WO2023155030A1 - Polyimide membrane, preparation method therefor and use thereof - Google Patents
Polyimide membrane, preparation method therefor and use thereof Download PDFInfo
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- WO2023155030A1 WO2023155030A1 PCT/CN2022/000071 CN2022000071W WO2023155030A1 WO 2023155030 A1 WO2023155030 A1 WO 2023155030A1 CN 2022000071 W CN2022000071 W CN 2022000071W WO 2023155030 A1 WO2023155030 A1 WO 2023155030A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the invention relates to the technical field of polyimide film preparation, in particular to a polyimide film with hydrophilicity on one side and non-hydrophilicity on the other side, a manufacturing method and application thereof.
- Polyimide films generally have good heat resistance and can be used as substrates for flexible electronic devices (such as touch screens, displays, etc.). Usually, the polyimide film is first polymerized on the glass substrate, and then the circuit is formed on the polyimide film through coating, photolithography and other processes, and finally the polyimide film is peeled off from the glass substrate. The aforementioned flexible electronic device is obtained.
- the problem to be solved by this invention is to provide a kind of polyimide film and its manufacture method, this polyimide film has hydrophilicity on one side, the other side has non-hydrophilicity, makes this polyimide film as When the substrate of flexible electronic devices is used, the circuit on the film has good adhesion, and it is also easy to peel off the polyimide film from the glass substrate.
- the technical scheme adopted is as follows:
- a polyimide film is characterized in that the polyimide film is a fully aromatic copolymerized polyimide polymer prepared by alternating copolymerization of diamine compounds and dianhydride compounds, and its chemical structure is simple.
- the formula is:
- X is a reactive residue of a hydrophobic diamine compound
- Y is a reactive residue of a hydrophobic dianhydride compound
- m and n represent the degree of polymerization
- m and n are both integers greater than 0, and the aromatic type
- the copolymerized polyimide polymer forms the polyimide film by coating or casting, and an electric field is applied before polymerization so that one side of the polyimide film has m>n, and the other side has n>m .
- hydrophilic properties are formed on both sides of the polyimide film: when m ⁇ n, the hydrophilic property of this surface is stronger, and it is suitable for forming circuits on this surface by processes such as coating and photolithography ; And when m>n, the hydrophilic property of the surface is weak, and it is easy to peel off from the glass substrate.
- the diamine compound includes a hydrophilic diamine compound and a hydrophobic diamine compound, wherein the hydrophilic diamine compound is 9,9-bis(2-methoxyethoxy)
- the molar ratio of methyl-2,7-diaminofluorene to 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene is 1-60%.
- membrane surfaces with different hydrophilic properties can be obtained, because 9,9-bis(2-methoxyethoxy)methyl -2,7-diaminofluorene has a group with relatively high electronegative property, which will drift under the action of a strong electric field before polymerization and gather to the high potential side.
- the hydrophobic diamine compound includes at least one of the following compounds: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3 , 3'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2'-bistrifluoromethyl-4, 4'-diphenyl ether diamine, 2,2'-bistrifluoromethyl-4,4'-diphenylsulfide diamine, 2,2'-bistrifluoromethyl-4,4'-diphenyl Sul
- the hydrophobic dianhydride compound includes 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride in a molar ratio of 1-50%.
- the dianhydride compound also includes at least one of 3,3',4,4'-biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride.
- the molar ratio of the diamine compound to the dianhydride compound is 1:0.98 ⁇ 1:1.02.
- the present invention also provides the preparation method of described polyimide film, it is characterized in that comprising the following steps:
- Step 1 Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in a strong polar aprotic solvent in a polymerization bottle, then add 2,2' -bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, and 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene with 2,2'-bis (3,4-dicarboxylic acid) hexafluoropropane dianhydride is in an equimolar ratio, and the stirring reaction is carried out for 5 to 10 hours under a reaction environment of 20 to 60 ° C and normal pressure to obtain the first polyamic acid solution;
- Step 2 Dissolve the second diamine compound completely in a strong polar aprotic solvent in the polymerization bottle, and the second diamine compound is a hydrophobic diamine compound; then add the second dianhydride compound, Stirring and reacting for 5-10 hours under a reaction environment of 20-60°C and normal pressure to obtain the second polyamic acid solution;
- Step 3 Evenly mix the first polyamic acid solution with the second polyamic acid solution and apply it on the glass substrate to form a coating, apply an electric field perpendicular to the glass substrate on the coating, and the glass substrate in the electric field The potential on the outside is higher than the potential inside the glass substrate, and then heat-baked at 60-80°C under the condition of maintaining the electric field to remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate from room temperature to 250-350°C, the heating time is 1-5 hours, and the heating rate is 1-10°C/min, then naturally cool to 25-80°C, and remove the film to obtain the polyimide Amine film.
- the potential on the outside of the glass substrate is higher and the film is formed as a coated polyimide solution, which has higher hydrophilicity, while the potential inside the glass substrate is lower and has lower hydrophilicity, thus forming double-sided hydrophilicity Different polyimide films.
- the second dianhydride compound is 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, or 2,2'-bis(3,4-di Carboxylic acid) an equal proportion mixture of hexafluoropropane dianhydride and at least one of 3,3',4,4'-biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride.
- the molar ratio of the second diamine compound to the second dianhydride compound is 1:0.98 ⁇ 1:1.02.
- Hydrophobic diamine compounds include at least one of the following compounds: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, diaminodiphenyl ether, Phenylsulfone, 4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-bis(trifluoromethane base) biphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2'-bistrifluoromethyl-4,4'-diphenyl ether diamine, 2,2'-bistrifluoromethyl-4,4'-diphenylsulfidediamine, 2,2'-bistrifluoromethyl-4,4'-diphenylsulfon
- the strong polar aprotic solvent includes N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone A mixture of one or more than two solvents.
- the polyimide film of the present invention is applied to a flexible touch substrate.
- the present invention has the following advantages: the polyimide film of the present invention and the manufacturing method thereof form different hydrophilic properties on both sides of the polyimide film through different degrees of polymerization, and one side has a hydrophilic property. The other side has non-hydrophilicity, so that when this polyimide film is used as the substrate of flexible electronic devices, the circuit on the film has good adhesion, and it is also easy to remove the polyimide film from the glass peeled off the substrate.
- Fig. 1 is the schematic diagram of step 3 in each embodiment of the present invention; Wherein, each mark is: 1- glass substrate, 2- two kinds of polyamic acid solution mixed coatings, 3- upper electrode, 4- lower electrode, 5- coating Glue scraper (for glass substrate coating), 6-infrared lamp for drying, 7-roller (for conveying glass substrate).
