CN117820640A - Cross-linked polyimide dielectric film material and preparation method thereof - Google Patents
Cross-linked polyimide dielectric film material and preparation method thereof Download PDFInfo
- Publication number
- CN117820640A CN117820640A CN202410019381.1A CN202410019381A CN117820640A CN 117820640 A CN117820640 A CN 117820640A CN 202410019381 A CN202410019381 A CN 202410019381A CN 117820640 A CN117820640 A CN 117820640A
- Authority
- CN
- China
- Prior art keywords
- film material
- monomer
- thin film
- polyimide
- dielectric thin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 45
- 239000004642 Polyimide Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 150000004985 diamines Chemical class 0.000 claims abstract description 28
- 238000004132 cross linking Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 35
- 239000010408 film Substances 0.000 claims description 28
- 150000008064 anhydrides Chemical class 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 18
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000006114 decarboxylation reaction Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- -1 hexafluoroisopropyl Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims 1
- 239000003989 dielectric material Substances 0.000 abstract description 17
- 230000000911 decarboxylating effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229920001601 polyetherimide Polymers 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 22
- 239000004697 Polyetherimide Substances 0.000 description 21
- 238000004146 energy storage Methods 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- 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
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the technical field of dielectric material preparation, and discloses a cross-linked polyimide dielectric film material, which is prepared by introducing diamine monomer copolycondensation with carboxyl into polyimide material, and then imidizing and decarboxylating cross-linking. According to the preparation method of the cross-linked polyimide dielectric film, which is provided by the invention, no additional process technology is added on the basis of synthesizing commercial polyimide dielectric, and the surface and the cross section of the prepared dielectric film are flat and smooth and have no obvious defects.
Description
Technical Field
The invention relates to the technical field of dielectric material preparation, in particular to a cross-linked polyimide dielectric film material and a preparation method thereof.
Background
At present, with the increasing demands of social production and development, more and more electrostatic capacitors are applied to extreme environments at high temperature and high pressure, such as hybrid cars, petroleum gas exploration and aerospace equipment, and polymer dielectrics are resistant to high voltage compared with inorganic ceramic dielectricsThe advantages of the property, low dielectric loss (tan delta), light weight, good flexibility and the like become the preferred materials in the field of electrostatic capacitors. However, commercial polymer capacitors currently on the market are difficult to stably operate in a high temperature environment. For example, typical commercial polymer dielectric biaxially oriented polypropylene (BOPP) has an operating temperature of not more than 105 ℃, and particularly when the practical application temperature is more than 85 ℃, the breakdown strength (E b ) And the energy storage efficiency (eta) is severely reduced, thereby reducing the capacitance performance of the capacitor, and BOPP has another well-known disadvantage, namely the energy storage density (U) caused by low dielectric constant e ) Low, which inevitably increases the volume of the energy storage device in practical applications. Ferroelectric polyvinylidene fluoride (PVDF) due to its high dipole polarization and high U e Another typical polymer dielectric that is popular but has high ferroelectric loss due to its high dipole density, especially when the molecular chains undergo severe movement and thermal degradation in high temperature environments, the ferroelectric loss causes a severe decrease in the storage density. The development of polymeric dielectric materials that can be used in extreme environments for long periods of time and that have excellent energy storage properties is therefore a key challenge for current research.
To meet new requirements of advanced electronic devices and power systems that are lightweight, low cost, high throughput, scalable and stable operation under severe conditions, the market continues to develop polymeric dielectric materials with high temperature, high Ue and high η, such as high glass transition temperature (T g ) Commercial polyimides (Kapton), fluorene Polyesters (FPE), and Polyetherimides (PEI), and the like, and composites thereof. But these dielectric materials are at high temperatures [ ], however>Leakage current is increased under a high field of 150 ℃, conduction loss is increased, discharge efficiency is reduced, and energy storage and conversion under an extreme environment are not facilitated.
