CN113549234B - Production process of hydrophobic polyimide film - Google Patents

Production process of hydrophobic polyimide film Download PDF

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CN113549234B
CN113549234B CN202110831433.1A CN202110831433A CN113549234B CN 113549234 B CN113549234 B CN 113549234B CN 202110831433 A CN202110831433 A CN 202110831433A CN 113549234 B CN113549234 B CN 113549234B
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polyimide film
flask
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diamine monomer
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CN113549234A (en
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邹伟民
刘承伟
陆妮
徐海
徐寅
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Jiangsu Transimage Technology Co Ltd
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Abstract

The invention discloses a production process of a hydrophobic polyimide film, which belongs to the technical field of preparation of modified polyimide films, and comprises the following steps: preparing a diamine monomer A; diamine monomer A reacts with dianhydride monomer to prepare polyamic acid solution; imidizing to obtain a polyimide film; the diamine monomer A is prepared, so that the prepared polyimide has a C-F bond and a siloxane chain with excellent hydrophobic performance, the middle of the diamine monomer A is provided with an ester group, the structural symmetry degree of the diamine monomer A is higher, a polymer can locally form microcrystals, due to the existence of the local microcrystals, water molecules diffuse and are blocked in the polymer, when the water molecules encounter the local microcrystals of the high molecular chain, the inner high molecular chain segments of a crystalline structure are tightly piled up, so that the water molecules cannot permeate and diffuse, the progress of the water molecules is blocked finally, and the hydrophobic performance of the film is further improved.

Description

Production process of hydrophobic polyimide film
Technical Field
The invention relates to the technical field of preparation of modified polyimide films, in particular to a production process of a hydrophobic polyimide film.
Background
Polyimide is one of organic high molecular materials with optimal comprehensive performance, and has excellent performances of high strength, low dielectric, high modulus, high temperature resistance, radiation resistance and the like, and has been paid attention to and application. Among aromatic heterocyclic polymer materials, aromatic polyimide materials are representative of high-performance polymer materials due to the characteristics of excellent heat resistance stability, radiation resistance, excellent mechanical properties, lower dielectric properties, processability and the like, and are widely applied to high-tech fields such as aviation, aerospace, microelectronics and the like.
Although the polyimide has higher chemical stability, the polyimide known at present still can absorb certain moisture, so that the problems of metal corrosion, package rupture, film and metal adhesion failure, dielectric property reduction and the like are caused, and the dielectric property is obviously reduced due to the water absorption of the polyimide, so that the polyimide is limited to be further applied to the field of rapidly-developed electronic products.
Disclosure of Invention
The invention aims to provide a production process of a hydrophobic polyimide film, which is used for solving the technical problems that the existing polyimide film has certain water absorption and the application range of the existing polyimide film is limited.