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in N,N-dimethylformamide in a polymerization bottle, then add etc. 2,2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride in molar ratio, stirred and reacted for 8 hours under a reaction environment of 50° C. and normal pressure, to obtain polyamic acid solution A;
- Step 2 Dissolve p-phenylenediamine completely in N, N-dimethylformamide in the polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropanedianhydride, in Stirring reaction was carried out for 8 hours under a reaction environment of 50° C. and normal pressure to obtain polyamic acid solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 320° C. for 4 hours at a rate of 8° C./min, then naturally cool to 40° C. and remove the film to obtain a polyimide film.
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in N,N-dimethylformamide in a polymerization bottle, then add etc. 2,2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride in molar ratio, stirred and reacted for 6 hours under a reaction environment of 50° C. and normal pressure to obtain polyamic acid solution A;
- Step 2 Dissolve m-phenylenediamine completely in N, N-dimethylformamide in the polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, in Stirring and reacting for 10 hours under a reaction environment of 50° C. and normal pressure to obtain a polyamic acid solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 350° C. for 3 hours at a rate of 2° C./min, then naturally cool to 60° C. and remove the film to obtain a polyimide film.
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in dimethyl sulfoxide in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 8 hours at 60° C. and normal pressure reaction environment to obtain polyamic acid solution A;
- Step 2 Completely dissolve 4,4'-diaminodiphenyl ether in dimethyl sulfoxide in a polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride , carrying out a stirring reaction for 6 hours under a reaction environment of 50° C. and normal pressure to obtain a polyamic acid solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 300° C. for 2 hours at a rate of 4° C./min, then naturally cool to 40° C. and remove the film to obtain a polyimide film.
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in N-methylpyrrolidone in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 6 hours at 30° C. and normal pressure reaction environment to obtain polyamic acid solution A;
- Step 2 Dissolve diaminodiphenylsulfone completely in N-methylpyrrolidone in a polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride and 3,3' , 4,4'-biphenyl-type tetracarboxylic dianhydride mixed solvent in equal proportions, stirred and reacted for 6 hours under a reaction environment of 60° C. and normal pressure, to obtain polyamic acid solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 270° C. for 2 hours at a rate of 1° C./min, then naturally cool to 25° C. and remove the film to obtain a polyimide film.
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in N,N-dimethylformamide in a polymerization bottle, then add etc. 2,2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride in molar ratio, stirred and reacted for 10 hours under a reaction environment of 50° C. and normal pressure to obtain polyamic acid solution A;
- Step 2 Completely dissolve 4,4'-diaminobiphenyl in N,N-dimethylformamide in a polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid)hexafluoro A mixed solvent of propane dianhydride and 3,3',4,4'-biphenyl tetracarboxylic dianhydride in equal proportions was stirred and reacted for 5 hours under a reaction environment of 60°C and normal pressure to obtain a polyamic acid solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 250° C. for 1 hour at a rate of 5° C./min, then naturally cool to 70° C. and remove the film to obtain a polyimide film.
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in dimethyl sulfoxide in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 5 hours at 40° C. and normal pressure reaction environment to obtain polyamic acid solution A;
- Step 2 Completely dissolve 4,4'-diamino-3,3'-dimethylbiphenyl in dimethyl sulfoxide in a polymerization bottle, then add 2,2'-bis(3,4-bis Carboxylic acid) an equal proportion mixed solvent of hexafluoropropane dianhydride and 3,3',4,4'-biphenyl type tetracarboxylic dianhydride, carried out a stirring reaction for 8 hours under a reaction environment of 30° C. and normal pressure, Obtain polyamic acid solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 350° C. for 4 hours at a rate of 4° C./min, then naturally cool to 40° C. and remove the film to obtain a polyimide film.
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in N-methylpyrrolidone in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 7 hours at 20° C. and normal pressure reaction environment to obtain polyamic acid solution A;
- Step 2 Completely dissolve 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl in N-methylpyrrolidone in a polymerization bottle, then add 2,2'-bis(3 , 4-dicarboxylic acid) an equal proportion mixed solvent of hexafluoropropane dianhydride and pyromellitic dianhydride was stirred and reacted for 10 hours at 30° C. and under normal pressure reaction environment to obtain polyamic acid solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 320° C. for 5 hours at a rate of 3° C./min, then naturally cool to 80° C. and remove the film to obtain a polyimide film.
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in N,N-dimethylformamide in a polymerization bottle, then add etc. 2,2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride in molar ratio, stirred and reacted for 6 hours under a reaction environment of 50° C. and normal pressure to obtain polyamic acid solution A;
- Step 2 Completely dissolve 2,2'-bistrifluoromethyl-4,4'-diphenylsulfide diamine in N,N-dimethylformamide in a polymerization bottle, then add 2,2' - A mixed solvent of bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride and pyromellitic dianhydride in equal proportions, stirred and reacted for 9 hours under a reaction environment of 40°C and normal pressure to obtain polyamic acid Solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 280° C. for 4 hours at a rate of 6° C./min, then naturally cool to 30° C. and remove the film to obtain a polyimide film.
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in dimethyl sulfoxide in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 8 hours at 30° C. and normal pressure reaction environment to obtain polyamic acid solution A;
- Step 2 Completely dissolve 2,2'-bistrifluoromethyl-4,4'-diphenylsulfonediamine in dimethyl sulfoxide in a polymerization bottle, then add 2,2'-bis(3, 4-dicarboxylic acid) a mixed solvent of hexafluoropropane dianhydride and pyromellitic dianhydride in equal proportions was stirred and reacted for 9 hours under a reaction environment of 40° C. and normal pressure to obtain a polyamic acid solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 320° C. for 3 hours at a rate of 8° C./min, then naturally cool to 50° C. and remove the film to obtain a polyimide film.
- This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
- Step 1 Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in N-methylpyrrolidone in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 10 hours at 60° C. under a normal pressure reaction environment to obtain polyamic acid solution A;
- Step 2 Completely dissolve 4,4'-diaminodiphenylmethane in N-methylpyrrolidone in a polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride , 3,3 ', 4,4'-biphenyl type tetracarboxylic dianhydride and pyromellitic dianhydride mixed solvent in equal proportions, carried out stirring reaction for 10 hours at 20°C and normal pressure reaction environment, to obtain Polyamic acid solution B;
- Step 3 As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
- Step 4 Gradually raise the temperature of the glass substrate 1 from room temperature to 350° C. for 3 hours at a rate of 10° C./min, then naturally cool to 30° C. and remove the film to obtain a polyimide film.
- the polyamic acid solution A uses a hydrophilic diamine compound
- the polyamic acid solution B uses a hydrophobic diamine compound.
- electric fields with different potentials are applied on both sides of the glass substrate.