In general, for the energy storage density (U e ) The calculation formula of (2) is as follows: u (U) e = ≡ EdD, where E is the applied electric field and D is the electric displacement. U for linear dielectrics e It can also be expressed as the formula:wherein ε is 0 For vacuum dielectric constant, ε r Is a book of materialsCharacterization of dielectric constant, E b To break down the electric field. From the above, it can be seen that by E b And epsilon r Is a key factor for improving the dielectric energy storage density, and is remarkable in that E b The impact on dielectric energy storage is more pronounced.
In recent years, many researches adopt a crosslinking means to inhibit molecular chain movement at high temperature to obtain a polymer dielectric with high Tg, and meanwhile, a crosslinked network can be used for capturing a transmitted carrier and inhibiting leakage current, so that the breakdown field intensity is effectively improved. Thus, constructing a crosslinked network in a polymeric dielectric material to improve its high temperature resistance and dielectric energy storage properties is a simple and effective strategy. However, conventional thermal crosslinking generally requires the additional introduction of a toxic and expensive crosslinking agent, and particularly, a crosslinking by-product which is difficult to remove is inevitably generated during the crosslinking process, which is not only associated with environmental protection and cost problems in practical production, but also may result in degradation of Eb and significant degradation of energy storage properties. In addition, the crosslinking agent introduced into the polyimide-based polymer may act as a blocking agent for the polymer molecular chain, resulting in low polymer molecular weight and reduced heat resistance. Therefore, it is a major technical challenge to build cross-linked structures in polymer dielectrics simply and efficiently and to enable excellent capacitive properties in extreme environments.
Disclosure of Invention
In view of the above, the invention provides a cross-linked polyimide dielectric film material and a preparation method thereof, wherein the preparation method is simple and easy to operate and has controllable reaction, and the prepared cross-linked polyimide dielectric film material has excellent high-temperature energy storage performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
on one hand, the invention provides a cross-linked polyimide dielectric film material, which is prepared by introducing diamine monomer copolycondensation with carboxyl into polyimide material, and then imidizing and decarboxylating cross-linking.
Preferably, the diamine monomer with carboxyl is 3, 5-diaminobenzoic acid, which is hereinafter referred to as DBA monomer.
Preferably, the thickness of the cross-linked polyimide-based dielectric thin film material is 9-25 μm.
On the other hand, the invention also provides a preparation method of the cross-linked polyimide dielectric film material, which comprises the following steps:
(1) Dissolving an anhydride monomer in an organic reagent to obtain an anhydride solution for standby;
(2) Dissolving diamine monomer and DBA monomer in an organic reagent to obtain a diamine mixed solution for standby;
(3) Mixing and stirring the anhydride solution and the diamine mixed solution to obtain a prepolymer solution;
(4) And uniformly coating the prepolymer solution on a glass plate, and carrying out imidization and decarboxylation crosslinking in a vacuum oven to obtain the crosslinked polyimide dielectric film material.
Preferably, the acid anhydride monomer in the step (1) includes any one or more of 4,4' - (4, 4' -isopropyldiphenoxy) diphthalic anhydride (i.e. BPADA), 4' - (hexafluoroisopropyl) diphthalic anhydride (6 FDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), and 3, 4-diphenyl sulfone tetracarboxylic dianhydride (DSDA);
the organic reagent comprises any one of N-methyl pyrrolidone (NMP), N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF) and m-phenol;
the temperature at which the anhydride monomer is dissolved in the organic reagent is 15-25 ℃.
Preferably, the ratio of diamine monomer to DBA monomer in step (2) is (1-100): 1-100;
the diamine monomer comprises any one or more of 1, 3-phenylenediamine, 4 '-diaminodiphenyl ether, 1, 4-phenylenediamine and 4,4' -diaminodiphenyl sulfone.
Preferably, the ratio of the sum of the amounts of the diamine monomer and DBA monomer to the amount of anhydride monomer species in step (3) is (1-1.02): 1-1.02.
