CN113549234A

CN113549234A - Production process of hydrophobic polyimide film

Info

Publication number: CN113549234A
Application number: CN202110831433.1A
Authority: CN
Inventors: 邹伟民; 刘承伟; 陆妮; 徐海; 徐寅
Original assignee: Jiangsu Transimage Technology Co Ltd
Current assignee: Jiangsu Transimage Technology Co Ltd
Priority date: 2021-07-22
Filing date: 2021-07-22
Publication date: 2021-10-26
Anticipated expiration: 2041-07-22
Also published as: CN113549234B

Abstract

The invention discloses a production process of a hydrophobic polyimide film, belonging to the technical field of modified polyimide film preparation, and the production process of the hydrophobic polyimide film comprises the following steps: preparing a diamine monomer A; diamine monomer A and dianhydride monomer react to prepare polyamic acid solution; imidizing to obtain a polyimide film; the prepared polyimide has C-F bonds and siloxane chains with excellent hydrophobic property, ester groups are arranged in the middle of the diamine monomer A, the structural symmetry degree of the diamine monomer A is high, the polymer can form microcrystals locally, diffusion of water molecules in the polymer is hindered due to the existence of the local microcrystals, when the water molecules meet the local microcrystals of the high molecular chains, high molecular chain segments in the crystalline structure are tightly piled, the water molecules cannot permeate and diffuse, the water molecules are finally retarded to advance, and the hydrophobic property 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 a polymer containing imide ring (-CO-N-CO-) on the main chain, is one of organic polymer materials with the best comprehensive performance, has excellent performances such as high strength, low dielectric, high modulus, high temperature resistance and radiation resistance, and attracts attention and application due to the excellent performances such as high strength, low dielectric, high modulus, high temperature resistance and radiation resistance. 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 the high and new technology fields of aviation, aerospace, microelectronics and the like.

Despite its high chemical stability, the polyimide still absorbs some moisture, causing problems of metal corrosion, package cracking, film-to-metal adhesion failure, and dielectric property degradation, and the dielectric property thereof is significantly degraded due to its water absorption, which limits its further application in the rapidly developing electronic product field.

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 limits the application range of the polyimide film.

The purpose of the invention can be realized 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 4-5h at the temperature of 115 ℃ and 120 ℃, after the reaction is finished, cooling a reaction product to 70 ℃, transferring the reaction product into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, shaking, standing for 30min for layering, adding an organic phase into the flask, carrying out reduced pressure distillation to remove the toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid, the p-methylphenol, the p-sulfobenzoic acid and the toluene is 0.05 mol: 0.05 mol: 1.8 g: 45 mL;

the reaction process is as follows:

step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and performing 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 molar ratio of the intermediate 1 to the potassium permanganate is 1:1, the dosage ratio of the intermediate 2, DMF and thionyl chloride is 1 mol: 0.5 mL: 2.1 mol;

the reaction process is as follows:

step S3: adding 3, 5-dihydroxybenzoic acid and DMF (dimethyl formamide) into a flask, then adding aminopropyltriethoxysilane, then adding a catalyst, and stirring to react for 2 hours at the temperature of 30 ℃ to obtain an intermediate 4; the dosage ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane and catalyst is 0.1 mol: 100mL of: 0.11 mol: 0.5g, the catalyst is EDCI/HOBt with a molar ratio of 1: 1;

the reaction process is as follows:

step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reacting for 3 hours to obtain an intermediate 5; the dosage ratio of the intermediate 4, the 2-chloro-5-nitrobenzotrifluoride and the toluene is 2 mmol: 2 mmol: 10 mL;

the reaction process is as follows:

step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring and reacting at the temperature of 0-5 ℃ 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 1 mmol: 1 mmol: 10mL of: 1mmol of the active component;

the reaction process is as follows:

step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 30-32h, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10 percent Pd/C catalyst and the 1, 4-dioxane is 0.03 mol: 1.3 g: 300 mL;

the reaction process is as follows:

step S7: adding a diamine monomer A and DMF (dimethyl formamide) into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, vacuum-drying at the temperature of 60 ℃ to remove a solvent, then introducing nitrogen, heating to the temperature of 140 ℃ and 150 ℃, and keeping for 1h to obtain a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is as follows: 1 mmol: 5mL of: 1mmol of the active component;

the reaction process is as follows:

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 has prepared a polyimide film, prepare a diamine monomer A at first, and then react with dianhydride monomer 3,3 ', 4, 4' -benzophenone tetracarboxylic acid dianhydride by diamine monomer A, make polyamic acid solution, imidize and make polyimide film, wherein diamine monomer A is reacted by p-methylbenzoic acid and p-methylphenol esterification at first, make intermediate 1, then oxidize methyl of both ends of intermediate 1, become carboxyl, and then acidylate, make carboxyl turn into acyl chloride group, make intermediate 3, then utilize amino of aminopropyl triethoxysilane and carboxyl of 3, 5-dihydroxy benzoic acid to react, make intermediate 4, intermediate 4 and one active chlorine of 2-chloro-5-nitro benzotrifluoride take place the substitution reaction, make intermediate 5, then make hydroxyl of intermediate 5 react with acyl chloride of both ends of intermediate 3, preparing an intermediate 6, converting nitro groups of the intermediate 6 into amino groups under the action of a catalyst to prepare a diamine monomer A, wherein the amino groups at two ends of the diamine monomer A can participate in a reaction to prepare polyimide, the middle of the diamine monomer A is provided with an ester group, the structural symmetry of the diamine monomer A is high, the polymer can locally form microcrystals, due to the existence of the local microcrystals, diffusion of water molecules in the polymer is hindered, when the water molecules meet the local microcrystals of a high molecular chain, polymer chain segments in a crystalline structure are tightly piled up, the water molecules cannot permeate and diffuse, and finally the water molecules are retarded, meanwhile, the polymer in the crystalline structure forms good steric hindrance due to the existence of the crystalline structure, adsorption sites of the water molecules are reduced, the hydrogen bond water absorption effect is weakened, meanwhile, the diamine monomer also has a siloxane structure, and the introduction of the siloxane chain can reduce the glass transition temperature of the polymer, the diamine monomer A also has a C-F bond with high electronegativity, and fluorine atoms are difficult to form a hydrogen bond with hydrogen in water molecules as an electron donor, so that the hydrophobic property of the prepared polyimide is further improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present 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 is finished, cooling a reaction product to 70 ℃, transferring the reaction product into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, shaking, standing for 30min for layering, adding an organic phase into the flask, distilling under reduced pressure to remove the toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid, the p-methylphenol, the p-sulfobenzoic acid and the toluene is 0.05 mol: 0.05 mol: 1.8 g: 45 mL;

step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring and reacting at the temperature of 0 ℃ 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 1 mmol: 1 mmol: 10mL of: 1mmol of the active component;

step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 30 hours, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10 percent Pd/C catalyst and the 1, 4-dioxane is 0.03 mol: 1.3 g: 300 mL.

Example 2

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 117.5 ℃, after the reaction is finished, cooling a reaction product to 70 ℃, transferring the reaction product into a separating funnel, adding a saturated sodium chloride aqueous solution at 70 ℃, shaking, standing for 30min for layering, adding an organic phase into the flask, distilling under reduced pressure to remove the toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid, the p-methylphenol, the p-sulfobenzoic acid and the toluene is 0.05 mol: 0.05 mol: 1.8 g: 45 mL;

step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring and reacting at the temperature of 3 ℃ 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 1 mmol: 1 mmol: 10mL of: 1mmol of the active component;

step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 31 hours, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10 percent Pd/C catalyst and the 1, 4-dioxane is 0.03 mol: 1.3 g: 300 mL.

Example 3

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 is finished, cooling a reaction product to 70 ℃, transferring the reaction product into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, shaking, standing for 30min for layering, adding an organic phase into the flask, distilling under reduced pressure to remove the toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid, the p-methylphenol, the p-sulfobenzoic acid and the toluene is 0.05 mol: 0.05 mol: 1.8 g: 45 mL;

step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring and reacting at the temperature of 5 ℃ 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 1 mmol: 1 mmol: 10mL of: 1mmol of the active component;

step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 32 hours, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10 percent Pd/C catalyst and the 1, 4-dioxane is 0.03 mol: 1.3 g: 300 mL.