- the potential of the upper electrode 3 is higher than that of the lower electrode 4, therefore, the polyimide membranes prepared in Examples 1 to 10 all have hydrophilicity on one side and non-hydrophilicity on the other side.
- Example 1 40 89 49
- Example 2 56 94 38
- Example 3 37
- Example 4 42
- Example 5 38
- Example 6 64
- Example 7 56
- Example 8 34
- 93 59
- Example 9 36
- Example 10 50
- 54 54
- the relationship between the above water drop contact angle and hydrophilicity and hydrophobicity is: when the water drop contact angle is obviously less than 90°, it is hydrophilic; when the water drop contact angle is close to or exceeds 90°, it is hydrophobic. A small water droplet contact angle indicates that the surface has high hydrophilicity, and a large water droplet contact angle indicates that the surface has high hydrophobicity.
- the inner and outer surfaces of the samples from Examples 1 to 10 show hydrophobicity and hydrophilicity respectively, so that when the samples from Examples 1 to 10 are used as substrates for flexible electronic devices, The circuit on the film has good adhesion, and it is also easy to peel the polyimide film from the glass substrate.
- the molar ratio of the second diamine compound to the second dianhydride compound can be adjusted according to actual production needs, as long as the molar ratio of the corresponding diamine compound to the dianhydride compound is within 1 :0.98 ⁇ 1:1.02 is enough.
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Abstract
The present invention relates to a polyimide membrane, a preparation method therefor and use thereof. Both sides of the polyimide membrane are formed with different hydrophilic properties by means of different degrees of polymerization. One side is hydrophilic and the other side is non-hydrophilic, so that when the polyimide membrane is used as the substrate of a flexible electronic device, the electrical circuit on the membrane has good adhesion, and the polyimide membrane can also be easily peeled from the mother glass.
Description
本发明涉及聚酰亚胺膜制备技术领域,尤其涉及一种一面具有亲水性、另一面具有非亲水性的聚酰亚胺膜及其制造方法与应用。The invention relates to the technical field of polyimide film preparation, in particular to a polyimide film with hydrophilicity on one side and non-hydrophilicity on the other side, a manufacturing method and application thereof.
聚酰亚胺膜一般具有良好的耐热性,可作为柔性电子器件(比如触摸屏、显示器等)的基底。通常情况下,先在玻璃基板上聚合形成聚酰亚胺膜,然后在聚酰亚胺膜上通过镀膜、光刻等制程形成电路,最后再将聚酰亚胺膜从玻璃基板上剥离下来,得到前述的柔性电子器件。Polyimide films generally have good heat resistance and can be used as substrates for flexible electronic devices (such as touch screens, displays, etc.). Usually, the polyimide film is first polymerized on the glass substrate, and then the circuit is formed on the polyimide film through coating, photolithography and other processes, and finally the polyimide film is peeled off from the glass substrate. The aforementioned flexible electronic device is obtained.
不过,聚酰亚胺膜的亲水性能却与膜上电路的附着性能存在矛盾:如果聚酰亚胺膜具有良好的亲水性,在聚酰亚胺膜上形成的电路虽然具有很好的附着性,但是在将聚酰亚胺膜剥离玻璃基板时,很难将聚酰亚胺膜从玻璃基板上剥离下来;相反地,如果聚酰亚胺膜具有良好的疏水性,在将聚酰亚胺膜从玻璃基板上剥离下来时非常容易,而聚酰亚胺膜上形成的电路的附着性较差。However, there is a contradiction between the hydrophilic property of the polyimide film and the adhesion performance of the circuit on the film: if the polyimide film has good hydrophilicity, although the circuit formed on the polyimide film has a good Adhesion, but when the polyimide film is peeled off the glass substrate, it is difficult to peel off the polyimide film from the glass substrate; on the contrary, if the polyimide film has good hydrophobicity, The imide film is very easy to peel off from the glass substrate, but the adhesion of the circuit formed on the polyimide film is poor.
发明内容Contents of the invention
本发明所要解决的问题是提供一种聚酰亚胺膜及其制造方法,这种聚酰亚胺膜一面具有亲水性、另一面具有非亲水性,使得这种聚酰亚胺膜作为柔性电子器件的基底使用时,膜上的电路具有很好的附着性,同时也很容易将聚酰亚胺膜从玻璃基板上剥离。采用的技术方案如下:The problem to be solved by this invention is to provide a kind of polyimide film and its manufacture method, this polyimide film has hydrophilicity on one side, the other side has non-hydrophilicity, makes this polyimide film as When the substrate of flexible electronic devices is used, the circuit on the film has good adhesion, and it is also easy to peel off the polyimide film from the glass substrate. The technical scheme adopted is as follows:
一种聚酰亚胺膜,其特征在于所述聚酰亚胺膜是由二胺化合物和二酐化合物交替共聚反应制备而成的全芳香型共聚型聚酰亚胺聚合物,其化学结构简式为:A polyimide film is characterized in that the polyimide film is a fully aromatic copolymerized polyimide polymer prepared by alternating copolymerization of diamine compounds and dianhydride compounds, and its chemical structure is simple. The formula is:
其中,X为具有疏水性的二胺化合物的反应残基,Y为具有疏水性的二酐化合物的反应残基;m和n表示聚合度,m、n均为大于0的整数,全芳香型共聚型聚酰亚胺聚合物通过涂布或流延的方式形成所述聚酰亚胺膜,并且在聚合前施加电场使得聚酰亚胺膜的一面具有m>n、另一面具有n>m。Among them, X is a reactive residue of a hydrophobic diamine compound, Y is a reactive residue of a hydrophobic dianhydride compound; m and n represent the degree of polymerization, m and n are both integers greater than 0, and the aromatic type The copolymerized polyimide polymer forms the polyimide film by coating or casting, and an electric field is applied before polymerization so that one side of the polyimide film has m>n, and the other side has n>m .
通过不同的聚合度,使聚酰亚胺膜的两面形成不相同的亲水性能:当m<n时,该面的亲水性能较强,适合在该面上镀膜、光刻等制程形成电路;而当m>n时,该面的亲水性能较弱,容易从玻璃基板上剥离。Through different degrees of polymerization, different hydrophilic properties are formed on both sides of the polyimide film: when m<n, the hydrophilic property of this surface is stronger, and it is suitable for forming circuits on this surface by processes such as coating and photolithography ; And when m>n, the hydrophilic property of the surface is weak, and it is easy to peel off from the glass substrate.