Preferably, the conditions of mixing and stirring in the step (3) are as follows: stirring and reacting for 12-36h under ice bath condition.
Preferably, the vacuum oven in the step (4) adopts a heating program to carry out imidization and decarboxylation crosslinking, wherein the heating program is as follows:
preserving heat for 2-3h at 75-85 ℃;
heating from 75-85deg.C to 95-110deg.C, and maintaining for 1-2h;
heating from 95-110deg.C to 140-160deg.C, and maintaining for 0.8-1 hr;
heating from 140-160deg.C to 190-210 deg.C, and maintaining for 0.8-1 hr;
heating from 190-210 deg.c to 240-280 deg.c and maintaining for 0.8-1 hr;
heating to 330-370 deg.C from 240-280 deg.C, and maintaining for 1-2h.
Preferably, before step (4) is performed, the method further comprises: the precursor solution is evacuated to remove the gas.
The invention provides a cross-linked polyimide dielectric film material and a preparation method thereof, which have the beneficial effects that compared with the prior art:
according to the preparation method of the cross-linked polyimide dielectric film, which is provided by the invention, no additional process technology is added on the basis of synthesizing commercial polyimide dielectric, and the surface and the cross section of the prepared dielectric film are flat and smooth and have no obvious defects.
The carboxyl in the invention is used as a crosslinking functional group, the control of the crosslinking degree among molecular chains can be realized by adjusting the content of DBA, the thermal expansion coefficient and the free volume of the polyimide dielectric film are reduced by crosslinking, the thermal dimensional stability of the dielectric material in an extreme environment is facilitated, the injection and the transportation of carriers under high temperature and high field are inhibited, and the leakage current is reduced; in addition, the carboxyl which is not crosslinked can be used as a functional group with dipole and high electron affinity for improving dipole polarization and adsorbing injected electrons and inhibiting conductivity loss, so that the breakdown electric field and the energy storage density of the commercial polyimide dielectric material under extreme environments are comprehensively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the synthesis principle of a cross-linked polyimide-based dielectric thin film material;
FIG. 2 is a FT-I R of the crosslinked polyetherimide of example 1;
FIG. 3 is a TGA graph of the cross-linked polyetherimide of example 1;
FIG. 4 is an SEM image of a crosslinked polyetherimide of example 1;
FIG. 5 is a TMA graph of the crosslinked polyetherimide of example 1;
FIG. 6 is a positron annihilation lifetime spectrum of the crosslinked polyetherimide of example 1;
FIG. 7 is a dielectric spectrum of the crosslinked polyetherimide of example 1;
FIG. 8 is a graph of the energy storage properties of the crosslinked polyetherimide of example 1 at 250 ℃;
fig. 9 is a graph of the performance of dielectric materials of uncrosslinked PEI and crosslinked system 80 PEI.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
On one hand, the embodiment of the invention provides a cross-linked polyimide dielectric film material, which is prepared by introducing diamine monomer copolycondensation with carboxyl into polyimide material, and then imidizing and decarboxylating cross-linking.
Specifically, the preparation method of the cross-linked polyimide dielectric film material comprises the following steps:
s100, under the nitrogen atmosphere, dissolving an anhydride monomer in an organic reagent, and stirring and dissolving in a low-temperature environment to obtain an anhydride solution for later use.
In this step, the acid anhydride monomer includes any one or more of 4,4' - (4, 4' -isopropyldiphenoxy) diphthalic anhydride (i.e., BPADA), 4' - (hexafluoroisopropyl) diphthalic anhydride (6 FDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3, 4-diphenyl sulfone tetracarboxylic dianhydride (DSDA);
the organic reagent comprises any one of N-methyl pyrrolidone (NMP), N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF) and m-phenol;
the temperature at which the acid anhydride monomer is dissolved in the organic reagent is 15 to 25℃and may be, for example, 15℃and 20℃and 25 ℃.
