CN113201136B - Preparation method of polyimide resin and film thereof - Google Patents
Preparation method of polyimide resin and film thereof Download PDFInfo
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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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
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Abstract
The invention relates to the field of polyimide, in particular to a preparation method of polyimide resin, which comprises the following steps: s1, dissolving a first batch of poly-diamine in a solvent under an inert gas atmosphere, adding 105-110% of poly-dianhydride of the total mole amount of the first batch of poly-diamine in a low-temperature environment of 30 ℃ or below for polymerization to form a resin solution, and controlling the viscosity of the resin solution at 50000-70000 cps; s2, monitoring the viscosity of the resin solution and gradually raising the temperature within 30-80 ℃, and gradually adding the second poly-diamine in batches of more poly-diamine and less poly-diamine until the viscosity of the resin solution is 180000-; s3, adding a fluorine-containing end-capping reagent, uniformly mixing, defoaming in high vacuum to obtain a polyimide resin solution, wherein the formed polyimide coating has high thermal stability and a thermal expansion coefficient close to that of the base film.
Description
Technical Field
The invention relates to the field of polyimide films, in particular to a preparation method of polyimide resin and a film thereof.
Background
At present, diamine and dianhydride are added in equal molar amounts in a proper organic solvent to carry out low-temperature polycondensation reaction to synthesize polyamic acid, then a film is cast on a substrate, and finally the film is imidized to form a film, but the preparation method ensures that the apparent viscosity of the polyamic acid is difficult to control in an ideal range with larger viscosity, the length of polymer molecular chain segments is not uniform, the viscosity of the resin is difficult to stabilize, the bubble amount of the resin is larger, and the experiment process shows that the viscosity can jump like an index when the dianhydride and the diamine are close to equal molar ratio, so the conventional feeding mode is difficult to control the apparent viscosity of the resin in a polymerization manner in a low-temperature environment, the extremely trace dianhydride is often added to increase the viscosity to exceed the expected range, or the viscosity is obviously reduced in a short period at normal temperature, great difficulty is brought to industrial batch production, and the phenomenon of difficult local high-degree polycondensation is easily caused by directly adding diamine solid to control the viscosity agglomeration, the performance quality of the polyimide resin is reduced, and the film prepared therefrom is not excellent.
Disclosure of Invention
The invention provides a preparation method of polyimide with stable performance and viscosity under long-term storage, which comprises the following steps:
s1, dissolving a first batch of poly-diamine in a solvent under an inert gas atmosphere, adding 105-110% of poly-dianhydride of the total mole amount of the first batch of poly-diamine in a low-temperature environment of 30 ℃ or below for polymerization to form a resin solution, and controlling the viscosity of the resin solution at 50000-70000 cps;
s2, monitoring the viscosity of the resin solution and gradually raising the temperature within 30-80 ℃, and gradually adding the second poly-diamine in batches of more poly-diamine and less poly-diamine until the viscosity of the resin solution is 180000-;
and S3, adding a fluorine-containing end-capping reagent, mixing, and defoaming in high vacuum to obtain the polyimide resin solution. The invention also provides a film, and the preparation method comprises the following steps: the polyimide resin is selected, and a catalyst and a dehydrating agent are sequentially added into the polyimide resin and then coated on at least one side of a base film.
Another object of the present invention is to provide a thin film, which is prepared by a method comprising: the polyimide resin is selected, and a catalyst and a dehydrating agent are sequentially added into the polyimide resin and then coated on at least one side of a base film.
The invention has the beneficial effects that:
the problem of viscosity control and viscosity stability is solved, and the polyimide resin obtained by the preparation method is uniform and stable, can be stored in a natural environment at normal temperature and normal pressure for a long time, and the viscosity and the performance are hardly changed; the problem that end chain anhydride is easy to hydrolyze is solved by the fluorine-containing end capping agent, end chain capping is carried out by adding monoamine aromatic organic matters with a proper molar ratio, an end chain structure is an amino structure, the problem that end groups are hydrolyzed is completely avoided, the problem that the dielectric constant of common polyimide resin is high is solved simultaneously, and because the fluorine-containing compound has the effect of reducing the dielectric constant, the dielectric constant can be effectively reduced by adding proper amount of fluorine-containing amine organic matters, so that the electric leakage, the heating and the inter-wire capacitance effect of an integrated circuit are reduced.
When the polyimide resin prepared by the invention is coated on a base film to prepare a film, the formed polyimide coating has stronger thermal stability and thermal expansion coefficient close to that of the base film, and the problem that the edge of the film is easy to curl due to larger difference of the thermal expansion coefficients is solved.
Detailed Description
Before the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is intended as a preferred example for purposes of illustration only and is not intended to limit the scope of the present disclosure, so it is to be understood that other equivalents and modifications may be made without departing from the spirit and scope of the present disclosure.