作为本发明的优选方案,所述二胺化合物包括亲水型二胺化合物和疏水型二胺化合物,其中,亲水型二胺化合物为9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴,9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴的摩尔比为1~60%。通过在薄膜的不同侧调节亲水型二胺化合物和疏水型二胺化合物的配比,获得亲水性能不同的膜面,由于9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴存在负电性较大的基团,在聚合前会在强电场的作用下会发生漂移而聚集到高电位的一侧。As a preferred version of the present invention, the diamine compound includes a hydrophilic diamine compound and a hydrophobic diamine compound, wherein the hydrophilic diamine compound is 9,9-bis(2-methoxyethoxy) The molar ratio of methyl-2,7-diaminofluorene to 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene is 1-60%. By adjusting the ratio of hydrophilic diamine compound and hydrophobic diamine compound on different sides of the film, membrane surfaces with different hydrophilic properties can be obtained, because 9,9-bis(2-methoxyethoxy)methyl -2,7-diaminofluorene has a group with relatively high electronegative property, which will drift under the action of a strong electric field before polymerization and gather to the high potential side.
作为本发明进一步的优选方案,所述疏水型二胺化合物包括以下化合物中的至少一种:对苯二胺、间苯二胺、4,4’-二氨基二苯醚、3,3’-二氨基二苯醚、二氨基二苯砜、4,4’-二氨基联苯、4,4’-二氨基-3,3’-二甲基联苯、4,4’-二氨基-3,3’-二(三氟甲基)联苯、4,4’-二氨基-2,2’-二(三氟甲基)联苯、2,2’-双三氟甲基-4,4’-二苯醚二胺、2,2’-双三氟甲基-4,4’-二苯硫醚二胺、2,2’-双三氟甲基-4,4’-二苯砜二胺、4,4’-二氨基二苯甲烷。As a further preferred solution of the present invention, the hydrophobic diamine compound includes at least one of the following compounds: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3 , 3'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2'-bistrifluoromethyl-4, 4'-diphenyl ether diamine, 2,2'-bistrifluoromethyl-4,4'-diphenylsulfide diamine, 2,2'-bistrifluoromethyl-4,4'-diphenyl Sulfonediamine, 4,4'-diaminodiphenylmethane.
作为本发明进一步的优选方案,所述具有疏水性的二酐化合物包括摩尔比为1~50%的2,2′-双(3,4-二羧酸)六氟丙烷二酐。As a further preferred solution of the present invention, the hydrophobic dianhydride compound includes 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride in a molar ratio of 1-50%.
作为本发明更进一步的优选方案,所述二酐化合物还包括3,3’,4,4’-联苯型四羧酸二酐、均苯四甲酸二酐的至少一种。As a further preferred solution of the present invention, the dianhydride compound also includes at least one of 3,3',4,4'-biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride.
作为本发明的优选方案,所述二胺化合物与所述二酐化合物的摩尔比为1∶0.98~1∶1.02。As a preferred solution of the present invention, the molar ratio of the diamine compound to the dianhydride compound is 1:0.98˜1:1.02.
另外,本发明还提供了所述聚酰亚胺膜的制备方法,其特征在于包括以下步骤:In addition, the present invention also provides the preparation method of described polyimide film, it is characterized in that comprising the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于强极性非质子溶剂中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐,并且9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴与2,2′-双(3,4-二羧酸)六氟丙烷二酐为等摩尔比,在20~60℃、常压的反应环境下进行5~10小时的搅拌反应,得到第一种聚酰胺酸溶液;Step 1: Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in a strong polar aprotic solvent in a polymerization bottle, then add 2,2' -bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, and 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene with 2,2'-bis (3,4-dicarboxylic acid) hexafluoropropane dianhydride is in an equimolar ratio, and the stirring reaction is carried out for 5 to 10 hours under a reaction environment of 20 to 60 ° C and normal pressure to obtain the first polyamic acid solution;
步骤2:在聚合瓶中将第二种二胺化合物完全溶解于强极性非质子溶剂中,并且第二种二胺化合物为疏水型二胺类化合物;然后加入第二种二酐化合物,在20~60℃、常压的反应环境下进行5~10小时的搅拌反应,得到第二种聚酰胺酸溶液;Step 2: Dissolve the second diamine compound completely in a strong polar aprotic solvent in the polymerization bottle, and the second diamine compound is a hydrophobic diamine compound; then add the second dianhydride compound, Stirring and reacting for 5-10 hours under a reaction environment of 20-60°C and normal pressure to obtain the second polyamic acid solution;
步骤3:将第一种聚酰胺酸溶液与第二种聚酰胺酸溶液均匀混合后涂布到玻璃基板上形成涂层,在涂层上施加垂直于玻璃基板的电场,并且在电场中玻璃基板外侧的电位高于玻璃基板内部的电位,然后在保持电场的条件下进行60~80℃的热烘以除掉部分有机溶剂;Step 3: Evenly mix the first polyamic acid solution with the second polyamic acid solution and apply it on the glass substrate to form a coating, apply an electric field perpendicular to the glass substrate on the coating, and the glass substrate in the electric field The potential on the outside is higher than the potential inside the glass substrate, and then heat-baked at 60-80°C under the condition of maintaining the electric field to remove part of the organic solvent;
步骤4:将玻璃基板从室温逐渐升温至250~350℃,升温时间1~5小时,升温速率为1-10℃/min, 然后自然冷却至25~80℃,脱膜得到所述聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate from room temperature to 250-350°C, the heating time is 1-5 hours, and the heating rate is 1-10°C/min, then naturally cool to 25-80°C, and remove the film to obtain the polyimide Amine film.
玻璃基板外侧的电位较高而作为涂布聚酰亚胺溶液形成薄膜,具有更高的亲水性,而玻璃基板内部的电位较低,具有较低的亲水性,从而形成两面亲水性不同的聚酰亚胺膜。The potential on the outside of the glass substrate is higher and the film is formed as a coated polyimide solution, which has higher hydrophilicity, while the potential inside the glass substrate is lower and has lower hydrophilicity, thus forming double-sided hydrophilicity Different polyimide films.
作为本发明的优选方案,所述第二种二酐化合物为2,2′-双(3,4-二羧酸)六氟丙烷二酐、或者2,2′-双(3,4-二羧酸)六氟丙烷二酐与3,3’,4,4’-联苯型四羧酸二酐、均苯四甲酸二酐中的至少一种的等比例混合物。其中,第二种二胺化合物与第二种二酐化合物的摩尔比为1∶0.98~1∶1.02。疏水型二胺类化合物包括以下化合物中的至少一种:对苯二胺、间苯二胺、4,4’-二氨基二苯醚、3,3’-二氨基二苯醚、二氨基二苯砜、4,4’-二氨基联苯、4,4’-二氨基-3,3’-二甲基联苯、4,4’-二氨基-3,3’-二(三氟甲基)联苯、4,4’-二氨基-2,2’-二(三氟甲基)联苯、2,2’-双三氟甲基-4,4’-二苯醚二胺、2,2’-双三氟甲基-4,4’-二苯硫醚二胺、2,2’-双三氟甲基-4,4’-二苯砜二胺、4,4’-二氨基二苯甲烷。As a preferred version of the present invention, the second dianhydride compound is 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, or 2,2'-bis(3,4-di Carboxylic acid) an equal proportion mixture of hexafluoropropane dianhydride and at least one of 3,3',4,4'-biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride. Wherein, the molar ratio of the second diamine compound to the second dianhydride compound is 1:0.98˜1:1.02. Hydrophobic diamine compounds include at least one of the following compounds: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, diaminodiphenyl ether, Phenylsulfone, 4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-bis(trifluoromethane base) biphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2'-bistrifluoromethyl-4,4'-diphenyl ether diamine, 2,2'-bistrifluoromethyl-4,4'-diphenylsulfidediamine, 2,2'-bistrifluoromethyl-4,4'-diphenylsulfonediamine, 4,4'- Diaminodiphenylmethane.
