CN108841003B - Polyimide dielectric film and preparation method and application thereof - Google Patents

Polyimide dielectric film and preparation method and application thereof Download PDF

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CN108841003B
CN108841003B CN201810599986.7A CN201810599986A CN108841003B CN 108841003 B CN108841003 B CN 108841003B CN 201810599986 A CN201810599986 A CN 201810599986A CN 108841003 B CN108841003 B CN 108841003B
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佟辉
徐菊
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Institute of Electrical Engineering of CAS
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract

A polyimide dielectric film is prepared by condensation polymerization of diamine monomer containing polar groups and/or flexible bonding structure and dianhydride monomer containing polar groups and/or flexible bonding structure, and subsequent thermal imidization treatment, and the preparation method comprises the following steps: under the protection of inert gas, dissolving a diamine monomer in an organic solvent, adding a dianhydride monomer, stirring to obtain a homogeneous solution, and continuously reacting for 4-10 hours at a certain temperature to obtain a polyamide acid (PAA) solution. Coating a polyamic acid solution on a substrate, heating, drying, immersing in deionized water for stripping, and drying again to obtain the polyimide dielectric film. The polyimide dielectric film can resist the high temperature of 230 ℃. The polyimide dielectric film of the present invention is used for a metallized film capacitor.

Description

Polyimide dielectric film and preparation method and application thereof
Technical Field
The invention relates to the technical field of film capacitors, in particular to a high-temperature-resistant polyimide dielectric film for a film capacitor, and a preparation method and application thereof.
Background
Polymer thin film capacitors are widely used in microelectronic devices and power systems, including power electronics in electric and hybrid electric vehicles, grid inverters/converters, pulse power supply equipment, and the like. Taking an electric vehicle or a hybrid pneumatic vehicle as an example, energy storage and power regulation become more and more necessary due to the demand of next generation power electronics for rapid charging and discharging of a large amount of energy, and polymer dielectric films are required to have properties such as high breakdown strength, high dielectric constant and low dielectric loss. The performance of polypropylene dielectric in the existing film capacitor can not meet the temperature requirement, for example, polypropylene has poor temperature resistance and large shrinkage rate, the long-term use temperature is about 105 ℃, and the application environment temperature of an electric automobile is over 115 ℃, so that the internal temperature of the polypropylene capacitor is increased along with the lengthening of the working time, and the stability of the polypropylene capacitor is sharply reduced or even loses efficacy. Therefore, the glass transition temperature (T) is consideredg)>The high-performance polymer with the temperature of 150 ℃ is used as a dielectric film material in a harsh environment.
Patent CN201180045116.1 discloses a film for film capacitors based on vinylidene fluoride resin, but the resin has high dielectric loss, complicated preparation process, high pressure operation design and high energy loss. Patent CN 102930982A discloses a capacitor foil based on block polystyreneHowever, the dielectric constant of the film is low (1.7-3.3), which is not favorable for improving the energy storage density of the film capacitor. Ma et al designed polyimide molecular structures containing different groups such as-NH-, -C (═ O) -and-O-, etc. The highest dielectric constant can reach 7.8, and the energy density is 15J/cm3But their TgVery low, difficult to use for long periods at 150 ℃ (Rui Ma, Aaron F. Baldwin, Chenche Wang, Ido Offenbach, Mukerrem Cakmak, Rampirasad, and Gregory Allen Sonz.Rationally signed polymers for High Energy Density Capacitor applications ACS Applied Materials and Interfaces 2014,6(13): 10445-10451).
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-temperature-resistant polyimide dielectric film for a film capacitor, and a preparation method and application of the dielectric film.