Based on the problem that the performance and viscosity of the polyimide resin prepared at home at present cannot be preserved for a long time at normal temperature and normal pressure, the invention provides a preparation method of the polyimide resin, which comprises the following steps:
s1, dissolving a first batch of poly-diamine in a solvent under an inert gas atmosphere, adding 105-110% of poly-dianhydride of the total mole amount of the first batch of poly-diamine in a low-temperature environment of 30 ℃ or below for polymerization to form a resin solution, and controlling the viscosity of the resin solution at 50000-70000 cps;
s2, monitoring the viscosity of the resin solution and gradually raising the temperature within 30-80 ℃, and gradually adding the second poly-diamine in batches of more poly-diamine and less poly-diamine until the viscosity of the resin solution is 180000-;
and S3, adding a fluorine-containing end-capping reagent, uniformly mixing, and defoaming in high vacuum to obtain the polyimide resin solution.
Firstly polymerizing a first batch of polybasic diamine and polybasic dianhydride into a low-viscosity resin solution at low temperature, and then gradually heating the solution at 30-80 ℃, which is different from the conventional batch feeding of the polybasic diamine, the invention emphasizes that a second batch of the polybasic diamine is gradually added into the resin solution within different temperature gradients by adopting a difference method, so that the process of continuously reforming, homogenizing and lengthening a high molecular chain segment is realized, when the lengths of all the chain segments are kept to be balanced, the chain segments are not easy to rearrange, and the polyimide resin solution prepared by the preparation method is uniform and stable, as shown in table 1, compared with the polyimide resin solution prepared by the prior art, the viscosity of the polyimide resin solution can be kept unchanged for a long time, and the polyimide resin solution can be stored for a long time; meanwhile, the fluorine-containing end capping agent can effectively reduce the hydrolysis of the end chain of the polyimide resin solution, further improve the viscosity stability of the polyimide resin solution, ensure that the structure of a subsequently prepared film is more stable, correspondingly enhance the tensile strength of the film, reduce the dielectric constant of the fluorine-containing compound, and reduce the electric leakage, the heat generation and the capacitance effect between leads of an integrated circuit when the polyimide solution is prepared into the film in the subsequent process and applied to a circuit board.
The monitoring method for monitoring the resin is not limited to any method capable of controlling the viscosity of the polyimide resin at any time, and can be listed as conventional means in the field such as a viscosity testing system with a viscosity probe, a multi-stage sampling bottle external test and the like.
The total molar weight of the first lot of the polybasic diamine and the second lot of the polybasic diamine is close to the total molar weight of the polybasic dianhydride, the addition amount of the second lot of the polybasic diamine is based on that the resin viscosity reaches 180000-200000cps, and the ratio of the total molar weight of the first lot of the polybasic diamine and the second lot of the polybasic diamine to the total molar weight of the polybasic dianhydride is 0.9-1.0: 1.0.
The low temperature environment in the step S1 of the present invention is-20 to 30 ℃, and when the poly-diamine and the poly-dianhydride are primarily polymerized to form the resin solution, the reaction is a reaction in which the exothermic entropy increases, so that the low temperature contributes to the polymerization reaction of the molecular chain segment, and the reaction is promoted to proceed toward the forward direction, so that the molecular chain segment is continuously grown and the viscosity is increased, and therefore, the low temperature environment is further preferably-20 to-10 ℃,10 to 0 ℃, 0 to 10 ℃ and 10 to 30 ℃.
As a specific operation method for adding the second batch of the poly-diamine in batches in the S2 step, the adding amount of the second batch of the poly-diamine in the S2 step is 5-10% of the total mole amount of the first batch of the poly-diamine, and the adding in batches is specifically operated as follows: adding 40 percent of the molar total amount of the second poly-diamine in a temperature gradient of 30-35 ℃, adding 25 percent of the molar total amount of the second poly-diamine in a temperature gradient of 45-50 ℃, adding 20 percent of the molar total amount of the second poly-diamine in a temperature gradient of 65-70 ℃, adding 10 percent of the molar total amount of the second poly-diamine in a temperature gradient of 75-80 ℃, continuously stirring and monitoring the viscosity of the resin solution, stopping feeding if the viscosity of the resin is stabilized within a specified value range, and otherwise, continuously adding the rest of the second poly-diamine until the viscosity of the resin reaches the specified value.
To control the amount of the fluorine-containing capping agent added, the molar total amount of the fluorine-containing capping agent plus the molar amount of the first plurality of diamines and the molar amount of the second plurality of diamines may be further defined to be about equal to the molar amount of the polyanhydrides.
In the preparation method, the preparation method emphasizes that the polybasic diamine composed of at least two kinds of diamine and the polybasic dianhydride composed of at least two kinds of dianhydride are used, and the heat expansion coefficient can be adjusted by matching the polybasic copolymerization mode with different amine anhydride molar ratios, so that the heat expansion coefficient of the prepared polyimide resin solution after film formation can be equivalent to that of a base film, and the phenomenon of curling of the edge of the film due to larger difference of the heat expansion coefficients is avoided. A first diamine: … …: n-th diamine = (0.1-0.9): … …: (0.1-0.9), a first dianhydride: … …: the nth dianhydride = (0.1-0.9): … …: (0.1-0.9), n is more than or equal to 2; as shown in table 1, polyimide films having different thermal expansion coefficients can be obtained by changing the compounding ratio of the polyvalent diamines and the compounding ratio of the polyvalent dianhydrides with the same polyvalent diamines and polyvalent dianhydrides.