作为本发明进一步的优选方案,所述强极性非质子溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜或N-甲基吡咯烷酮中的一种或者二种以上混合而成的混合溶剂。As a further preferred solution of the present invention, the strong polar aprotic solvent includes N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone A mixture of one or more than two solvents.
另外,本发明所述聚酰亚胺膜应用于柔性触控基底。In addition, the polyimide film of the present invention is applied to a flexible touch substrate.
本发明与现有技术相比,具有如下优点:本发明聚酰亚胺膜及其制造方法通过不同的聚合度,使聚酰亚胺膜的两面形成不相同的亲水性能,一面具有亲水性、另一面具有非亲水性,使得这种聚酰亚胺膜作为柔性电子器件的基底使用时,膜上的电路具有很好的附着性,同时也很容易将聚酰亚胺膜从玻璃基板上剥离。Compared with the prior art, the present invention has the following advantages: the polyimide film of the present invention and the manufacturing method thereof form different hydrophilic properties on both sides of the polyimide film through different degrees of polymerization, and one side has a hydrophilic property. The other side has non-hydrophilicity, so that when this polyimide film is used as the substrate of flexible electronic devices, the circuit on the film has good adhesion, and it is also easy to remove the polyimide film from the glass peeled off the substrate.
图1为本发明各实施例中步骤3的示意图;其中,各标示为:1-玻璃基板,2-两种聚酰胺酸溶液混合涂层,3-上电极,4-下电极,5-涂胶刮刀(用于玻璃基板涂布),6-烘干用红外灯,7-滚轮(用于输送玻璃基板)。Fig. 1 is the schematic diagram of step 3 in each embodiment of the present invention; Wherein, each mark is: 1- glass substrate, 2- two kinds of polyamic acid solution mixed coatings, 3- upper electrode, 4- lower electrode, 5- coating Glue scraper (for glass substrate coating), 6-infrared lamp for drying, 7-roller (for conveying glass substrate).
实施例一Embodiment one
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于N,N-二甲基甲酰胺中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在50℃、常压的反应环境下进行8小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in N,N-dimethylformamide in a polymerization bottle, then add etc. 2,2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride in molar ratio, stirred and reacted for 8 hours under a reaction environment of 50° C. and normal pressure, to obtain polyamic acid solution A;
步骤2:在聚合瓶中将对苯二胺完全溶解于N,N-二甲基甲酰胺中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐,在50℃、常压的反应环境下进行8小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Dissolve p-phenylenediamine completely in N, N-dimethylformamide in the polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropanedianhydride, in Stirring reaction was carried out for 8 hours under a reaction environment of 50° C. and normal pressure to obtain polyamic acid solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场的条件下进行70℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至320℃,升温时间4小时,升温速率为8℃/min,然后自然冷却至40℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 320° C. for 4 hours at a rate of 8° C./min, then naturally cool to 40° C. and remove the film to obtain a polyimide film.
实施例二Embodiment two
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于N,N-二甲基甲酰胺中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在50℃、常压的反应环境下进行6小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in N,N-dimethylformamide in a polymerization bottle, then add etc. 2,2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride in molar ratio, stirred and reacted for 6 hours under a reaction environment of 50° C. and normal pressure to obtain polyamic acid solution A;
步骤2:在聚合瓶中将间苯二胺完全溶解于N,N-二甲基甲酰胺中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐,在50℃、常压的反应环境下进行10小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Dissolve m-phenylenediamine completely in N, N-dimethylformamide in the polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, in Stirring and reacting for 10 hours under a reaction environment of 50° C. and normal pressure to obtain a polyamic acid solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场的条件下进行80℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至350℃,升温时间3小时,升温速率为2℃/min,然后自然冷却至60℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 350° C. for 3 hours at a rate of 2° C./min, then naturally cool to 60° C. and remove the film to obtain a polyimide film.
实施例三Embodiment three
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于二甲基亚砜中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在60℃、常压的反应环境下进行8小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in dimethyl sulfoxide in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 8 hours at 60° C. and normal pressure reaction environment to obtain polyamic acid solution A;
步骤2:在聚合瓶中将4,4’-二氨基二苯醚完全溶解于二甲基亚砜中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐,在50℃、常压的反应环境下进行6小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Completely dissolve 4,4'-diaminodiphenyl ether in dimethyl sulfoxide in a polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride , carrying out a stirring reaction for 6 hours under a reaction environment of 50° C. and normal pressure to obtain a polyamic acid solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场 的条件下进行65℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至300℃,升温时间2小时,升温速率为4℃/min,然后自然冷却至40℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 300° C. for 2 hours at a rate of 4° C./min, then naturally cool to 40° C. and remove the film to obtain a polyimide film.
实施例四Embodiment four
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于N-甲基吡咯烷酮中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在30℃、常压的反应环境下进行6小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in N-methylpyrrolidone in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 6 hours at 30° C. and normal pressure reaction environment to obtain polyamic acid solution A;
步骤2:在聚合瓶中将二氨基二苯砜完全溶解于N-甲基吡咯烷酮中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐与3,3′,4,4′-联苯型四羧酸二酐的等比例混合溶剂,在60℃、常压的反应环境下进行6小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Dissolve diaminodiphenylsulfone completely in N-methylpyrrolidone in a polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride and 3,3' , 4,4'-biphenyl-type tetracarboxylic dianhydride mixed solvent in equal proportions, stirred and reacted for 6 hours under a reaction environment of 60° C. and normal pressure, to obtain polyamic acid solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场的条件下进行60℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至270℃,升温时间2小时,升温速率为1℃/min,然后自然冷却至25℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 270° C. for 2 hours at a rate of 1° C./min, then naturally cool to 25° C. and remove the film to obtain a polyimide film.