The aim of the invention can be achieved by the following technical scheme:
a production process of a hydrophobic polyimide film comprises the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, reacting for 4-5 hours at the temperature of 115-120 ℃, after the reaction, cooling the reaction product to 70 ℃, transferring into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, standing for 30min for layering after oscillating, adding an organic phase into the flask, distilling under reduced pressure to remove toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid to the p-methylphenol to the p-sulfobenzoic acid to the toluene is 0.05mol:0.05mol:1.8g:45mL;
the reaction process is as follows:
Figure BDA0003175707060000021
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and carrying out reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3; the dosage mole ratio of the intermediate 1 to the potassium permanganate is 1:1, the dosage ratio of the intermediate 2 to DMF to thionyl chloride is 1mol:0.5mL:2.1mol;
the reaction process is as follows:
Figure BDA0003175707060000022
step S3: adding 3, 5-dihydroxybenzoic acid and DMF into a flask, then adding aminopropyl triethoxysilane, then adding a catalyst, and stirring at 30 ℃ for reaction for 2 hours to prepare an intermediate 4; the dosage ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane and the catalyst is 0.1mol:100mL:0.11mol:0.5g of catalyst, wherein the catalyst is EDCI/HOBt with the mol ratio of 1:1;
the reaction process is as follows:
Figure BDA0003175707060000031
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reaction for 3 hours to obtain an intermediate 5; the dosage ratio of the intermediate 4, the 2-chloro-5-nitrobenzotrifluoride to the toluene is 2mmol:2mmol:10mL;
the reaction process is as follows:
Figure BDA0003175707060000032
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring at the temperature of 0-5 ℃ for reaction for 3 hours, and obtaining an intermediate 6 after the reaction is finished; the dosage ratio of the intermediate 3 to the intermediate 5 to the tetrahydrofuran to the pyridine is 1mmol:1mmol:10mL:1mmol;
the reaction process is as follows:
Figure BDA0003175707060000033
step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, then reacting for 30-32h at 38 ℃, removing the catalyst and the solvent after the reaction is finished, and recrystallizing by using absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10% Pd/C catalyst and the 1, 4-dioxane is 0.03mol:1.3g:300mL;
the reaction process is as follows:
Figure BDA0003175707060000041
step S7: adding diamine monomer A and DMF into a flask, then adding 3,3', 4' -benzophenone tetracarboxylic dianhydride, reacting for 24 hours at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, drying in vacuum at the temperature of 60 ℃ to remove a solvent, then introducing nitrogen, heating to 140-150 ℃, and keeping for 1 hour to obtain a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3', 4' -benzophenone tetracarboxylic dianhydride is as follows: 1mmol:5mL:1mmol;
the reaction process is as follows:
Figure BDA0003175707060000042
the invention provides a production process of a hydrophobic polyimide film. Compared with the prior art, the method has the following beneficial effects: the invention prepares a polyimide film, firstly prepares a diamine monomer A, then reacts diamine monomer A and dianhydride monomer 3,3', 4' -benzophenone tetracarboxylic dianhydride to prepare polyamide acid solution, then imidizes to prepare polyimide film, wherein diamine monomer A firstly reacts with p-methyl phenol by p-methylbenzoic acid to prepare intermediate 1, then oxidizes methyl at two ends of intermediate 1 to form carboxyl, then acylates to convert carboxyl into acyl chloride, then prepares intermediate 3, then reacts with amino of aminopropyl triethoxy silane and carboxyl of 3, 5-dihydroxybenzoic acid to prepare intermediate 4, then reacts with active chlorine of 2-chloro-5-nitrobenzotrifluoride to prepare intermediate 5, then reacts with acyl chloride at two ends of intermediate 5 to prepare intermediate 6, converts nitro of intermediate 6 into amino under the action of catalyst to prepare diamine monomer A, the two ends of diamine monomer A are provided with amino groups to be converted into acyl chloride groups, and the amino groups can be adsorbed with water molecules of water molecules, and the molecular structure can not be absorbed by partial crystalline structure of the microcrystalline is reduced, and the molecular structure is blocked by water molecules, and the molecular structure is high, the molecular structure is blocked by the molecular structure is high, and the molecular structure is blocked by the microcrystalline structure of the microcrystalline molecule, at the same time, the molecular structure is blocked by the molecular structure is high, and the molecular structure is blocked by the molecular structure is formed, the introduction of siloxane chain can reduce the glass transition temperature of the polymer, provide good thermal stability, ultraviolet stability and tolerance in severe environment, and simultaneously reduce the water absorbability of the polymer, in addition, diamine monomer A also has high electronegativity C-F bond, fluorine atom is difficult to be used as electron donor to form hydrogen bond with hydrogen in water molecule, and further improve the hydrophobicity of the prepared polyimide.