The diamine of the present invention is not particularly limited, and may be any diamine known in the art, and specific examples thereof include p-phenylenediamine and its ring-fluorinated compound, benzidine and its ring-fluorinated compound, 4 '-oxydianiline, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (2-aminophenoxy) benzene, 4' -bis (3-aminophenoxy) biphenyl, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (5-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (2-aminophenoxy) phenyl) sulfone, bis (4-aminophenoxy) phenyl) sulfone, and the like, 4,4' -diaminodiphenylethane, 4' -diaminodiphenylisopropane, 4' -diaminophenylsulfide, 3' -diaminodiphenylsulfone, 4' -diaminodiphenylsulfone, 3' -oxydianiline, 3,4' -oxydianiline, 2,4' -oxydianiline, 4' -diaminodiphenyldiethylsilane, 4' -diaminodiphenylsilane, 4' -diaminodiphenylethylphosphine oxide, 4' -diaminodiphenyl-N-methylamine, 4' -diaminodiphenyl-N-aniline, 1, 3-diaminobenzene, 1, 2-diaminobenzene, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 2,4' -diaminodiphenylisopropyl-phenyl-4, 4' -diaminodiphenylisopropyl-4, 4' -oxydianiline, 4' -diaminodiphenylethyl-N-aniline, 1, 3-diaminobenzene, 1, 2' -diaminobenzene, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 2,4' -diaminodiphenyl-methyl-o-phenyl ] propane, 4' -diaminodiphenyl-ethyl-phenyl-1, 4' -diaminodiphenyl-phenyl-ethyl-phenyl-1, 4' -diaminodiphenyl-phenyl-4, 4' -diaminodiphenyl, 4' -diaminodiphenyl, 4' -diaminodiphenyl, 4' -diaminodiphenyl, 4' -diaminodiphenyl, 4, 2,2' -bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, 4' -diamino-2, 2' -bistrifluoromethylbiphenyl.
The dianhydride of the present invention is not particularly limited, and may be any dianhydride known in the art, and specific examples thereof include pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) ethane dianhydride, hydroxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, ethylenebis (trimellitic acid anhydride), monoester dianhydride, Bisphenol a bis (trimellitic acid monoester anhydride), 4,4' -oxydiphthalic anhydride, 4,4' -thiobisphthalic anhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride.
The fluorine-containing end-capping agent of the present invention is a fluorine-containing monoamine aromatic organic compound, and reacts with the terminal anhydride structure of the polyimide resin solution to perform end-capping, so that the terminal structure of the polyimide resin solution is the amino structure of the fluorine-containing end-capping agent, thereby preventing hydrolysis of the polyimide resin solution, and examples of the fluorine-containing end-capping agent include m-bis (trifluoromethyl) aniline, 4- (4' -fluorophenyl) benzonitrile, p-trifluoromethylaniline, 2, 6-difluoro-3-methylaniline, cyanoacetyl-p-trifluoromethylaniline, 4-methyl-2- (trifluoromethyl) aniline, 3-fluoro-2- (trifluoromethyl) aniline, 5-fluoro-2-trifluoromethylaniline, 4-fluoro-2-nitro-5- (trifluoromethyl) -aniline, and the like, Any one of trifluoroaniline, N-ethyl-2, 3, 5-trifluoroaniline, 2,3, 4-trifluorophenylacetamide and 2,3, 4-trifluoro-6-nitroaniline.
The solvent is not particularly limited in the present invention, and N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, cyclohexane, methylcyclohexane, tetrahydrofuran, isohexane, N-heptane, dichloromethane, trichloroethylene, carbon tetrachloride, epichlorohydrin, methyl methacrylate, and dimethyl sulfoxide can be exemplified.
After the polyimide resin solution with stable and strong viscosity is obtained, a film with more excellent performance is more expected to be obtained, and the specific preparation method is that the catalyst and the dehydrating agent are sequentially added into the polyimide resin solution obtained by adopting any technical scheme to enable polyimide acid to be quickly dehydrated, imidized and formed into a film, so that the production efficiency is improved, and when the film is coated on at least one side of the base film, the tensile strength of the film is increased.
The invention also extends to the catalyst types which are not used in the field at present on the basis of the catalyst types commonly used in the field, the invention emphasizes that the catalyst can be a monocyclic or fused ring compound, such as pyridazine, pyrimidine, diazine and 1, 10-phenanthroline, as shown in table 1, when the catalyst emphasized by the invention is selected, a polyimide film with more excellent tensile strength can be obtained, preferably, the catalytic performance is the most excellent by selecting the pyridazine and the pyridine, and the mass ratio of the two catalysts is 1: 4.
in the preparation process, the optimal ratio of the catalyst to the polyimide resin solution can be controlled within the range of 1:95-105 by mass.
The base film is not particularly limited, and may be a base film commonly used in the art, such as a carbon nanofiber copper foil, a carbon nanofiber silver foil, a carbon nanofiber aluminum foil, and a carbon nanofiber gold foil, but the carbon nanofiber copper foil has excellent heat dissipation performance, high strength, exceptionally stable chemical properties, low price, and the like, so that the problems of heat dissipation and oxidation of a circuit board can be solved well, and the cost can be saved, and thus the carbon nanofiber copper foil is further preferred.