实施例五Embodiment five
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于N,N-二甲基甲酰胺中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在50℃、常压的反应环境下进行10小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in N,N-dimethylformamide in a polymerization bottle, then add etc. 2,2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride in molar ratio, stirred and reacted for 10 hours under a reaction environment of 50° C. and normal pressure to obtain polyamic acid solution A;
步骤2:在聚合瓶中将4,4’-二氨基联苯完全溶解于N,N-二甲基甲酰胺中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐与3,3′,4,4′-联苯型四羧酸二酐的等比例混合溶剂,在60℃、常压的反应环境下进行5小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Completely dissolve 4,4'-diaminobiphenyl in N,N-dimethylformamide in a polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid)hexafluoro A mixed solvent of propane dianhydride and 3,3',4,4'-biphenyl tetracarboxylic dianhydride in equal proportions was stirred and reacted for 5 hours under a reaction environment of 60°C and normal pressure to obtain a polyamic acid solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场的条件下进行60℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至250℃,升温时间1小时,升温速率为5℃/min,然后自然冷却至70℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 250° C. for 1 hour at a rate of 5° C./min, then naturally cool to 70° C. and remove the film to obtain a polyimide film.
实施例六Embodiment six
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于二甲基亚砜中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在40℃、常压的反应环境下进行5小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in dimethyl sulfoxide in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 5 hours at 40° C. and normal pressure reaction environment to obtain polyamic acid solution A;
步骤2:在聚合瓶中将4,4’-二氨基-3,3’-二甲基联苯完全溶解于二甲基亚砜中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐与3,3′,4,4′-联苯型四羧酸二酐的等比例混合溶剂,在30℃、常压的反应环境下进行8小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Completely dissolve 4,4'-diamino-3,3'-dimethylbiphenyl in dimethyl sulfoxide in a polymerization bottle, then add 2,2'-bis(3,4-bis Carboxylic acid) an equal proportion mixed solvent of hexafluoropropane dianhydride and 3,3',4,4'-biphenyl type tetracarboxylic dianhydride, carried out a stirring reaction for 8 hours under a reaction environment of 30° C. and normal pressure, Obtain polyamic acid solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场的条件下进行75℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至350℃,升温时间4小时,升温速率为4℃/min,然后自然冷却至40℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 350° C. for 4 hours at a rate of 4° C./min, then naturally cool to 40° C. and remove the film to obtain a polyimide film.
实施例七Embodiment seven
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于N-甲基吡咯烷酮中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在20℃、常压的反应环境下进行7小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in N-methylpyrrolidone in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 7 hours at 20° C. and normal pressure reaction environment to obtain polyamic acid solution A;
步骤2:在聚合瓶中将4,4’-二氨基-2,2’-二(三氟甲基)联苯完全溶解于N-甲基吡咯烷酮中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐与均苯四甲酸二酐的等比例混合溶剂,在30℃、常压的反应环境下进行10小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Completely dissolve 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl in N-methylpyrrolidone in a polymerization bottle, then add 2,2'-bis(3 , 4-dicarboxylic acid) an equal proportion mixed solvent of hexafluoropropane dianhydride and pyromellitic dianhydride was stirred and reacted for 10 hours at 30° C. and under normal pressure reaction environment to obtain polyamic acid solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场的条件下进行80℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至320℃,升温时间5小时,升温速率为3℃/min,然后自然冷却至80℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 320° C. for 5 hours at a rate of 3° C./min, then naturally cool to 80° C. and remove the film to obtain a polyimide film.
实施例八Embodiment eight
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于N,N-二甲基甲 酰胺中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在50℃、常压的反应环境下进行6小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in N,N-dimethylformamide in a polymerization bottle, then add etc. 2,2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride in molar ratio, stirred and reacted for 6 hours under a reaction environment of 50° C. and normal pressure to obtain polyamic acid solution A;
步骤2:在聚合瓶中将2,2’-双三氟甲基-4,4’-二苯硫醚二胺完全溶解于N,N-二甲基甲酰胺中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐与均苯四甲酸二酐的等比例混合溶剂,在40℃、常压的反应环境下进行9小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Completely dissolve 2,2'-bistrifluoromethyl-4,4'-diphenylsulfide diamine in N,N-dimethylformamide in a polymerization bottle, then add 2,2' - A mixed solvent of bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride and pyromellitic dianhydride in equal proportions, stirred and reacted for 9 hours under a reaction environment of 40°C and normal pressure to obtain polyamic acid Solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场的条件下进行70℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至280℃,升温时间4小时,升温速率为6℃/min,然后自然冷却至30℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 280° C. for 4 hours at a rate of 6° C./min, then naturally cool to 30° C. and remove the film to obtain a polyimide film.
实施例九Embodiment nine
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于二甲基亚砜中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在30℃、常压的反应环境下进行8小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in dimethyl sulfoxide in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 8 hours at 30° C. and normal pressure reaction environment to obtain polyamic acid solution A;
步骤2:在聚合瓶中将2,2’-双三氟甲基-4,4’-二苯砜二胺完全溶解于二甲基亚砜中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐与均苯四甲酸二酐的等比例混合溶剂,在40℃、常压的反应环境下进行9小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Completely dissolve 2,2'-bistrifluoromethyl-4,4'-diphenylsulfonediamine in dimethyl sulfoxide in a polymerization bottle, then add 2,2'-bis(3, 4-dicarboxylic acid) a mixed solvent of hexafluoropropane dianhydride and pyromellitic dianhydride in equal proportions was stirred and reacted for 9 hours under a reaction environment of 40° C. and normal pressure to obtain a polyamic acid solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场的条件下进行80℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至320℃,升温时间3小时,升温速率为8℃/min,然后自然冷却至50℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 320° C. for 3 hours at a rate of 8° C./min, then naturally cool to 50° C. and remove the film to obtain a polyimide film.