In order to achieve the purpose, the invention provides the following technical scheme:
a molecular structure of the polyimide dielectric film is composed of a dianhydride monomer unit and a diamine monomer unit, wherein the dianhydride monomer unit contains a polar group and/or a flexible bonding structure, and the diamine monomer unit contains a polar group and/or a flexible bonding structure. The polyimide dielectric film has a structural general formula shown in the following formula I:
Figure BDA0001692930140000021
in the formula I, Ar1Selected from any one of formula II or formula III:
Figure BDA0001692930140000022
wherein B1 is selected from the group consisting of-, -O-),
Figure BDA0001692930140000023
Any one of the above;
Figure BDA0001692930140000024
wherein, B2Is selected from-O-),
Figure BDA0001692930140000025
Any one of (1), B3Is selected from-O-),
Figure BDA0001692930140000026
Any one of (1), B2、B3The same or different;
Ar2selected from any one of formula IV, formula V or formula VI:
Figure BDA0001692930140000027
wherein R is1is-O-, -CH 2-),
Figure BDA0001692930140000031
Any one of the above;
Figure BDA0001692930140000032
wherein R is2Is selected from-O-),
Figure BDA0001692930140000033
Any one of (1), R3Is selected from-O-),
Figure BDA0001692930140000034
Figure BDA0001692930140000035
Any one of (1), R2And R3The same or different;
Figure BDA0001692930140000036
wherein R is4Is selected from-O-or
Figure BDA0001692930140000037
Any one of (1), R5Is selected from-O-or
Figure BDA0001692930140000038
Any one of (1), R6Is selected from-O-or
Figure BDA0001692930140000039
Any one of (1), R4、R5And R6The same or different;
n is an integer of 15 to 200.
Number average molecular weight (M) of polyimide as described in formula In) Is 8000-80000 g/mol.
The polyimide film dielectric has outstanding heat resistance, the glass transition temperature is 280-390 ℃, and the thermal decomposition temperature is above 580 ℃.
The polyimide dielectric film has excellent dielectric property, the relative dielectric constant is within the range of 4.15-7.27, the dielectric loss is within the range of 0.12% -0.39%, and the breakdown strength can reach 640MV/m at most.
The method for preparing the polyimide dielectric film comprises the following steps: under the protection of inert gas, dissolving a diamine monomer based on a structure shown in a formula IV or a formula V or a formula VI in an organic solvent, then adding a dianhydride monomer based on a formula II or a formula III, stirring until the diamine monomer is completely dissolved to obtain a homogeneous solution, and continuously reacting at a certain temperature to obtain a polyamide acid (PAA) solution. And coating the polyamic acid solution on a substrate, heating, drying, immersing in deionized water for stripping, and drying again to obtain the polyimide dielectric film.
In the preparation method, the dianhydride monomer based on the formula II is selected from any one of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, 3 ', 4, 4' -diphenyl ether tetracarboxylic dianhydride, 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride and 3,3 ', 4, 4' -diphenyl sulfone tetracarboxylic dianhydride;
the dianhydride monomer based on formula III is selected from one of 3,3 ', 4, 4' -diphenyl (p-phenylene ether) tetracarboxylic dianhydride, 3 ', 4, 4' -diphenyl (m-phenylene ether) tetracarboxylic dianhydride, ditrimellitic anhydride terephthalate, ditrimellitic anhydride resorcinol ester, terephthalic acid di (hydroxy phthalic anhydride) ester or isophthalic acid di (hydroxy phthalic anhydride) ester.
In the preparation method, the diamine monomer based on the formula IV is selected from one of 4,4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl methane, 4 ' -diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfone or 4,4 ' -diaminobenzanilide.
Based on a diamine monomer of formula V selected from one of 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4- (4-aminophenoxy) phenyl-4-aminophenyl ketone, bis (4-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, hydroquinone 1, 4-bis (4-aminobenzoate) or hydroquinone 1, 3-bis (4-aminobenzoate).
The diamine monomer based on formula VI is selected from one of 4,4 '-bis (4-aminophenoxy) diphenyl ether or 4, 4' -bis (4-aminobenzoyl) diphenyl ether.
The organic solvent is selected from one or a mixture of two of N-methylpyrrolidone (NMP), gamma-butyrolactone, dimethyl sulfoxide (DMSO), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), Dichloromethane (DCM) or Trichloromethane (TCM).
The feeding molar ratio of the dianhydride monomer based on the formula II or the formula III to the diamine monomer based on the formula IV or the formula V or the formula VI is 0.95-1.05: 1.
The solid content of the homogeneous solution is 10-30 wt.%.
The reaction temperature is room temperature; the reaction pressure is normal pressure.
The reaction time is 4-10 hours.
The substrate material is a glass plate or a silicon wafer.
In the drying treatment step, the temperature is 50-300 ℃ and the time is 3.5-6.5 hours.