Example 1
Weighing 245.98g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere, weighing 0.09981mol of p-phenylenediamine and 0.04275mol of 4,4 '-diphenyl ether diamine, and completely dissolving the p-phenylenediamine and the 0.04275mol of 4,4' -diphenyl ether diamine in the flask; 0.01500mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.13509mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃.
After 120min of reaction, heating a water bath to 80 ℃, weighing 0.00528mol of p-phenylenediamine and 0.00225mol of 4,4' -diphenyl ether diamine to be dissolved in 20g N, N-dimethylformamide under the nitrogen atmosphere, adding 40% of the prepared mixed solution by a difference method in a mode of adding more than one times and less than one times, adding 25% of the mixed solution at 30-35 ℃, adding 25% of the mixed solution at 45-50 ℃, adding 20% of the mixed solution at 65-70 ℃, adding 10% of the mixed solution at 75-80 ℃, stirring the rest part of the mixed solution at 80 ℃ for 1h, adding the mixed solution according to the viscosity condition, controlling the PAA apparent viscosity to be about 200000cP, after fully reacting for 240min, adding 1.38% of m-bis (trifluoromethyl) aniline for end capping, cooling to room temperature after fully reacting for 60min, weighing 86.02gN, weighing N-dimethylformamide to gradually dilute the resin viscosity to be about 50000cP, taking 100g of the diluted resin, adding 0.2g of pyridazine and 0.8g of pyridine, stirring at a constant speed for 5min, then quickly defoaming in high vacuum, respectively coating films (the thickness of the film is controlled to be about 20 mu m) on a glass substrate and a carbon nanofiber copper foil by adopting a tape casting method, and removing acetic anhydride and a solvent in an oxygen-free vacuum oven at 250 ℃ after chemical imidization. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
Example 2
Weighing 307.85g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere, weighing 0.08321mol of p-phenylenediamine and 0.08321mol of 4,4 '-diphenyl ether diamine, and completely dissolving the p-phenylenediamine and the 0.08321mol of 4,4' -diphenyl ether diamine in the flask; 0.03502mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.14007mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃. After 120min of reaction, heating a water bath to 80 ℃, weighing 0.00438mol of p-phenylenediamine and 0.00438mol of 4,4' -diphenyl ether diamine to be dissolved in 4g N and N-dimethylformamide under the nitrogen atmosphere, adding 40% of the prepared mixed solution at 30-35 ℃, 25% of the prepared mixed solution at 45-50 ℃, 20% of the prepared mixed solution at 65-70 ℃, 10% of the prepared mixed solution at 75-80 ℃ by a difference method, stirring the rest part of the mixed solution at 80 ℃ for 1h, adding the mixed solution according to the viscosity condition, wherein the stirring speed is 15rad/min, the apparent viscosity of PAA is controlled to be about 200000cP, after fully reacting for 240min, adding 1.26% of blocking agent m-bis (trifluoromethyl) aniline, fully reacting for 60min, cooling to room temperature, weighing 107.57gN, gradually diluting the resin viscosity to 50000cP by N-dimethylformamide, taking 100g of diluted resin, adding 0.2g of pyridazine and 0.8g of pyridine, stirring at a constant speed for 5min, then quickly defoaming in high vacuum, respectively coating films (the thickness of the film is controlled to be about 20 mu m) on a glass substrate and a carbon nanofiber copper foil by adopting a tape casting method, and removing acetic anhydride and a solvent in an oxygen-free vacuum oven at 250 ℃ after chemical imidization. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
Example 3
291.95g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere are weighed, 0.09509mol of p-phenylenediamine and 0.06332mol of 4,4' -diphenyl ether diamine are weighed and completely dissolved in the flask; 0.05003mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.11674mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃. After 120min of reaction, heating a water bath to 80 ℃, weighing 0.00500mol of p-phenylenediamine and 0.00333mol of 4,4' -diphenyl ether diamine to be dissolved in 4g N and N-dimethylformamide under the nitrogen atmosphere, adding 40% of the prepared mixed solution at 30-35 ℃, 25% of the prepared mixed solution at 45-50 ℃, 20% of the prepared mixed solution at 65-70 ℃, 10% of the prepared mixed solution at 75-80 ℃ by a difference method, stirring the rest part of the mixed solution at 80 ℃ for 1h, adding the mixed solution according to the viscosity condition, wherein the stirring rate is 15rad/min, controlling the apparent viscosity of PAA to be about 200000cP, after fully reacting for 240min, adding 0.79% of m-bis (trifluoromethyl) aniline serving as a blocking agent in a molar ratio, fully reacting for 60min, cooling to room temperature, weighing 166.37gN, weighing N-dimethylformamide to gradually dilute the viscosity of the resin to 50000cP, taking 100g of the diluted resin, adding 0.2g of pyridazine and 0.8g of pyridine, stirring at a constant speed for 5min, then quickly defoaming in high vacuum, respectively coating films (the thickness of the film is controlled to be about 20 mu m) on a glass substrate and a carbon nanofiber copper foil by adopting a tape casting method, and removing acetic anhydride and a solvent in an oxygen-free vacuum oven at 250 ℃ after chemical imidization. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
Example 4