实施例十Embodiment ten
本实施例公开了一种聚酰亚胺膜的制备方法,包括以下步骤:This embodiment discloses a kind of preparation method of polyimide membrane, comprises the following steps:
步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于N-甲基吡咯烷酮中,然后加入等摩尔比的2,2′-双(3,4-二羧酸)六氟丙烷二酐,在60℃、常压的反应环境下进行10小时的搅拌反应,得到聚酰胺酸溶液A;Step 1: Dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene completely in N-methylpyrrolidone in a polymerization bottle, and then add an equimolar ratio of 2 , 2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, stirred and reacted for 10 hours at 60° C. under a normal pressure reaction environment to obtain polyamic acid solution A;
步骤2:在聚合瓶中将4,4’-二氨基二苯甲烷完全溶解于N-甲基吡咯烷酮中,然后加入2,2′- 双(3,4-二羧酸)六氟丙烷二酐、3,3′,4,4′-联苯型四羧酸二酐和均苯四甲酸二酐的等比例混合溶剂,在20℃、常压的反应环境下进行10小时的搅拌反应,得到聚酰胺酸溶液B;Step 2: Completely dissolve 4,4'-diaminodiphenylmethane in N-methylpyrrolidone in a polymerization bottle, then add 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride , 3,3 ', 4,4'-biphenyl type tetracarboxylic dianhydride and pyromellitic dianhydride mixed solvent in equal proportions, carried out stirring reaction for 10 hours at 20°C and normal pressure reaction environment, to obtain Polyamic acid solution B;
步骤3:如图1所示,将聚酰胺酸溶液A与聚酰胺酸溶液B均匀混合后涂布到玻璃基板1上形成涂层2,在涂层2上施加垂直于玻璃基板1的电场,并且玻璃基板1外侧(对应图1中的上电极3)的电位高于玻璃基板1内部(对应图1中的下电极4)的电位,然后在保持电场的条件下进行80℃的热烘以除掉部分有机溶剂;Step 3: As shown in Figure 1, the polyamic acid solution A and the polyamic acid solution B are evenly mixed and coated on the glass substrate 1 to form a coating 2, and an electric field perpendicular to the glass substrate 1 is applied on the coating 2, And the potential on the outside of the glass substrate 1 (corresponding to the upper electrode 3 in FIG. 1 ) is higher than the potential inside the glass substrate 1 (corresponding to the lower electrode 4 in FIG. 1 ). Remove part of the organic solvent;
步骤4:将玻璃基板1从室温逐渐升温至350℃,升温时间3小时,升温速率为10℃/min,然后自然冷却至30℃,脱膜得到聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate 1 from room temperature to 350° C. for 3 hours at a rate of 10° C./min, then naturally cool to 30° C. and remove the film to obtain a polyimide film.
上述实施例一至实施例十中,聚酰胺酸溶液A均采用亲水型二胺化合物,而聚酰胺酸溶液B均采用疏水型二胺类化合物,同时在玻璃基板两侧施加不同电位的电场,上电极3的电位均高于下电极4的电位,因此,实施例一至实施例十所制得的聚酰亚胺膜均为一面具有亲水性、另一面具有非亲水性。In the above-mentioned Examples 1 to 10, the polyamic acid solution A uses a hydrophilic diamine compound, and the polyamic acid solution B uses a hydrophobic diamine compound. At the same time, electric fields with different potentials are applied on both sides of the glass substrate. The potential of the upper electrode 3 is higher than that of the lower electrode 4, therefore, the polyimide membranes prepared in Examples 1 to 10 all have hydrophilicity on one side and non-hydrophilicity on the other side.
同时,采用接触角测量仪测量实施例一至实施例十的样品的两个面的水滴接触角,测量结果如下:Simultaneously, adopt contact angle meter to measure the water droplet contact angle of two faces of the sample of embodiment one to embodiment ten, measurement result is as follows:
the | 外侧面接触角(°)Outer surface contact angle (°) | 内侧面接触角(°)Medial surface contact angle (°) | 内外侧面接触角差(°)Contact angle difference between inner and outer surfaces (°) |
实施例1Example 1 | 4040 | 8989 | 4949 |
实施例2Example 2 | 5656 | 9494 | 3838 |
实施例3Example 3 | 3737 | 7676 | 3939 |
实施例4Example 4 | 4242 | 9898 | 5656 |
实施例5Example 5 | 3838 | 9595 | 5757 |
实施例6Example 6 | 6464 | 102102 | 3838 |
实施例7Example 7 | 5656 | 8989 | 3333 |
实施例8Example 8 | 3434 | 9393 | 5959 |
实施例9Example 9 | 3636 | 9696 | 6060 |
实施例10Example 10 | 5050 | 104104 | 5454 |
上述水滴接触角的数值与亲水性、疏水性的关系为:当水滴接触角明显小于90°则为亲水性,当水滴接触角接近或超过90°则为疏水性。水滴接触角小说明表面具有较高的亲水性,水滴接触角大说明表面具有较高的疏水性。根据上表测试显示,实施例一至实施例十的样品的内侧面和外侧面分别表现出了疏水性和亲水性,使得实施例一至实施例十的样品在作为柔性电子器件的基底使用时,膜上的电路具有很好的附着性,同时也很容易将聚酰亚胺膜从玻璃基板上剥离。The relationship between the above water drop contact angle and hydrophilicity and hydrophobicity is: when the water drop contact angle is obviously less than 90°, it is hydrophilic; when the water drop contact angle is close to or exceeds 90°, it is hydrophobic. A small water droplet contact angle indicates that the surface has high hydrophilicity, and a large water droplet contact angle indicates that the surface has high hydrophobicity. According to the test shown in the table above, the inner and outer surfaces of the samples from Examples 1 to 10 show hydrophobicity and hydrophilicity respectively, so that when the samples from Examples 1 to 10 are used as substrates for flexible electronic devices, The circuit on the film has good adhesion, and it is also easy to peel the polyimide film from the glass substrate.
另外,在各个实施例中,第二种二胺化合物与第二种二酐化合物的摩尔比均可根据实际生产需要进行调整,只需满足相应的二胺化合物与二酐化合物的摩尔比在1∶0.98~1∶1.02即可。In addition, in each embodiment, the molar ratio of the second diamine compound to the second dianhydride compound can be adjusted according to actual production needs, as long as the molar ratio of the corresponding diamine compound to the dianhydride compound is within 1 :0.98~1:1.02 is enough.
此外,需要说明的是,本说明书中所描述的具体实施例,其各部分名称等可以不同,凡依本发明专利构思所述的构造、特征及原理所做的等效或简单变化,均包括于本发明专利的保护范围内。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离本发明的结构或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。In addition, it should be noted that, in the specific embodiments described in this specification, the names of various parts may be different, and all equivalent or simple changes made according to the structure, features and principles described in the patent concept of the present invention include Within the protection scope of the patent of the present invention. Those skilled in the art to which the present invention belongs can make various modifications or supplements to the described specific embodiments or adopt similar methods to replace them, as long as they do not deviate from the structure of the present invention or exceed the scope defined in the claims. All should belong to the protection scope of the present invention.
Claims (8)
- 一种聚酰亚胺膜,其特征在于所述聚酰亚胺膜是由二胺化合物和二酐化合物交替共聚反应制备而成的全芳香型共聚型聚酰亚胺聚合物,其化学结构简式为:A polyimide film is characterized in that the polyimide film is a fully aromatic copolymerized polyimide polymer prepared by alternating copolymerization of diamine compounds and dianhydride compounds, and its chemical structure is simple. The formula is:其中,X为具有疏水性的二胺化合物的反应残基,Y为具有疏水性的二酐化合物的反应残基;m和n表示聚合度,m、n均为大于0的整数,全芳香型共聚型聚酰亚胺聚合物通过涂布或流延的方式形成所述聚酰亚胺膜,并且在聚合前施加电场使得聚酰亚胺膜的一面具有m>n、另一面具有n>m。Among them, X is a reactive residue of a hydrophobic diamine compound, Y is a reactive residue of a hydrophobic dianhydride compound; m and n represent the degree of polymerization, m and n are both integers greater than 0, and the aromatic type The copolymerized polyimide polymer forms the polyimide film by coating or casting, and an electric field is applied before polymerization so that one side of the polyimide film has m>n, and the other side has n>m .