The thickness of the polyimide dielectric film is 2-50 μm, preferably 2-15 μm.
The polyimide dielectric film can bear the highest temperature of 230 ℃ and can be used for a long time at the temperature of 230 ℃.
The polyimide dielectric film is used for a metalized film capacitor.
The invention has the beneficial effects that:
compared with the polypropylene and polyester dielectrics used at present, the polyimide dielectric film provided by the invention has more outstanding heat resistance and excellent dielectric property, and can be applied to the fields with higher temperature requirements such as electric automobiles and the like. Specifically, the polyimide dielectric film is prepared from a dianhydride monomer containing a polar group and/or a flexible bonding structure in a molecular structure and a diamine monomer containing a polar group and/or a flexible bonding structure in a molecular structure, and the polar group and the flexible bonding structure in the molecular structure enable the polyimide dielectric film to have high dielectric constant, low dielectric loss and dielectric breakdown strength. Meanwhile, the aromatic structure and the ring structure in the molecular structure endow the heat resistance to the coating.
Drawings
FIG. 1 is a FT-IR diagram of a polyimide prepared in example 1.
Detailed Description
The process of the present invention is a conventional process unless otherwise specified. The starting materials are commercially available from published sources unless otherwise specified. In the present invention, the percentage content and the percentage concentration are both the mass percentage content and the mass percentage concentration unless otherwise specified.
Example 1 preparation of polyimide dielectric film
1.9623 g of 0.0098 mol of 4,4 ' -diaminodiphenyl ether and 40.1 g of N-methylpyrrolidone (NMP) are added into a three-neck round-bottom flask which is provided with a mechanical stirrer and a nitrogen inlet and outlet at room temperature and normal pressure, the mixture is stirred under the protection of nitrogen until the mixture is completely dissolved, 2.4922 g of 0.01 mol of 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride is added to obtain a homogeneous solution with the solid content of 10 wt%, and the reaction is continued for 6 hours to obtain a polyamic acid solution.
And (2) filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 2 hours and 50 ℃, 1 hour and 100 ℃, 1 hour and 200 ℃, and 0.5 hour and 250 ℃ to perform imidization reaction to obtain the polyimide film. And (3) placing the glass plate in deionized water to enable the film to be automatically stripped, and performing vacuum drying to obtain the polyimide dielectric film with the thickness of 3 microns.
The Fourier transform infrared spectrum of the polyimide dielectric film thus obtained is shown in FIG. 1.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Carrying out physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and then carrying out dielectric test to obtain a dielectric constant (epsilon) and a dielectric loss (tan delta); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
Example 2 preparation of polyimide dielectric film
1.9826 g of 0.01 mol of 4,4 ' -diaminodiphenylmethane and 28.8 g of dimethyl sulfoxide (DMSO) are added into a three-neck round-bottom flask with mechanical stirring and a nitrogen inlet and outlet at room temperature and normal pressure, the mixture is stirred under the protection of nitrogen until the mixture is completely dissolved, 3.1020 g of 0.01 mol of 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride is added to obtain a homogeneous solution with a solid content of 15 wt%, and the reaction is continued for 8 hours to obtain a polyamic acid solution.
And (2) filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a silicon wafer with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 2 hours and 50 ℃, 1 hour and 100 ℃, 1 hour and 150 ℃, 1 hour and 200 ℃, 1 hour and 250 ℃, and 0.5 hour and 300 ℃ to perform imidization reaction to obtain the polyimide film. And (3) placing the silicon wafer in deionized water to enable the film to be automatically stripped, and drying in vacuum to obtain the polyimide dielectric film with the thickness of 5 microns.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Carrying out physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and then carrying out dielectric test to obtain a dielectric constant (epsilon) and a dielectric loss (tan delta); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
Example 3 preparation and characterization of polyimide dielectric films
3.5571 g of 0.0095 mol of 1, 4-bis (4-aminobenzoic acid) hydroquinone ester, 20.3 g of a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) and the volume ratio of DMSO to DMF (1: 1) are added into a three-neck round-bottom flask with a mechanical stirrer and a nitrogen inlet and outlet at room temperature and normal pressure, the mixture is stirred under the protection of nitrogen until the mixture is completely dissolved, 3.2223 g of 0.01 mol of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is added to obtain a homogeneous solution with the solid content of 25 wt%, and the reaction is continued for 6 hours to obtain a polyamic acid solution.