Example 4

The preparation method of the hydrophobic polyimide film comprises the following steps:

adding the diamine monomer A prepared in the example 2 and DMF into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h 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 ℃, and keeping for 1h to prepare a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is as follows: 1 mmol: 5mL of: 1 mmol.

Example 5

adding the diamine monomer A prepared in the example 2 and DMF into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h 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 145 ℃, and keeping for 1h to obtain a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is as follows: 1 mmol: 5mL of: 1 mmol.

Example 6

adding the diamine monomer A prepared in the example 2 and DMF into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h 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 150 ℃, and keeping for 1h to prepare a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is as follows: 1 mmol: 5mL of: 1 mmol.

Comparative example 1: compared to example 5, 4' -diaminodiphenyl sulfone was used as diamine monomer.

Comparative example 2: compared to example 5, hexafluoromethyl diphenyl diamine was used as the diamine monomer.

Comparative example 3: 1, 3-bis (3-aminopropyl) tetramethyldisiloxane was used as the diamine monomer compared to example 5.

The examples 4 to 6 and comparative examples 1 to 3 were subjected to the performance test, and the results are shown in the following table:

the tensile strength and elongation at break were tested in reference to GB13022-91, and the hydrophobicity was judged by measuring the contact angle, the results are given 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°

The table shows that examples 4-6 have good mechanical properties and hydrophobic properties.

It is noted that, herein, relational terms such as first and second, and the like may be 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. Also, 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 appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. A production process of a hydrophobic polyimide film is characterized by comprising the following steps:

adding a diamine monomer A and DMF (dimethyl formamide) into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h 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, heating to the temperature of 140 ℃ and 150 ℃, and keeping for 1h to obtain the polyimide film.

2. The process for preparing a hydrophobic polyimide film according to claim 1, wherein the diamine monomer A, DMF and the 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride are used in the following ratio: 1 mmol: 5mL of: 1 mmol.

3. The process for producing a hydrophobic polyimide film according to claim 1, 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, and reacting for 4-5h at the temperature of 115 ℃ and 120 ℃ to obtain an intermediate 1;

step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and performing 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 (dimethyl formamide) into a flask, then adding aminopropyltriethoxysilane, then adding a catalyst, and stirring to react for 2 hours at the temperature of 30 ℃ to obtain an intermediate 4;

step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reacting 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 and reacting at the temperature of 0-5 ℃ for 3 hours, and obtaining an intermediate 6 after the reaction is finished;

step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 30-32h, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain the diamine monomer A.

4. The process of claim 3, wherein the amount ratio of p-toluic acid, p-methylphenol, p-sulfanylbenzoic acid, and toluene in step S1 is 0.05 mol: 0.05 mol: 1.8 g: 45 mL.

5. The process for preparing a hydrophobic polyimide film according to claim 3, wherein the molar ratio of the intermediate 1 to the potassium permanganate used in step S2 is 1:1, the dosage ratio of the intermediate 2, DMF and thionyl chloride is 1 mol: 0.5 mL: 2.1 mol.

6. The process of claim 3, wherein the amount ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane, and catalyst used in step S3 is 0.1 mol: 100mL of: 0.11 mol: 0.5g, the catalyst is EDCI/HOBt with a molar ratio of 1: 1.

7. The process of claim 3, wherein the ratio of the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene in step S4 is 2 mmol: 2 mmol: 10 mL.

8. The process of claim 3, wherein the ratio of the intermediate 3, the intermediate 5, the tetrahydrofuran and the pyridine in step S5 is 1 mmol: 1 mmol: 10mL of: 1 mmol.

9. The process of claim 3, wherein the intermediate 6, the 10% Pd/C catalyst, and the 1, 4-dioxane are used in a ratio of 0.03 mol: 1.3 g: 300 mL.