- 根据权利要求1所述的聚酰亚胺膜,其特征在于:所述二胺化合物包括亲水型二胺化合物和疏水型二胺化合物,其中,亲水型二胺化合物为9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴,9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴的摩尔比为1~60%。The polyimide film according to claim 1, wherein the diamine compound comprises a hydrophilic diamine compound and a hydrophobic diamine compound, wherein the hydrophilic diamine compound is 9,9-diamine compound (2-methoxyethoxy) methyl-2,7-diaminofluorene, the molar ratio of 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene is 1 to 60%.
- 根据权利要求2所述的聚酰亚胺膜,其特征在于:所述疏水型二胺化合物包括以下化合物中的至少一种:对苯二胺、间苯二胺、4,4’-二氨基二苯醚、3,3’-二氨基二苯醚、二氨基二苯砜、4,4’-二氨基联苯、4,4’-二氨基-3,3’-二甲基联苯、4,4’-二氨基-3,3’-二(三氟甲基)联苯、4,4’-二氨基-2,2’-二(三氟甲基)联苯、2,2’-双三氟甲基-4,4’-二苯醚二胺、2,2’-双三氟甲基-4,4’-二苯硫醚二胺、2,2’-双三氟甲基-4,4’-二苯砜二胺、4,4’-二氨基二苯甲烷。The polyimide film according to claim 2, wherein the hydrophobic diamine compound comprises at least one of the following compounds: p-phenylenediamine, m-phenylenediamine, 4,4'-diamino Diphenyl ether, 3,3'-diaminodiphenyl ether, diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2' -Bistrifluoromethyl-4,4'-diphenyl ether diamine, 2,2'-bistrifluoromethyl-4,4'-diphenylsulfide diamine, 2,2'-bistrifluoromethyl Base-4,4'-diphenylsulfonediamine, 4,4'-diaminodiphenylmethane.
- 根据权利要求1所述的聚酰亚胺膜,其特征在于:所述二胺化合物与所述二酐化合物的摩尔比为1∶0.98~1∶1.02。The polyimide film according to claim 1, characterized in that: the molar ratio of the diamine compound to the dianhydride compound is 1:0.98˜1:1.02.
- 一种权利要求1所述的聚酰亚胺膜的制备方法,其特征在于包括以下步骤:A kind of preparation method of polyimide membrane described in claim 1 is characterized in that comprising the following steps:步骤1:在聚合瓶中将9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴完全溶解于强极性非质子溶剂中,然后加入2,2′-双(3,4-二羧酸)六氟丙烷二酐,并且9,9-二(2-甲氧基乙氧基)甲基-2,7-二氨基芴与2,2′-双(3,4-二羧酸)六氟丙烷二酐为等摩尔比,在20~60℃、常压的反应环境下进行5~10小时的搅拌反应,得到第一种聚酰胺酸溶液;Step 1: Completely dissolve 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene in a strong polar aprotic solvent in a polymerization bottle, then add 2,2' -bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, and 9,9-bis(2-methoxyethoxy)methyl-2,7-diaminofluorene with 2,2'-bis (3,4-dicarboxylic acid) hexafluoropropane dianhydride is in an equimolar ratio, and the stirring reaction is carried out for 5 to 10 hours under a reaction environment of 20 to 60 ° C and normal pressure to obtain the first polyamic acid solution;步骤2:在聚合瓶中将第二种二胺化合物完全溶解于强极性非质子溶剂中,并且 第二种二胺化合物为疏水型二胺类化合物;然后加入第二种二酐化合物,在20~60℃、常压的反应环境下进行5~10小时的搅拌反应,得到第二种聚酰胺酸溶液;Step 2: Dissolve the second diamine compound completely in a strong polar aprotic solvent in the polymerization bottle, and the second diamine compound is a hydrophobic diamine compound; then add the second dianhydride compound, Stirring and reacting for 5-10 hours under a reaction environment of 20-60°C and normal pressure to obtain the second polyamic acid solution;步骤3:将第一种聚酰胺酸溶液与第二种聚酰胺酸溶液均匀混合后涂布到玻璃基板上形成涂层,在涂层上施加垂直于玻璃基板的电场,并且在电场中玻璃基板外侧的电位高于玻璃基板内部的电位,然后在保持电场的条件下进行60~80℃的热烘以除掉部分有机溶剂;Step 3: Evenly mix the first polyamic acid solution with the second polyamic acid solution and apply it on the glass substrate to form a coating, apply an electric field perpendicular to the glass substrate on the coating, and the glass substrate in the electric field The potential on the outside is higher than the potential inside the glass substrate, and then bake at 60-80°C under the condition of maintaining the electric field to remove part of the organic solvent;步骤4:将玻璃基板从室温逐渐升温至250~350℃,升温时间1~5小时,升温速率为1-10℃/min,然后自然冷却至25~80℃,脱膜得到所述聚酰亚胺膜。Step 4: Gradually raise the temperature of the glass substrate from room temperature to 250-350°C, the heating time is 1-5 hours, the heating rate is 1-10°C/min, then naturally cool to 25-80°C, and remove the film to obtain the polyimide Amine film.
- 根据权利要求5所述的制备方法,其特征在于:所述步骤2中,所述第二种二酐化合物为2,2′-双(3,4-二羧酸)六氟丙烷二酐、或者2,2′-双(3,4-二羧酸)六氟丙烷二酐与3,3’,4,4’-联苯型四羧酸二酐、均苯四甲酸二酐中的至少一种的等比例混合物。The preparation method according to claim 5, characterized in that: in the step 2, the second dianhydride compound is 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, Or at least one of 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride and 3,3',4,4'-biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride A mixture of equal proportions.
- 根据权利要求5或6所述的制备方法,其特征在于:所述强极性非质子溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜或N-甲基吡咯烷酮中的一种或者二种以上混合而成的混合溶剂。The preparation method according to claim 5 or 6, characterized in that: the strong polar aprotic solvent comprises N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide Or a mixed solvent of one or more than two kinds of N-methylpyrrolidone.
- 一种权利要求1所述的聚酰亚胺膜的应用,其特征在于:所述聚酰亚胺膜应用于柔性触控基底。An application of the polyimide film according to claim 1, characterized in that: the polyimide film is applied to a flexible touch base.
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