And (2) filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 2 hours and 50 ℃, 1 hour and 100 ℃, 1 hour and 150 ℃, and 0.5 hour and 200 ℃ to perform imidization reaction to obtain the polyimide film. And (3) placing the glass plate in deionized water to enable the film to be automatically stripped, and performing vacuum drying to obtain the polyimide dielectric film with the thickness of 5 microns.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Performing physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and performing dielectric test to obtain the polyimide dielectric filmDielectric constant (. epsilon.) and dielectric loss (tan. delta.); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
Polyimide dielectric films having similar properties were obtained by the same preparation method except that 1, 4-bis (4-aminobenzoic acid) hydroquinone ester was replaced with 1, 3-bis (4-aminobenzoic acid) hydroquinone ester in the above examples.
Example 4 preparation and characterization of polyimide dielectric films
4.0845 g of 0.01 mol of 4,4 ' -bis (4-aminobenzoyl) diphenyl ether and 30.7 g of N, N-Dimethylformamide (DMF) are added into a three-neck round-bottom flask with mechanical stirring and a nitrogen inlet and outlet at room temperature and normal pressure, stirred under the protection of nitrogen until complete dissolution, 3.5828 g of 0.01 mol of 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic dianhydride is added to obtain a homogeneous solution with a solid content of 20 wt.%, and the reaction is continued for 6 hours to obtain a polyamic acid solution.
And (2) filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 2 hours 50 ℃, 1 hour 100 ℃, 1 hour 150 ℃, 1 hour 200 ℃, 1 hour 250 ℃ and 0.5 hour 300 ℃ to perform imidization reaction to obtain the polyimide film. And (3) placing the glass plate in deionized water to enable the film to be automatically stripped, and performing vacuum drying to obtain the polyimide dielectric film with the thickness of 8 microns.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Carrying out physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and then carrying out dielectric test to obtain a dielectric constant (epsilon) and a dielectric loss (tan delta); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
Example 5 preparation of polyimide dielectric film
2.5327 g of 0.0102 mol of 4,4 ' -diaminodiphenyl sulfone and 15.3 g of Trichloromethane (TCM) are added into a three-neck round-bottom flask with mechanical stirring and a nitrogen inlet and outlet at room temperature and normal pressure, the mixture is stirred under the protection of nitrogen until the mixture is completely dissolved, 4.0213 g of 0.01 mol of 3,3 ', 4,4 ' -diphenyl (p-phenylene ether) tetracarboxylic dianhydride is added to obtain a homogeneous solution with the solid content of 30 wt.%, and the reaction is continued for 4 hours to obtain a polyamic acid solution.
And filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a silicon wafer with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 2 hours and 50 ℃, 1 hour and 100 ℃, 1 hour and 150 ℃, 1 hour and 200 ℃ and 0.5 hour and 250 ℃ to perform imidization reaction, thereby obtaining the polyimide film. And (3) placing the silicon wafer in deionized water to enable the film to be automatically stripped, and drying in vacuum to obtain the polyimide dielectric film with the thickness of 6 microns.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Carrying out physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and then carrying out dielectric test to obtain a dielectric constant (epsilon) and a dielectric loss (tan delta); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
By replacing 4,4 '-diaminodiphenyl sulfone in the above examples with 3, 3' -diaminodiphenyl sulfone and using the same preparation method, polyimide dielectric films with similar properties can be obtained.
Example 6 preparation of polyimide dielectric film
2.9233 g of 0.01 mol of 1, 4-bis (4-aminophenoxy) benzene and 30.0 g of Dichloromethane (DCM) were added to a three-necked round-bottomed flask equipped with a mechanical stirrer and a nitrogen inlet and outlet at room temperature and normal pressure, stirred under nitrogen protection until completely dissolved, 4.5833 g of 0.01 mol of ditrimellitic anhydride terephthalate was added to obtain a homogeneous solution having a solid content of 20 wt.%, and the reaction was continued for 8 hours to obtain a polyamic acid solution.