S200, dissolving diamine monomer and DBA monomer in an organic reagent to obtain a diamine mixed solution for standby.
In this step, the diamine monomer includes any one or more of 1, 3-Phenylenediamine (PDA), 4 '-diaminodiphenyl ether (ODA), 1, 4-phenylenediamine (p-PDA), 4' -diaminodiphenyl sulfone (BOS).
The proportion of the diamine monomer to the DBA is (1-100): (100-1), for example, the proportion can be 10:90, 20:80, 40:60, 50:50, 60:40, 80:20, 90:10 and the like, the crosslinking degree of the polymer is increased along with the increase of the proportion, the mechanical property such as Young modulus of the obtained polymer is improved, the heat resistance is greatly improved, and therefore the application of the polymer dielectric material in an extreme environment is improved, but the proportion is too large, the crosslinking degree is too large, the biphenyl structure of the polymer can lead to shallow traps, the energy storage in the extreme environment is not facilitated, and therefore, the crosslinking degree needs to be moderately controlled.
S300, mixing and stirring the anhydride solution and the diamine mixed solution, and fully stirring and reacting for 12-36h under the ice bath condition to obtain a viscous precursor solution.
In the step, the ratio of the sum of the amounts of the diamine monomer and the DBA monomer to the amount of the anhydride monomer is (1-1.02): 1-1.02), the obtained prepolymer solution is a terpolymer, and the reaction can be carried out under the ice bath condition so as to promote the prepolymerization reaction to be carried out in the direction of generating a polymer chain.
The carboxyl in the invention is used as a crosslinking functional group, the control of the crosslinking degree among molecular chains can be realized by adjusting the content of DBA, the thermal expansion coefficient and the free volume of the polyimide dielectric film are reduced by crosslinking, the thermal dimensional stability of the dielectric material in an extreme environment is facilitated, the injection and the transportation of carriers under high temperature and high field are inhibited, and the leakage current is reduced; in addition, the carboxyl which is not crosslinked can be used as a functional group with dipole and high electron affinity for improving dipole polarization and adsorbing injected electrons and inhibiting conductivity loss, so that the breakdown electric field and the energy storage density of the commercial polyimide dielectric material under extreme environments are comprehensively improved.
S400, vacuumizing the precursor solution to remove gas in the solution, uniformly coating the precursor solution on a clean glass plate, and carrying out imidization and decarboxylation crosslinking in a vacuum oven to obtain the crosslinked polyimide dielectric film material.
In the step, imidization and decarboxylation crosslinking are carried out in the vacuum oven by adopting a heating program, wherein the heating program is as follows:
preserving heat for 2-3h at 75-85 ℃;
heating from 75-85deg.C to 95-110deg.C, and maintaining for 1-2h;
heating from 95-110deg.C to 140-160deg.C, and maintaining for 0.8-1 hr;
heating from 140-160deg.C to 190-210 deg.C, and maintaining for 0.8-1 hr;
heating from 190-210 deg.c to 240-280 deg.c and maintaining for 0.8-1 hr;
heating to 330-370 deg.C from 240-280 deg.C, and maintaining for 1-2h.
The invention adopts heating under vacuum condition, which can effectively avoid the influence of air and other impurities, and the slow gradient heating process is beneficial to the imine cyclization of the polymer.
In another aspect of the present invention, a crosslinked polyimide-based dielectric thin film material prepared by the method described above, having a thickness of 9 to 25 μm, is provided. Thus, the crosslinked polyimide-based dielectric thin film material has all the features and advantages of the method described above, and will not be described in detail herein. In general, the cross-linked polyimide dielectric film material has outstanding high-temperature energy storage performance, stable and reliable performance, and is suitable for industrialized mass production.