Weighing 305.89g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere, weighing 0.06342mol of p-phenylenediamine and 0.09500mol of 4,4 '-diphenyl ether diamine, and completely dissolving the p-phenylenediamine and the 0.09500mol of 4,4' -diphenyl ether diamine in the flask; 0.05003mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.11674mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃. After 120min of reaction, heating a water bath to 80 ℃, weighing 0.00334mol of p-phenylenediamine and 0.00500mol of 4,4' -diphenyl ether diamine to be dissolved in 4g N and N-dimethylformamide under the nitrogen atmosphere, adding 40% of the prepared mixed solution at 30-35 ℃, 25% of the prepared mixed solution at 45-50 ℃, 20% of the prepared mixed solution at 65-70 ℃, 10% of the prepared mixed solution at 75-80 ℃ by a difference method, stirring the rest part of the mixed solution at 80 ℃ for 1h, adding the mixed solution according to the viscosity condition, wherein the stirring rate is 15rad/min, controlling the apparent viscosity of PAA to be about 200000cP, after fully reacting for 240min, adding 1.34% of blocking agent m-bis (trifluoromethyl) aniline, fully reacting for 60min, cooling to room temperature, weighing 106.95gN, weighing N-dimethylformamide to gradually dilute the resin viscosity to 50000cP, taking 100g of the diluted resin, adding 0.2g of pyridazine and 0.8g of pyridine, stirring at a constant speed for 5min, then quickly defoaming in high vacuum, respectively coating films (the thickness of the film is controlled to be about 20 mu m) on a glass substrate and a carbon nanofiber copper foil by adopting a tape casting method, and removing acetic anhydride and a solvent in an oxygen-free vacuum oven at 250 ℃ after chemical imidization. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
Example 5
Weighing 223.04g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere, weighing 0.07134mol of p-phenylenediamine and 0.04750mol of 4,4 '-diphenyl ether diamine, and completely dissolving the p-phenylenediamine and the 0.04750mol of 4,4' -diphenyl ether diamine in the flask; 0.05003mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.07505mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃. After 120min of reaction, heating a water bath to 80 ℃, weighing 0.00375mol of p-phenylenediamine and 0.00250mol of 4,4 '-diphenyl ether diamine to be dissolved in 4g N, N-dimethylformamide under the nitrogen atmosphere, adding 40% of the prepared mixed solution by a difference method in a mode of adding more than one of p-phenylenediamine and 0.00250mol of 4,4' -diphenyl ether diamine for a plurality of times, adding 25% of the mixed solution at 30-35 ℃, adding 25% of the mixed solution at 45-50 ℃, adding 20% of the mixed solution at 65-70 ℃, adding 10% of the mixed solution at 75-80 ℃, stirring the rest part of the mixed solution at 80 ℃ for 1h, adding the mixed solution according to the viscosity condition, controlling the apparent viscosity of PAA to be about 200000cP, after fully reacting for 240min, adding 0.98% of m-bis (trifluoromethyl) as a blocking agent in a molar ratio, fully reacting for 60min, cooling to room temperature, weighing 127.25gN, gradually diluting the resin viscosity to 50000cP by N-dimethylformamide, taking 100g of the diluted resin, adding 0.2g of pyridazine and 0.8g of pyridine, stirring at a constant speed for 5min, then quickly defoaming in high vacuum, respectively coating films (the thickness of the film is controlled to be about 20 mu m) on a glass substrate and a carbon nanofiber copper foil by adopting a tape casting method, and removing acetic anhydride and a solvent in an oxygen-free vacuum oven at 250 ℃ after chemical imidization. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
Comparative example 1
Weighing 245.98g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere, weighing 0.09981mol of p-phenylenediamine and 0.04275mol of 4,4 '-diphenyl ether diamine, and completely dissolving the p-phenylenediamine and the 0.04275mol of 4,4' -diphenyl ether diamine in the flask; 0.01500mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.13509mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃. After 120min of reaction, 0.00528mol of p-phenylenediamine and 0.00225mol of 4,4' -diphenyl ether diamine are weighed and dissolved in 20g N N-dimethylformamide under the nitrogen atmosphere, the prepared mixed solution is added into a flask, the addition amount is controlled according to experience, the viscosity is controlled to be about 200000cP, after 240min of reaction, 86.02g of N, N-dimethylformamide is weighed to gradually dilute the viscosity of the resin to about 50000cP, 100g of diluted resin is taken for high-vacuum rapid defoaming, a glass substrate is coated with a film by a tape casting method (the thickness of the film is controlled to be about 20 micrometers), and the film is formed by an oxygen-free vacuum oven at 500 ℃. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
Comparative example 2
Weighing 307.85g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere, weighing 0.08321mol of p-phenylenediamine and 0.08321mol of 4,4 '-diphenyl ether diamine, and completely dissolving the p-phenylenediamine and the 0.08321mol of 4,4' -diphenyl ether diamine in the flask; 0.03502mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.14007mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃. After 120min of reaction, 0.00438mol of p-phenylenediamine and 0.00438mol of 4,4' -diphenyl ether diamine are weighed and dissolved in 4g N and N-dimethylformamide under the nitrogen atmosphere, the prepared mixed solution is added into a flask, the addition amount is controlled according to experience, the viscosity is controlled to be about 200000cP, after 240min of reaction, 86.02g of N and N-dimethylformamide are weighed to gradually dilute the viscosity of the resin to about 50000cP, 100g of diluted resin is taken for high-vacuum rapid defoaming, a film is coated on a glass substrate by a tape casting method (the thickness of the film is controlled to be about 20 micrometers), and the film is formed by imidization in an oxygen-free vacuum oven at 500 ℃. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
Comparative example 3
291.95g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere are weighed, 0.09509mol of p-phenylenediamine and 0.06332mol of 4,4' -diphenyl ether diamine are weighed and completely dissolved in the flask; 0.05003mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.11674mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃. After 120min of reaction, 0.00500mol of p-phenylenediamine and 0.00333mol of 4,4' -diphenyl ether diamine are weighed and dissolved in 4g N and N-dimethylformamide under the nitrogen atmosphere, the prepared mixed solution is added into a flask, the addition amount is controlled according to experience, the viscosity is controlled to be about 200000cP, after 240min of reaction, 86.02g of N and N-dimethylformamide are weighed to gradually dilute the viscosity of the resin to about 50000cP, 100g of diluted resin is taken for high-vacuum rapid defoaming, a film is coated on a glass substrate by a tape casting method (the thickness of the film is controlled to be about 20 micrometers), and the film is formed by imidization in an oxygen-free vacuum oven at 500 ℃. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
Comparative example 4
Weighing 305.89g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere, weighing 0.06342mol of p-phenylenediamine and 0.09500mol of 4,4 '-diphenyl ether diamine, and completely dissolving the p-phenylenediamine and the 0.09500mol of 4,4' -diphenyl ether diamine in the flask; 0.05003mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.11674mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃. After 120min of reaction, 0.00334mol of p-phenylenediamine and 0.00500mol of 4,4' -diphenyl ether diamine are weighed and dissolved in 4g N and N-dimethylformamide under the nitrogen atmosphere, the prepared mixed solution is added into a flask, the addition amount is controlled according to experience, the viscosity is controlled to be about 200000cP, after 240min of reaction, 86.02g of N and N-dimethylformamide are weighed to gradually dilute the viscosity of the resin to about 50000cP, 100g of diluted resin is taken for high-vacuum rapid defoaming, a film is coated on a glass substrate by a tape casting method (the thickness of the film is controlled to be about 20 micrometers), and the film is formed by imidization in an oxygen-free vacuum oven at 500 ℃. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
Comparative example 5
Weighing 223.04g N, N-dimethylformamide (analytically pure) and a flask in a high-purity nitrogen atmosphere, weighing 0.07134mol of p-phenylenediamine and 0.04750mol of 4,4 '-diphenyl ether diamine, and completely dissolving the p-phenylenediamine and the 0.04750mol of 4,4' -diphenyl ether diamine in the flask; 0.05003mol of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.07505mol of pyromellitic dianhydride are weighed and mixed to be added into a flask, and the reaction temperature is controlled to be about 0 ℃. After 120min of reaction, 0.00375mol of p-phenylenediamine and 0.00250mol of 4,4' -diphenyl ether diamine are weighed and dissolved in 4g N N-dimethylformamide under the nitrogen atmosphere, the prepared mixed solution is added into a flask, the addition amount is controlled according to experience, the viscosity is controlled to be about 200000cP, after 240min of reaction, 86.02g of N, N-dimethylformamide is weighed to gradually dilute the viscosity of the resin to be about 50000cP, 100g of diluted resin is taken for high-vacuum rapid defoaming, a glass substrate is coated with a film by a tape casting method (the thickness of the film is controlled to be about 20 micrometers), and the film is formed by an oxygen-free vacuum oven at 500 ℃. And testing the tensile strength, the thermal expansion coefficient, the water absorption, the dielectric constant and the edge curl degree of the film. The residual resin is stored in a sealing way at normal temperature and normal pressure, and the viscosity is detected after one month.
As can be seen from the above table, comparative examples 1 to 5, without adding an end-capping agent and without other control conditions, had a difficult initial apparent viscosity control, a large viscosity span, extreme instability, and poor reproducibility. The viscosity of the resin is reduced obviously after the polyimide resin solution prepared in the examples 1 to 5 is stored for one month at normal temperature, while the addition ratio of the diamine is controlled to be 98.6 to 99.3 percent, the addition ratio of the end capping agent is controlled to be 1.4 to 0.7 percent, the initial apparent viscosity can be controlled to be about 300000cP, the viscosity of the resin is not changed obviously after the polyimide resin solution is stored for one month at normal temperature, and the viscosity stability is excellent.
Meanwhile, the films prepared in the comparative examples 1 to 5 have low tensile strength, large difference between the thermal expansion coefficient and the copper foil, high water absorption rate and large dielectric constant, and the films have obvious curling phenomena, thus the industrial production requirements cannot be met. When the polyimide resin solution prepared in the embodiments 1 to 5 is used for preparing a film alone, the tensile strength is greater than 120MPa, the thermal expansion coefficient is close to that of a copper foil (18 x 10-6k-1), the water absorption is low and is less than 2%, the dielectric constant is less than 3, the film does not generate a curling phenomenon, and all the performances are good, when the graphene copper foil is used as a base film, the tensile strength of the prepared film is greatly increased by more than 320MPa, the thermal expansion coefficient is close to that of the copper foil (18 x 10-6k-1), the water absorption is low and is less than 2%, the dielectric constant is less than 3, and the extremely small curling phenomenon is generated on the outer side of the film, so that all the performances are good, and the requirements of microelectronic products are met.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of polyimide resin is characterized by comprising the following steps:
s1, dissolving a first batch of poly-diamine in a solvent under an inert gas atmosphere, adding 105-110% of poly-dianhydride of the total mole amount of the first batch of poly-diamine in a low-temperature environment of 30 ℃ or below for polymerization to form a resin solution, and controlling the viscosity of the resin solution at 50000-70000 cps;
s2, monitoring the viscosity of the resin solution and gradually raising the temperature within 30-80 ℃, and gradually adding the second poly-diamine in batches of more poly-diamine and less poly-diamine until the viscosity of the resin solution is 180000-;
s3, adding a fluorine-containing end-capping reagent, mixing, and defoaming in high vacuum to obtain a polyimide resin solution;
wherein the low-temperature environment in the step S1 is-20-30 ℃;
in the step S2, the adding amount of the second poly-diamine is 5-10% of the total mole amount of the first poly-diamine, and the adding amount in batches is specifically: adding 40 percent of the molar total amount of the second poly-diamine in a temperature gradient of 30-35 ℃, 25 percent of the molar total amount of the second poly-diamine in a temperature gradient of 45-50 ℃, 20 percent of the molar total amount of the second poly-diamine in a temperature gradient of 65-70 ℃,10 percent of the molar total amount of the second poly-diamine in a temperature gradient of 75-80 ℃, continuously stirring and monitoring the viscosity of the resin solution, stopping feeding if the viscosity of the resin is stabilized at 180000-200000cps, and otherwise, continuously adding the rest of the second poly-diamine until the viscosity of the resin is stabilized at 180000-200000 cps;
in the step S3, the fluorine-containing end-capping agent is a fluorine-containing monoamine aromatic organic substance, and reacts with the end-chain anhydride structure of the polyimide resin solution to perform end-chain end capping;
based on the molar total amount of the polybasic dianhydride, the adding proportion of the polybasic diamine is controlled to be 98.6-99.3%, the adding proportion of the end capping agent is controlled to be 1.4-0.7%, and the molar amount of the fluorine-containing end capping agent plus the molar amount of the first lot of the polybasic diamine and the molar amount of the second lot of the polybasic diamine is equal to the molar amount of the polybasic dianhydride.
2. The method for producing a polyimide resin according to claim 1, wherein the polyvalent diamine comprises p-phenylenediamine and its ring-fluorinated compound, benzidine and its ring-fluorinated compound, 4 '-oxydianiline, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (2-aminophenoxy) benzene, 4' -bis (3-aminophenoxy) biphenyl, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (5-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (2-aminophenoxy) phenyl) sulfone, bis (4-aminophenoxy) phenyl) sulfone, bis (3-aminophenoxy) phenyl) sulfone, or bis (3-aminophenoxy) phenyl) sulfone, 4,4' -diaminodiphenylethane, 4' -diaminodiphenylisopropane, 4' -diaminophenylsulfide, 3' -diaminodiphenylsulfone, 4' -diaminodiphenylsulfone, 3' -oxydianiline, 3,4' -oxydianiline, 2,4' -oxydianiline, 4' -diaminodiphenyldiethylsilane, 4' -diaminodiphenylsilane, 4' -diaminodiphenylethylphosphine oxide, 4' -diaminodiphenyl-N-methylamine, 4' -diaminodiphenyl-N-aniline, 1, 3-diaminobenzene, 1, 2-diaminobenzene, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 2,4' -diaminodiphenylisopropyl-phenyl-4, 4' -diaminodiphenylisopropyl-4, 4' -oxydianiline, 4' -diaminodiphenylethyl-N-aniline, 1, 3-diaminobenzene, 1, 2' -diaminobenzene, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 2,4' -diaminodiphenyl-methyl-o-phenyl ] propane, 4' -diaminodiphenyl-ethyl-phenyl-1, 4' -diaminodiphenyl-phenyl-ethyl-phenyl-1, 4' -diaminodiphenyl-phenyl-4, 4' -diaminodiphenyl, 4' -diaminodiphenyl, 4' -diaminodiphenyl, 4' -diaminodiphenyl, 4' -diaminodiphenyl, 4, any two or more of 2,2' -bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane and 4,4' -diamino-2, 2' -bistrifluoromethylbiphenyl.
3. The method for producing a polyimide resin according to claim 1, wherein the polybasic dianhydride comprises pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) ethane dianhydride, hydroxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, ethylenebis (trimellitic monoester anhydride), bisphenol A bis (trimellitic monoester anhydride), 4,4 '-oxydiphthalic anhydride, 4,4' -thiobisphthalic anhydride, bisphenol A bis (trimellitic monoester anhydride), or a mixture thereof, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride.
4. The method for preparing a polyimide resin according to claim 1, the fluorine-containing end-capping agent comprises any one of m-bis (trifluoromethyl) aniline, 4- (4' -fluorophenyl) benzonitrile, p-trifluoromethylaniline, 2, 6-difluoro-3-methylaniline, cyanoacetyl-p-trifluoromethylaniline, 4-methyl-2- (trifluoromethyl) aniline, 3-fluoro-2- (trifluoromethyl) aniline, 5-fluoro-2-trifluoromethylaniline, 4-fluoro-2-nitro-5- (trifluoromethyl) -aniline, trifluoroaniline, N-ethyl-2, 3, 5-trifluoroaniline, 2,3, 4-trifluorophenylacetamide and 2,3, 4-trifluoro-6-nitroaniline.
5. The method of preparing a polyimide resin according to claim 1, wherein the solvent includes any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, cyclohexane, methylcyclohexane, tetrahydrofuran, isohexane, N-heptane, dichloromethane, trichloroethylene, carbon tetrachloride, epichlorohydrin, methyl methacrylate, and dimethylsulfoxide.
6. A film, characterized in that the preparation method comprises: the polyimide resin according to any one of claims 1 to 5 is selected, and a catalyst and a dehydrating agent are sequentially added to the polyimide resin and then coated on at least one side of a base film.
7. The film of claim 6, wherein the catalyst comprises any one of pyridazine, pyrimidine, arsenopyridine, and 1, 10-phenanthroline.
8. The film of claim 6, wherein the mass ratio of the catalyst to the polyimide resin solution is from 1:95 to 105.
9. The film of claim 6, wherein the base film comprises any one of a carbon nanofiber copper foil, a carbon nanofiber silver foil, a carbon nanofiber aluminum foil, and a carbon nanofiber gold foil.
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| CN115260492B (en) * | 2022-06-14 | 2024-04-26 | 安徽国风新材料股份有限公司 | Preparation method of polyimide film with low thermal expansion coefficient |
| CN115354410B (en) * | 2022-10-19 | 2023-02-03 | 中国人民解放军空军特色医学中心 | Polyimide fiber, and preparation method and application thereof |
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| US6548179B2 (en) * | 2000-08-24 | 2003-04-15 | Dupont-Toray Co., Ltd. | Polyimide film, method of manufacture, and metal interconnect board with polyimide film substrate |
| US7041773B2 (en) * | 2003-09-26 | 2006-05-09 | General Electric Company | Polyimide sulfones, method and articles made therefrom |
| CN1978487A (en) * | 2005-12-02 | 2007-06-13 | 中国科学院化学研究所 | 4-styryl-3-Trifluoro methyl benzeneamine and its polyimide resin, and its preparing method |
| CN102766260B (en) * | 2012-07-18 | 2014-08-13 | 杭州塑盟特科技有限公司 | Method for preparing polyimide in supercritical carbon dioxide |
| CN104193993A (en) * | 2014-08-13 | 2014-12-10 | 南京理工大学 | Polyamide acid copolymer and polyimide film prepared from polyamide acid copolymer |
| CN105153445B (en) * | 2015-09-25 | 2018-02-02 | 中国科学院化学研究所 | A kind of method by reactive end-capped with phthalic anhydride resin-made for Kapton |
| CN106810692B (en) * | 2015-12-02 | 2020-02-11 | 株洲时代新材料科技股份有限公司 | Preparation method of polyamic acid solution and polyimide film |
| CN106750428B (en) * | 2016-11-30 | 2017-11-17 | 哈尔滨理工大学 | A kind of method that high corona-resistant film is prepared using chemical mixed nanometer technology |
| KR101912737B1 (en) * | 2017-05-23 | 2018-10-30 | 주식회사 대림코퍼레이션 | Method of manufacturing for polyamic acid resin having easily laser Ablation and high heat resistant and polyimide film using the same |
| CN107266688B (en) * | 2017-07-27 | 2020-06-09 | 河北工业大学 | Preparation method of sulfonated polyarylene sulfide sulfone/polyimide block type proton exchange membrane material |
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| CN109337100B (en) * | 2018-07-05 | 2021-04-09 | 安徽国风塑业股份有限公司 | Preparation method of high-thermal-conductivity condensed ring polyimide film |
| WO2020022410A1 (en) * | 2018-07-26 | 2020-01-30 | 日産化学株式会社 | Composition for forming protective film for transparent conductive film |
| JP6503508B2 (en) * | 2018-08-03 | 2019-04-17 | Ｊｘｔｇエネルギー株式会社 | Tetracarboxylic acid dianhydride, polyimide precursor resin, polyimide, polyimide precursor resin solution, polyimide solution and polyimide film |
| CN109337101A (en) * | 2018-08-06 | 2019-02-15 | 安徽国风塑业股份有限公司 | A kind of preparation method of Kapton |
| CN111961236B (en) * | 2019-05-20 | 2023-10-20 | 北京化工大学 | Low-dielectric polyimide film and preparation method and application thereof |
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| CN111635546B (en) * | 2020-06-24 | 2022-04-29 | 东莞东阳光科研发有限公司 | Preparation method of fluorine-containing polymer/polyimide composite film |
| CN112029099B (en) * | 2020-09-04 | 2022-10-04 | 吉林奥来德光电材料股份有限公司 | Preparation method of polyamide acid solution and polyimide film |
| CN113201136B (en) * | 2021-04-29 | 2022-01-07 | 上海瑞暨新材料科技有限公司 | Preparation method of polyimide resin and film thereof |
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