And (2) filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 2 hours 50 ℃, 1 hour 100 ℃, 1 hour 150 ℃, 1 hour 250 ℃ and 0.5 hour 300 ℃ to perform imidization reaction to obtain the polyimide film. And (3) placing the glass plate in deionized water to enable the film to be automatically stripped, and performing vacuum drying to obtain the polyimide dielectric film with the thickness of 10 microns.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Carrying out physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and then carrying out dielectric test to obtain a dielectric constant (epsilon) and a dielectric loss (tan delta); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
Polyimide dielectric films with similar properties can be obtained by replacing 1, 4-bis (4-aminophenoxy) benzene in the above examples with 1, 3-bis (4-aminophenoxy) benzene, and replacing bis trimellitic anhydride p-phenylene terephthalate with bis trimellitic anhydride resorcinol ester by the same preparation method.
Example 7 preparation of polyimide dielectric film
3.0130 g of 0.0099 mol of 4- (4-aminophenoxy) phenyl-4-aminophenyl ketone and 60.4 g of gamma-butyrolactone are added to a three-neck round-bottom flask equipped with a mechanical stirrer and a nitrogen inlet and outlet at room temperature and normal pressure, stirred under the protection of nitrogen until complete dissolution, 4.5833 g of 0.01 mol of bis (hydroxyphthalic anhydride) terephthalate are added to obtain a homogeneous solution with a solid content of 10 wt.%, and the reaction is continued for 10 hours to obtain a polyamic acid solution.
And (2) filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 2 hours 50 ℃, 1 hour 100 ℃, 1 hour 150 ℃, 1 hour 200 ℃, 1 hour 250 ℃ and 0.5 hour 300 ℃ to perform imidization reaction to obtain the polyimide film. And (3) placing the glass plate in deionized water to enable the film to be automatically stripped, and performing vacuum drying to obtain the polyimide dielectric film with the thickness of 15 microns.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Carrying out physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and then carrying out dielectric test to obtain a dielectric constant (epsilon) and a dielectric loss (tan delta); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
The same preparation method was used to replace the bis (hydroxyphthalic anhydride) terephthalate in the above examples with bis (hydroxyphthalic anhydride) isophthalate to obtain polyimide dielectric films with similar properties.
Example 8 preparation of polyimide dielectric film
2.3862 g of 0.0105 mol of 4,4 ' -diaminobenzanilide and 36.3 g of N, N-Dimethylformamide (DMF) are added into a three-necked round-bottomed flask equipped with a mechanical stirrer and a nitrogen inlet and outlet at room temperature and normal pressure, stirred under nitrogen protection until complete dissolution, 4.0231 g (0.01 mol) of 3,3 ', 4,4 ' -diphenyl (m-phenylene ether) tetracarboxylic dianhydride is added to obtain a homogeneous solution with a solid content of 15 wt.%, and the reaction is continued for 8 hours to obtain a polyamic acid solution.
And filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a silicon wafer with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 2 hours and 50 ℃, 1 hour and 100 ℃, 1 hour and 150 ℃, 1 hour and 200 ℃ and 0.5 hour and 250 ℃ to perform imidization reaction, thereby obtaining the polyimide film. And (3) placing the silicon wafer in deionized water to enable the film to be automatically stripped, and drying in vacuum to obtain the polyimide dielectric film with the thickness of 50 microns.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Carrying out physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and then carrying out dielectric test to obtain a dielectric constant (epsilon) and a dielectric loss (tan delta); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
Example 9 preparation of polyimide dielectric film
In a three-neck round bottom flask equipped with mechanical stirring and nitrogen inlet and outlet, 3.8192 g of 0.0102 mol of bis (4-aminophenyl) terephthalate and 39.9 g of N, N-dimethylacetamide (DMAc) were added under nitrogen protection and stirred until completely dissolved, 3.2223 g (0.01 mol) of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride were added to obtain a homogeneous solution with a solid content of 15 wt.%, and the reaction was continued for 8 hours at room temperature and atmospheric pressure to obtain a polyamic acid solution.
And (2) filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a silicon wafer with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 1 hour 100 ℃, 1 hour 150 ℃, 1 hour 250 ℃ and 0.5 hour 300 ℃ to perform imidization reaction to obtain the polyimide film. And (3) placing the silicon wafer in deionized water to enable the film to be automatically stripped, and drying in vacuum to obtain the polyimide dielectric film with the thickness of 30 microns.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Performing physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and performing dielectric test to obtain a dielectricA constant (. epsilon.) and a dielectric loss (tan. delta.); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
By replacing bis (4-aminophenyl) terephthalate in the above examples with bis (4-aminophenyl) isophthalate and adopting the same preparation method, polyimide dielectric films having similar properties were obtained.