The invention is illustrated below by means of specific examples, which are given for illustrative purposes only and do not limit the scope of the invention in any way, as will be understood by those skilled in the art. In addition, in the examples below, reagents and equipment used are commercially available unless otherwise specified. If in the following examples specific treatment conditions and treatment methods are not explicitly described, the treatment may be performed using conditions and methods well known in the art.
Example 1
(1) Adding 0.6mmo of BPADA under nitrogen atmosphere, adding 1-1.5mL of NMP, stirring and dissolving at 15-25 ℃ to obtain an anhydride solution, preparing PDA and DBA (total 0.6mmo of) according to a proportion, dissolving in 1-1.5mL of NMP, adding diamine mixed solution into the anhydride solution after the two monomers are completely dissolved, and stirring and reacting for 24 hours under ice bath condition after adding to obtain PAA solution;
(2) And (3) placing the PAA solution under vacuum to remove redundant gas, pouring the PAA solution on a clean glass plate for coating, placing the PAA solution on the clean glass plate for 80 ℃/2.5h, 100 ℃/1.5h, 150 ℃/1h, 200 ℃/1h, 250 ℃/1h, 350 ℃/1.5h, cooling, stripping the polymer by warm water, and drying the polymer at 80 ℃ to obtain the crosslinked polyetherimide film.
In this example, the study was performed with the ratio of PDA to DBA as a variable, and the specific ratio of PDA to DBA was 1:0 (PE I), 8:2 (20 PEI), 6:4 (40 PEI), 4:6 (60 PEI), 2:8 (80 PE I), 0:1 (100 PE I) and performance testing was performed on each of the resulting crosslinked polyetherimide films, see FIGS. 2-8 for results.
Wherein the electrical property test of the crosslinked polyetherimide film adopts the following method: designing a metal mask plate with a round hole diameter of 2mm, clamping the prepared dielectric material between 2 metal mask plates, symmetrically sputtering gold electrodes on the upper surface and the lower surface, sputtering the upper surface and the lower surface for 140s under the power of 120W, and then performing performance test by using a ferroelectric workstation and an impedance analyzer.
The presence of a crosslinked structure can be illustrated by the FT-I R plot of the crosslinked polyetherimide at each PDA and DBA ratio condition shown in FIG. 2;
the decarboxylated cross-linked structure can be illustrated by the TGA diagram of cross-linked polyetherimide at a PDA to DBA ratio of 2:8 as shown in FIG. 3;
as shown in fig. 4, which is an SEM image of the cross-linked polyetherimide at various PDA and DBA ratios, the cross-linked film was demonstrated to be free of significant defects;
FIG. 5 is a TMA graph of crosslinked polyetherimide at a PDA to DBA ratio of 2:8, illustrating the thermal dimensional stability of the crosslinked film;
FIG. 6 is a positron annihilation lifetime spectrum of a cross-linked polyetherimide at a PDA to DBA ratio of 2:8, demonstrating that cross-linking reduces free volume;
as shown in fig. 7, which shows the dielectric spectra of the crosslinked polyetherimide at various PDA and DBA ratios, it is demonstrated that the non-crosslinked carboxyl groups and crosslinked structure are beneficial to increase dipole density, thereby increasing polarization;
FIG. 8 is a graph showing the energy storage properties of crosslinked polyetherimide at 250℃at a PDA to DBA ratio of 2:8, showing that the optimum composition of the polymer dielectric material achieved 3.65J/cm at 250 ℃ 3 The efficiency (. Eta.) was 92.69%. This demonstrates that the presence of the crosslinked structure is advantageous for commercial polymers to highlight the service temperature limits of energy storage applications and to suppress losses, improving energy storage performance in extreme environments.
