (1):
in the formula (1), X is tetravalent residue after removal of four carboxyl groups by a tetracarboxylic dianhydride monomer; y is a divalent residue of a diamine monomer containing a pyrimidinone structure after removal of two amino groups;
and X is selected from one of the following groups:
and Y is selected from one of the following groups:
2. a polyimide film comprising the polyimide of claim 1.
3. A method for producing the polyimide film according to claim 2, comprising: carrying out polycondensation reaction on diamine monomer containing pyrimidinone structure and tetracarboxylic dianhydride monomer to obtain polyamic acid, and carrying out imidization reaction on the polyamic acid to obtain polyimide; the polyimide film is obtained after the polyimide film is formed.
4. The method for producing a polyimide film according to claim 3, wherein the diamine monomer having a pyrimidinone structure is 2, 5-diaminopyrimidin-4 (3H) -one, 2, 5-diureidopyrimidin-4 (3H) -one, or a combination thereof;
the tetracarboxylic dianhydride monomer comprises at least one of hydrogenated pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride;
the molar ratio of the diamine monomer containing the pyrimidinone structure to the tetracarboxylic dianhydride monomer is 1: (0.995-1.005).
5. The method for producing a polyimide film according to claim 3 or 4, comprising the steps of:
s1, adding diamine monomer containing pyrimidinone structure and tetracarboxylic dianhydride monomer into an organic solvent, and stirring for reaction to obtain polyamic acid solution;
s2, adding a dehydrating agent and a catalyst into the polyamic acid solution, and stirring for reaction to obtain a polyimide solution;
s3, coating the polyimide solution on a substrate, drying to obtain a gel film, and heating and orienting the gel film under the vacuumizing condition to obtain the polyimide film.
6. The method for producing a polyimide film according to claim 5, wherein the organic solvent is N, N-dimethylformamide, N-dimethylacetamide or a combination thereof;
the solid content of the polyamic acid solution is 15-25 wt% and the viscosity is 300-1200 poise.
7. The method for producing a polyimide film according to claim 5, wherein the dehydrating agent is acetic anhydride, and the molar ratio of the dehydrating agent to the diamine monomer having a pyrimidinone structure is (2 to 4): 1, a step of;
the catalyst is pyridine, isoquinoline or a combination thereof, and the molar ratio of the catalyst to the diamine monomer containing the pyrimidinone structure is (0.3-0.5): 1.
8. the method for preparing a polyimide film according to claim 5, wherein the reaction in step S1 is performed in an inert atmosphere at a reaction temperature of 30 to 50 ℃ for 60 to 120 minutes; the reaction time of the step S2 is 30-60 min; in the step S3, the drying temperature is 60-180 ℃ and the drying time is 30-60 min; the heating orientation temperature is 280-350 ℃, the vacuum degree is-0.097 to-0.090 MPa, and the time is 30-60 min.
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