Example 10 preparation of polyimide dielectric film
3.8443 g of 0.01 mol of 4,4 ' -bis (4-aminophenoxy) diphenyl ether and 66.8 g of N, N-dimethylacetamide (DMAc) were added to a three-neck round-bottom flask equipped with a mechanical stirrer and a nitrogen inlet and outlet at room temperature and normal pressure, stirred under nitrogen protection until complete dissolution, 3.5828 g of 0.01 mol of 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic dianhydride was added to obtain a homogeneous solution having a solid content of 10 wt.%, and the reaction was continued for 4 hours to obtain a polyamic acid solution.
And (2) filtering and vacuum defoaming the polyamic acid solution, coating the polyamic acid solution on a silicon wafer with a smooth surface, and heating the polyamic acid solution in the air atmosphere according to the steps of 2 hours to 100 ℃, 1 hour to 150 ℃, 1 hour to 200 ℃, 1 hour to 250 ℃ and 0.5 hour to 300 ℃ to perform imidization reaction to obtain the polyimide film. And (3) placing the silicon wafer in deionized water to enable the film to be automatically stripped, and drying in vacuum to obtain the polyimide dielectric film with the thickness of 2 microns.
The prepared polyimide dielectric film is subjected to differential scanning calorimetry analysis to obtain the glass transition temperature (T)g) (ii) a The thermal weight loss analysis was performed under a nitrogen atmosphere to obtain the thermal decomposition temperature (T) of the polyimide dielectric filmd) (ii) a Carrying out physical vacuum evaporation on the prepared polyimide dielectric film to form a metal electrode, and then carrying out dielectric test to obtain a dielectric constant (epsilon) and a dielectric loss (tan delta); the dielectric breakdown strength (E) of the polyimide dielectric film is obtained by adopting a program-controlled withstand voltage tester for testingb). The main properties of the polyimide film dielectric are shown in table 1.
TABLE 1 Properties of polyimide dielectric films
Figure BDA0001692930140000121

Claims (7)

1. A polyimide dielectric film is characterized in that the molecular structure of the dielectric film is composed of a dianhydride monomer unit and a diamine monomer unit, wherein the dianhydride monomer unit contains a polar group and/or a flexible bonding structure, and the diamine monomer unit contains a polar group and/or a flexible bonding structure; the polyimide film dielectric has a structural general formula shown in the following formula I:
Figure FDA0002779283130000011
wherein Ar is1Selected from any one of formula II or formula III:
Figure FDA0002779283130000012
wherein, B1Is selected from-O-),
Figure FDA0002779283130000013
Any one of the above;
Figure FDA0002779283130000014
wherein, B2Is selected from-O-),
Figure FDA0002779283130000015
Any one of (1), B3Is selected from-O-),
Figure FDA0002779283130000016
Any one of (1), B2、B3The same;
when Ar is1Selected from formula II, Ar2Selected from any one of formula V or formula VI:
Figure FDA0002779283130000017
wherein R is2Is selected from
Figure FDA0002779283130000021
Any one of (1), R3Is selected from
Figure FDA0002779283130000022
Figure FDA0002779283130000023
Any one of (1), R2And R3The same;
Figure FDA0002779283130000024
wherein R is4Is selected from-O-or
Figure FDA0002779283130000025
Any one of (1), R5Is selected from-O-or
Figure FDA0002779283130000026
Any one of (1), R6Is selected from-O-or
Figure FDA0002779283130000027
Any one of (1), R4、R5And R6The same;
when Ar is1Selected from formula III, Ar2Selected from any one of formula IV, formula V or formula VI:
Figure FDA0002779283130000028
wherein R is1is-O-, -CH2-、
Figure FDA0002779283130000029
Any one of the above;
Figure FDA00027792831300000210
wherein R is2Is selected from-O-),
Figure FDA00027792831300000211
Any one of (1), R3Is selected from-O-),
Figure FDA00027792831300000212
Figure FDA00027792831300000213
Any one of (1), R2And R3The same;
Figure FDA00027792831300000214
wherein R is4Is selected from-O-or
Figure FDA00027792831300000215
Any one of (1), R5Is selected from-O-or
Figure FDA00027792831300000216
Any one of (1), R6Is selected from-O-or
Figure FDA00027792831300000217
Any one of (1), R4、R5And R6The same;
n is an integer of 15 to 200;
number average molecular weight (M) of the polyimide dielectric filmn) Is 8000-80000 g/mol.