Comparative example 1
(1) Adding 0.6mmo of BPADA under nitrogen atmosphere, adding 1-3mL of NMP, stirring and dissolving at 15-25 ℃ to obtain an anhydride solution, preparing PDA and DBA (total 0.6mmo of) according to a ratio of 2:8, dissolving in 1-3mL of NMP, adding diamine mixed solution into the anhydride solution after the two monomers are completely dissolved, and stirring and reacting for 24 hours under ice bath condition after adding to obtain PAA solution;
(2) And (3) placing the PAA solution in a vacuum condition to remove redundant gas, pouring the PAA solution on a clean glass plate for coating, placing the PAA solution in a step-type temperature rising and heat preservation mode at 70-350 ℃ for 8.5 hours, cooling, stripping the polymer with warm water, and placing the polymer in a temperature of 80 ℃ for drying to obtain the cross-linked polyetherimide film.
Comparative example 2
The comparative example is a preparation method of a conventional crosslinked polyetherimide film in the current industry, and when the diamine monomer is only PDA, the preparation process is as follows:
(1) Adding 0.6mmo of BPADA under nitrogen atmosphere, adding 1-3mL of NMP, stirring and dissolving at 15-25 ℃ to obtain an anhydride solution, dissolving PDA (0.6 mmo) in 1-3mL of NMP, dropwise adding a diamine solution into the anhydride solution after the two monomers are completely dissolved, and stirring and reacting for 24 hours under ice bath condition after adding to obtain a prepolymer solution;
(2) The prepolymer solution was placed under vacuum to remove excess gas, then poured onto a clean glass plate for coating, then placed at 70-350 ℃ for a total of 8.5 hours of stepwise heating and heat preservation, cooled, the polymer was peeled off with warm water, and then placed at 80 ℃ for drying, thus obtaining a commercial polyetherimide film, namely PE I, with structural characterization and thermal characterization as shown in example 1.
The polyetherimide film prepared in comparative example 2 can only be applied at a temperature of no more than 200 ℃ and the polymer has poor capacitance performance, as shown in figure 9, and the result shows that PE I obtains 2.25J/cm at 200 DEG C 3 While the energy storage density of the crosslinked dielectric 80PEI is 5.67J/cm 3 。
In the description of the present specification, reference to the terms "one embodiment," "another embodiment," "yet another embodiment," "some embodiments," "other embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction. In addition, it should be noted that, in this specification, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A cross-linked polyimide dielectric film material is characterized in that diamine monomer copolycondensation with carboxyl is introduced into the polyimide material, and then imidization and decarboxylation cross-linking are carried out, so that the cross-linked polyimide dielectric film material is obtained.
2. The crosslinked polyimide-based dielectric thin film material according to claim 1, wherein the diamine monomer having a carboxyl group is 3, 5-diaminobenzoic acid.
3. The crosslinked polyimide-based dielectric thin film material according to claim 1, wherein the thickness of the crosslinked polyimide-based dielectric thin film material is 9 to 25 μm.
4. A method for producing the crosslinked polyimide-based dielectric thin film material according to any one of claims 1 to 3, comprising the steps of:
(1) Dissolving an anhydride monomer in an organic reagent to obtain an anhydride solution for standby;
(2) Dissolving diamine monomer and DBA monomer in an organic reagent to obtain a diamine mixed solution for standby;
(3) Mixing and stirring the anhydride solution and the diamine mixed solution to obtain a prepolymer solution;
(4) And uniformly coating the prepolymer solution on a glass plate, and carrying out imidization and decarboxylation crosslinking in a vacuum oven to obtain the crosslinked polyimide dielectric film material.
5. The method for producing a crosslinked polyimide-based dielectric thin film material according to claim 4, wherein the acid anhydride monomer in the step (1) comprises any one or more of 4,4' - (4, 4' -isopropyldiphenoxy) diphthalic anhydride, 4' - (hexafluoroisopropyl) diphthalic anhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, and 3, 4-diphenyl sulfone tetracarboxylic dianhydride;
the organic reagent comprises any one of N-methyl pyrrolidone, N-dimethylacetamide, N-dimethylformamide and m-phenol;
the temperature at which the anhydride monomer is dissolved in the organic reagent is 15-25 ℃.