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing a diamine monomer A, wherein the diamine monomer A is prepared by the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, reacting for 4 hours at the temperature of 115 ℃, after the reaction, cooling the reaction product to 70 ℃, transferring into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, standing for 30min for layering after shaking, adding an organic phase into the flask, distilling under reduced pressure to remove toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid to the p-methylphenol to the p-sulfobenzoic acid to the toluene is 0.05mol:0.05mol:1.8g:45mL;
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and carrying out reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3; the dosage mole ratio of the intermediate 1 to the potassium permanganate is 1:1, the dosage ratio of the intermediate 2 to DMF to thionyl chloride is 1mol:0.5mL:2.1mol;
step S3: adding 3, 5-dihydroxybenzoic acid and DMF into a flask, then adding aminopropyl triethoxysilane, then adding a catalyst, and stirring at 30 ℃ for reaction for 2 hours to prepare an intermediate 4; the dosage ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane and the catalyst is 0.1mol:100mL:0.11mol:0.5g of catalyst, wherein the catalyst is EDCI/HOBt with the mol ratio of 1:1;
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reaction for 3 hours to obtain an intermediate 5; the dosage ratio of the intermediate 4, the 2-chloro-5-nitrobenzotrifluoride to the toluene is 2mmol:2mmol:10mL;
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring at the temperature of 0 ℃ for reaction for 3 hours, and obtaining an intermediate 6 after the reaction is finished; the dosage ratio of the intermediate 3 to the intermediate 5 to the tetrahydrofuran to the pyridine is 1mmol:1mmol:10mL:1mmol;
step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, then reacting for 30 hours at the temperature of 38 ℃, removing the catalyst and the solvent after the reaction is finished, and recrystallizing by using absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10% Pd/C catalyst and the 1, 4-dioxane is 0.03mol:1.3g:300mL.
Example 2
Preparing a diamine monomer A, wherein the diamine monomer A is prepared by the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, reacting for 4.5 hours at the temperature of 117.5 ℃, after the reaction, cooling the reaction product to 70 ℃, transferring into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, standing for 30min for layering after oscillating, adding an organic phase into the flask, distilling under reduced pressure to remove toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid to the p-methylphenol to the p-sulfobenzoic acid to the toluene is 0.05mol:0.05mol:1.8g:45mL;
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and carrying out reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3; the dosage mole ratio of the intermediate 1 to the potassium permanganate is 1:1, the dosage ratio of the intermediate 2 to DMF to thionyl chloride is 1mol:0.5mL:2.1mol;
step S3: adding 3, 5-dihydroxybenzoic acid and DMF into a flask, then adding aminopropyl triethoxysilane, then adding a catalyst, and stirring at 30 ℃ for reaction for 2 hours to prepare an intermediate 4; the dosage ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane and the catalyst is 0.1mol:100mL:0.11mol:0.5g of catalyst, wherein the catalyst is EDCI/HOBt with the mol ratio of 1:1;
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reaction for 3 hours to obtain an intermediate 5; the dosage ratio of the intermediate 4, the 2-chloro-5-nitrobenzotrifluoride to the toluene is 2mmol:2mmol:10mL;
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring at the temperature of 3 ℃ for reaction for 3 hours, and obtaining an intermediate 6 after the reaction is finished; the dosage ratio of the intermediate 3 to the intermediate 5 to the tetrahydrofuran to the pyridine is 1mmol:1mmol:10mL:1mmol;
step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, then reacting for 31 hours at 38 ℃, removing the catalyst and the solvent after the reaction is finished, and recrystallizing by using absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10% Pd/C catalyst and the 1, 4-dioxane is 0.03mol:1.3g:300mL.