2. The polyimide dielectric film according to claim 1, wherein the polyimide dielectric film has a glass transition temperature of 280 to 390 ℃ and a thermal decomposition temperature of 580 ℃ or higher; the relative dielectric constant of the polyimide dielectric film is within the range of 4.15-7.27, the dielectric loss is within the range of 0.12% -0.39%, and the breakdown strength can reach as high as 640 MV/m.
3. The method for preparing the polyimide dielectric film according to claim 1 or 2, wherein the polyimide dielectric film is obtained by condensation polymerization of a dianhydride monomer containing a polar group and/or a flexible bonding structure and a diamine monomer containing a polar group and/or a flexible bonding structure, followed by imidization treatment, and the method comprises the following steps:
under the protection of inert gas, dissolving a diamine monomer based on a structure shown in a formula IV or a formula V or a formula VI in an organic solvent, then adding a dianhydride monomer based on a formula II or a formula III, stirring until the diamine monomer is completely dissolved to obtain a homogeneous solution, and continuously reacting at a certain temperature to obtain a polyamide acid (PAA) solution; and coating the polyamic acid solution on a substrate, heating, drying, immersing in deionized water for stripping, and drying again to obtain the polyimide dielectric film.
4. The method for preparing a polyimide dielectric film according to claim 3, wherein the dianhydride-based monomer of formula II is one selected from 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, 3 ', 4, 4' -diphenyl ether tetracarboxylic dianhydride, 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, or 3,3 ', 4, 4' -diphenyl sulfone tetracarboxylic dianhydride;
the dianhydride monomer based on the formula III is selected from one of 3,3 ', 4, 4' -diphenyl (p-phenylene ether) tetracid dianhydride, 3 ', 4, 4' -diphenyl (m-phenylene ether) tetracid dianhydride, ditrimellitic anhydride terephthalate, ditrimellitic anhydride resorcinol ester, terephthalic acid di (hydroxyl phthalic anhydride) ester or isophthalic acid di (hydroxyl phthalic anhydride) ester;
in the method, the diamine monomer based on the formula IV is selected from one of 4,4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl methane, 4 ' -diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfone or 4,4 ' -diaminobenzanilide;
based on the diamine monomer of the formula V, any one of 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4- (4-aminophenoxy) phenyl-4-aminophenyl ketone, bis (4-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, hydroquinone 1, 4-bis (4-aminobenzoate) or hydroquinone 1, 3-bis (4-aminobenzoate);
based on the diamine monomer of formula VI, one selected from 4,4 '-bis (4-aminophenoxy) diphenyl ether, 4' -bis (4-aminobenzoyl) diphenyl ether;
the organic solvent is selected from one or a mixture of two of N-methylpyrrolidone (NMP), gamma-butyrolactone, dimethyl sulfoxide (DMSO), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), Dichloromethane (DCM) or Trichloromethane (TCM);
the feeding molar ratio of the dianhydride monomer based on the formula II or the formula III to the diamine monomer based on the formula IV or the formula V or the formula VI is 0.95-1.05: 1;
the solid content of the homogeneous solution is 10-30 wt.%;
the reaction temperature is room temperature; the reaction pressure is normal pressure;
the reaction time is 4-10 hours;
the substrate material is a glass plate or a silicon wafer;
in the drying treatment step, the temperature is 50-300 ℃ and the time is 3.5-6.5 hours.
5. The method for preparing a polyimide dielectric film according to claim 4, wherein the thickness of the polyimide dielectric film prepared by the preparation method is 2-50 μm.
6. The polyimide dielectric film of claim 1, wherein the polyimide dielectric film can withstand a maximum temperature of 230 ℃.
7. The polyimide dielectric film of claim 1, wherein the polyimide dielectric film is used for a metalized film capacitor.
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