6. The method of producing a crosslinked polyimide-based dielectric thin film material according to claim 4, wherein the ratio of the diamine monomer to the DBA monomer in the step (2) is (1-100): 1-100;
the diamine monomer comprises any one or more of 1, 3-phenylenediamine, 4 '-diaminodiphenyl ether, 1, 4-phenylenediamine and 4,4' -diaminodiphenyl sulfone.
7. The method of producing a crosslinked polyimide-based dielectric thin film material according to claim 4, wherein the ratio of the sum of the amounts of the diamine monomer and the DBA monomer to the amount of the acid anhydride monomer in the step (3) is (1-1.02): 1-1.02.
8. The method for producing a crosslinked polyimide-based dielectric thin film material according to claim 4, wherein the conditions for mixing and stirring in the step (3) are: stirring and reacting for 12-36h under ice bath condition.
9. The method for producing a crosslinked polyimide-based dielectric thin film material according to claim 4, wherein the vacuum oven in step (4) is subjected to imidization and decarboxylation crosslinking by a temperature-increasing program of:
preserving heat for 2-3h at 75-85 ℃;
heating from 75-85deg.C to 95-110deg.C, and maintaining for 1-2h;
heating from 95-110deg.C to 140-160deg.C, and maintaining for 0.8-1 hr;
heating from 140-160deg.C to 190-210 deg.C, and maintaining for 0.8-1 hr;
heating from 190-210 deg.c to 240-280 deg.c and maintaining for 0.8-1 hr;
heating to 330-370 deg.C from 240-280 deg.C, and maintaining for 1-2h.
10. The method for producing a crosslinked polyimide-based dielectric thin film material according to claim 4, further comprising, before the step (4): the precursor solution is evacuated to remove the gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410019381.1A CN117820640A (en) | 2024-01-05 | 2024-01-05 | Cross-linked polyimide dielectric film material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410019381.1A CN117820640A (en) | 2024-01-05 | 2024-01-05 | Cross-linked polyimide dielectric film material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117820640A true CN117820640A (en) | 2024-04-05 |
Family
ID=90513271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410019381.1A Pending CN117820640A (en) | 2024-01-05 | 2024-01-05 | Cross-linked polyimide dielectric film material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117820640A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110269915A1 (en) * | 2008-06-16 | 2011-11-03 | Georgia Tech Research Corporation | Thermally crosslinked polymeric compositions and methods of making the same |
| KR20180032787A (en) * | 2016-09-23 | 2018-04-02 | 주식회사 엘지화학 | Polyimide precursor solution and method for preparing polyimide film using same |
| CN112625278A (en) * | 2020-12-08 | 2021-04-09 | 北京科技大学 | Low-dielectric polyimide film and preparation method thereof |
| CN113831582A (en) * | 2021-10-14 | 2021-12-24 | 浙江中烟工业有限责任公司 | Cross-linked polyimide-based composite aerogel and preparation method thereof |
-
2024
- 2024-01-05 CN CN202410019381.1A patent/CN117820640A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110269915A1 (en) * | 2008-06-16 | 2011-11-03 | Georgia Tech Research Corporation | Thermally crosslinked polymeric compositions and methods of making the same |
| KR20180032787A (en) * | 2016-09-23 | 2018-04-02 | 주식회사 엘지화학 | Polyimide precursor solution and method for preparing polyimide film using same |
| CN112625278A (en) * | 2020-12-08 | 2021-04-09 | 北京科技大学 | Low-dielectric polyimide film and preparation method thereof |
| CN113831582A (en) * | 2021-10-14 | 2021-12-24 | 浙江中烟工业有限责任公司 | Cross-linked polyimide-based composite aerogel and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| CHIEN-CHIANG CHEN ET AL.,: "Plasticization-resistant hollow fiber membranes for CO2/CH4 separation based on a thermally crosslinkable polyimide", 《JOURNAL OF MEMBRANE SCIENCE》, vol. 382, 16 August 2011 (2011-08-16), pages 212 - 221, XP028288225, DOI: 10.1016/j.memsci.2011.08.015 * |