Example 3
Preparing a diamine monomer A, wherein the diamine monomer A is prepared by the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, reacting for 5 hours at the temperature of 120 ℃, after the reaction, cooling the reaction product to 70 ℃, transferring into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, standing for 30min for layering after shaking, adding an organic phase into the flask, distilling under reduced pressure to remove toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid to the p-methylphenol to the p-sulfobenzoic acid to the toluene is 0.05mol:0.05mol:1.8g:45mL;
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and carrying out reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3; the dosage mole ratio of the intermediate 1 to the potassium permanganate is 1:1, the dosage ratio of the intermediate 2 to DMF to thionyl chloride is 1mol:0.5mL:2.1mol;
step S3: adding 3, 5-dihydroxybenzoic acid and DMF into a flask, then adding aminopropyl triethoxysilane, then adding a catalyst, and stirring at 30 ℃ for reaction for 2 hours to prepare an intermediate 4; the dosage ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane and the catalyst is 0.1mol:100mL:0.11mol:0.5g of catalyst, wherein the catalyst is EDCI/HOBt with the mol ratio of 1:1;
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reaction for 3 hours to obtain an intermediate 5; the dosage ratio of the intermediate 4, the 2-chloro-5-nitrobenzotrifluoride to the toluene is 2mmol:2mmol:10mL;
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring at the temperature of 5 ℃ for reaction for 3 hours, and obtaining an intermediate 6 after the reaction is finished; the dosage ratio of the intermediate 3 to the intermediate 5 to the tetrahydrofuran to the pyridine is 1mmol:1mmol:10mL:1mmol;
step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, then reacting for 32 hours at the temperature of 38 ℃, removing the catalyst and the solvent after the reaction is finished, and recrystallizing by using absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10% Pd/C catalyst and the 1, 4-dioxane is 0.03mol:1.3g:300mL.
Example 4
Preparing a hydrophobic polyimide film, wherein the hydrophobic polyimide film is specifically prepared by the following steps:
adding diamine monomer A prepared in example 2 and DMF into a flask, then adding 3,3', 4' -benzophenone tetracarboxylic dianhydride, reacting for 24 hours at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, drying in vacuum at the temperature of 60 ℃ to remove the solvent, then introducing nitrogen and heating to 140 ℃, and keeping for 1 hour to prepare a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3', 4' -benzophenone tetracarboxylic dianhydride is as follows: 1mmol:5mL:1mmol.
Example 5
Preparing a hydrophobic polyimide film, wherein the hydrophobic polyimide film is specifically prepared by the following steps:
adding diamine monomer A prepared in example 2 and DMF into a flask, then adding 3,3', 4' -benzophenone tetracarboxylic dianhydride, reacting for 24 hours at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, drying in vacuum at the temperature of 60 ℃ to remove the solvent, then introducing nitrogen and heating to 145 ℃, and keeping for 1 hour to prepare a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3', 4' -benzophenone tetracarboxylic dianhydride is as follows: 1mmol:5mL:1mmol.
Example 6
Preparing a hydrophobic polyimide film, wherein the hydrophobic polyimide film is specifically prepared by the following steps:
adding diamine monomer A prepared in example 2 and DMF into a flask, then adding 3,3', 4' -benzophenone tetracarboxylic dianhydride, reacting for 24 hours at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, drying in vacuum at the temperature of 60 ℃ to remove the solvent, then introducing nitrogen and heating to 150 ℃, and keeping for 1 hour to prepare a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3', 4' -benzophenone tetracarboxylic dianhydride is as follows: 1mmol:5mL:1mmol.
Comparative example 1: 4,4' -diaminodiphenyl sulfone was used as diamine monomer compared to example 5.
Comparative example 2: compared to example 5, hexafluoromethyl biphenyl diamine was used as diamine monomer.
Comparative example 3: in contrast to example 5, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane was used as diamine monomer.
Performance tests were conducted on examples 4-6 and comparative examples 1-3, and the results obtained are shown in the following table:
the tensile strength and elongation at break were measured with reference to GB13022-91, and the hydrophobicity was judged by measuring the contact angle, and the results are shown in the following table:
tensile Strength (MPa) Elongation at break (%) Contact angle
Example 4 181 49 153°
Example 5 180 49 154°
Example 6 182 50 151°
Comparative example 1 126 40 45°
Comparative example 2 131 42 70°
Comparative example 3 132 43 82°
From the above table, it is clear that examples 4-6 have good mechanical properties and hydrophobic properties.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1. The production process of the hydrophobic polyimide film is characterized by comprising the following steps of:
adding diamine monomer A and DMF into a flask, then adding 3,3', 4' -benzophenone tetracarboxylic dianhydride, reacting for 24 hours at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, drying in vacuum at the temperature of 60 ℃ to remove a solvent, then introducing nitrogen, heating to 140-150 ℃, and keeping for 1 hour to obtain a polyimide film;
diamine monomer A is prepared by the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, and reacting for 4-5h at 115-120 ℃ to prepare an intermediate 1;
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and carrying out reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3;
step S3: adding 3, 5-dihydroxybenzoic acid and DMF into a flask, then adding aminopropyl triethoxysilane, then adding a catalyst, and stirring at 30 ℃ for reaction for 2 hours to prepare an intermediate 4;
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reaction for 3 hours to obtain an intermediate 5;
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring at the temperature of 0-5 ℃ for reaction for 3 hours, and obtaining an intermediate 6 after the reaction is finished;
step S6: adding the intermediate 6, 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, then reacting for 30-32h at 38 ℃, removing the catalyst and the solvent after the reaction is finished, and recrystallizing by using absolute ethyl alcohol to obtain the diamine monomer A.
2. The process for producing a hydrophobic polyimide film according to claim 1, wherein the diamine monomer A, DMF, 3', 4' -benzophenone tetracarboxylic dianhydride is used in an amount ratio of: 1mmol:5mL:1mmol.
3. The process for producing a hydrophobic polyimide film according to claim 1, wherein the dosage ratio of p-methylbenzoic acid, p-methylphenol, p-toluenesulfonic acid and toluene in step S1 is 0.05mol:0.05mol:1.8g:45mL.
4. The process for producing a hydrophobic polyimide film according to claim 1, wherein the molar ratio of the intermediate 1 to the potassium permanganate in step S2 is 1:1, the dosage ratio of the intermediate 2 to DMF to thionyl chloride is 1mol:0.5mL:2.1mol.
5. The process for producing a hydrophobic polyimide film according to claim 1, wherein the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane, and catalyst in step S3 are used in an amount ratio of 0.1mol:100mL:0.11mol:0.5g of catalyst, the molar ratio of EDCI/HOBt is 1:1.
6. The process for producing a hydrophobic polyimide film according to claim 1, wherein the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene in the step S4 are used in an amount ratio of 2mmol:2mmol:10mL.
7. The process for producing a hydrophobic polyimide film according to claim 1, wherein the ratio of the amounts of intermediate 3, intermediate 5, tetrahydrofuran and pyridine in step S5 is 1mmol:1mmol:10mL:1mmol.
8. The process for producing a hydrophobic polyimide film according to claim 1, wherein the intermediate 6, 10% pd/C catalyst, 1, 4-dioxane are used in the step S6 in an amount ratio of 0.03mol:1.3g:300mL.
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CN108102094A (en) * 2017-12-24 2018-06-01 桂林理工大学 The method that Kapton is prepared using hexafluorodianhydride (6FDA)
WO2020175838A1 (en) * 2019-02-28 2020-09-03 주식회사 엘지화학 Diamine compound, and polyimide precursor and polyimide film using same

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US5340888A (en) * 1988-12-22 1994-08-23 Borden Inc. Phenolic resin composition
CN108017786A (en) * 2017-12-24 2018-05-11 桂林理工大学 The method that Kapton is prepared using benzophenone tetracarboxylic dianhydride
CN108102094A (en) * 2017-12-24 2018-06-01 桂林理工大学 The method that Kapton is prepared using hexafluorodianhydride (6FDA)
WO2020175838A1 (en) * 2019-02-28 2020-09-03 주식회사 엘지화학 Diamine compound, and polyimide precursor and polyimide film using same

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