| CHIEN-CHIANG CHEN ETAL.,: "Sub-Tg Cross-Linking of a Polyimide Membrane for Enhanced CO2 Plasticization Resistance for Natural Gas Separation", 《MACROMOLECULES》, vol. 44, 13 July 2011 (2011-07-13), pages 6046 - 6056 * |
| WULIN QIU ET AL.,: "Gas separation performance of 6FDA-based polyimides with different chemical structures", 《POLYMER》, vol. 54, 19 September 2013 (2013-09-19), pages 6226 - 6235, XP028734520, DOI: 10.1016/j.polymer.2013.09.007 * |
| 张良: "《复合材料原理》", vol. 1, 31 March 2021, 天津大学出版社, pages: 34 * |
| 谢希文 等: "《材料科学与工程导论》", vol. 1, 31 December 1991, 北京航空航天大学出版社, pages: 194 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11987670B2 (en) | Polyimide film for graphite sheet having improved thermal conductivity, method for manufacturing same, and graphite sheet manufactured using same | |
| JP6865687B2 (en) | Method for manufacturing polyimide film using particles with pores and polyimide film with low dielectric constant | |
| KR101831009B1 (en) | Aqueous polyimide precursor solution composition and method for producing aqueous polyimide precursor solution composition | |
| Han et al. | Enhanced dielectric properties of sandwich‐structured biaxially oriented polypropylene by grafting hyper‐branched aromatic polyamide as surface layers | |
| TW201936737A (en) | Polyimide film, manufacturing method thereof, graphite sheet prepared by using the same and electronic device | |
| CN108794748B (en) | Polyimide film with low dielectric constant and preparation method thereof | |
| CN113604043B (en) | Polyimide film with low moisture absorption and high cohesiveness and preparation method thereof | |
| JPH06107791A (en) | Low permittivity fluorinated polymer and its production | |
| CN108164699B (en) | Polymer film dielectric medium and preparation method and application thereof | |
| US20110220179A1 (en) | Assemblies comprising a thermally and dimensionally stable polyimide film, an electrode and an absorber layer, and methods relating thereto | |
| CN117285820B (en) | Polyimide high-temperature dielectric composite film and preparation method thereof | |
| CN108586740B (en) | Polyimide containing fluorene or fluorenone structure and preparation method and application thereof | |
| CN117801274A (en) | Cross-linked polyimide insulating medium film and preparation method and application thereof | |
| Li et al. | Preparation of fluorinated poly (benzoxazole-co-imide) with low dielectric constants based on the thermal rearrangement reaction of o-hydroxy polyimides | |
| CN111886285A (en) | Polyimide film including omni-directional polymer chain, method of manufacturing the same, and graphite sheet manufactured using the same | |
| CN108841003B (en) | Polyimide dielectric film and preparation method and application thereof | |
| CN117820640A (en) | Cross-linked polyimide dielectric film material and preparation method thereof | |
| CN112608597B (en) | High-energy-storage-density polymer composite material and preparation method thereof | |
| KR20100124624A (en) | High dielectric polyimide-inorganic composites and its preparation | |
| Bacosca et al. | Structure-property correlation of bromine substitution in polyimides | |
| Diaham et al. | Improvement of polyimide electrical properties during short-term of thermal aging | |
| Wang et al. | All organic polyimide‐based composite films with high intrinsic polarization for superior energy density and low dielectric loss | |
| CN113166453A (en) | Graphite sheet prepared from polyimide film having excellent orientation properties and method for preparing same | |
| US20170298185A1 (en) | Microporous polyimide sponge and method for producing the same | |
| CN118290785B (en) | Crosslinked polyetherimide dielectric film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |