CN115536880B - Polyarylether ketone-based dielectric film containing rigid annular structure, and preparation method and application thereof - Google Patents
Polyarylether ketone-based dielectric film containing rigid annular structure, and preparation method and application thereof Download PDFInfo
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- CN115536880B CN115536880B CN202211135971.8A CN202211135971A CN115536880B CN 115536880 B CN115536880 B CN 115536880B CN 202211135971 A CN202211135971 A CN 202211135971A CN 115536880 B CN115536880 B CN 115536880B
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- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004146 energy storage Methods 0.000 claims abstract description 25
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 10
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- FKVQQQMZAGNIRP-UHFFFAOYSA-N 2-[2-(1h-benzimidazol-2-yl)pyridin-3-yl]-1h-benzimidazole Chemical compound C1=CC=C2NC(C3=NC=CC=C3C=3NC4=CC=CC=C4N=3)=NC2=C1 FKVQQQMZAGNIRP-UHFFFAOYSA-N 0.000 claims description 6
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- NSTFTBDDHJZGLB-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-2-adamantyl]phenol Chemical compound C1=CC(O)=CC=C1C1C(C=2C=CC(O)=CC=2)(C2)CC3CC2CC1C3 NSTFTBDDHJZGLB-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- -1 methacryloxypropyl Chemical group 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 5
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005357 flat glass Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000009365 direct transmission Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000010248 power generation Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000137 annealing Methods 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000005266 casting Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
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- 230000010287 polarization Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4031—(I) or (II) containing nitrogen
- C08G65/4037—(I) or (II) containing nitrogen in ring structure, e.g. pyridine group
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4068—(I) or (II) containing elements not covered by groups C08G65/4018 - C08G65/4056
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
Abstract
The invention provides a polyaryletherketone-based dielectric film containing a rigid annular structure, and a preparation method and application thereof. The method is characterized in that a rigid cyclic structure is introduced into a molecular main chain of the polyaryletherketone in the synthesis process of the polyaryletherketone to obtain a novel polyaryletherketone copolymer, and the novel polyaryletherketone copolymer is further prepared into a dielectric film. The introduction of the rigid annular structure not only improves the heat resistance of the copolymer film, but also effectively reduces the leakage current and improves the breakdown field strength and the energy storage density. The copolymer film can be conveniently prepared by adopting a solution casting method, and the high-temperature-resistant high-energy-storage dielectric film is obtained after high-temperature annealing treatment. The stable use temperature of the dielectric film is not lower than 150 ℃, the breakdown strength of the dielectric film reaches 500-750MV/m, and the energy storage density reaches 5.0-10.0J/cm at high temperature 3 The energy release efficiency is not less than 90%. Meanwhile, after 5000 times of capacitor charge and discharge tests, the release efficiency is not lower than 90%, and the key indexes are superior to those of the existing high-temperature-resistant commercial engineering film.
Description
Technical Field
The invention relates to the technical field of organic dielectric film synthesis, in particular to a polyarylether ketone-based dielectric film containing a rigid ring structure, and a preparation method and application thereof.
Background
The pulse capacitor with high temperature resistance and high energy storage density has an indispensable important application in the field of army and civil high-end equipment such as ultra-high voltage, high-speed rail crossing, all-electric warship machines, electromagnetic energy equipment and the like. At present, biaxially oriented polypropylene (BOPP) has the advantages of high voltage resistance (700 MV/m), low loss (tan delta is about 0.02%), self-healing, low cost and the like, and is widely applied to various power systems and film capacitors for electronic equipment. But the BOPP has a low long-term usable temperature, less than 85 ℃, when the temperature is increased to more than 105 ℃, the leakage current is increased, the loss is increased sharply, and particularly under the action of high temperature and high electric field, the internal conductivity of the dielectric material is increased exponentially, the leakage current is increased suddenly, the energy storage density and the charge and discharge efficiency are reduced, the thermal instability state is generated in the capacitor, the electrical insulation failure is caused, and the service life is shortened greatly.
For example, a power inverter may convert dc power provided by a battery into ac power required to drive a traction motor, which is one of the important electronic components of an electric vehicle, and a key component in the inverter includes a pulse capacitor. BOPP is currently the best commercial dielectric film but can only operate at temperatures below 105 ℃. In the inverter, the operating temperature is higher than 140 ℃, so a secondary cooling system with the temperature set to 65 ℃ is required to be introduced into the inverter, so that the long-term stable operation of the inverter is ensured. The design of the electric power system is provided with extra weight and volume, and the cost reduction and efficiency improvement of the electric automobile are not facilitated. Therefore, the development of a novel high-temperature-resistant high-energy-storage dielectric film which replaces BOPP is urgently needed in the existing market, so that the aims of small volume and low cost are fulfilled.
Disclosure of Invention
The invention provides a novel high-temperature-resistant high-energy-storage PAEKs polyarylether ketone-based dielectric film containing rigid annular structures, and a preparation method and application thereof, and the specific technical scheme is as follows:
the invention provides a preparation method of a polyaryletherketone dielectric film containing a rigid annular structure, which comprises the steps of preparing a rigid annular structure monomer; then the rigid ring structure monomer is used as a raw material to prepare polyaryletherketone containing a rigid ring structure; finally, polyaryletherketone containing a rigid ring structure is used as a raw material to prepare the polyaryletherketone dielectric film containing the rigid ring structure.
Preferably, the method comprises the following specific steps: 1) Preparing a rigid cyclic structure monomer, wherein the rigid cyclic structure monomer is one or more of bis (2-benzimidazolyl) pyridine, bis (4-hydroxyphenyl) adamantane and methacryloxypropyl POSS; 2) Preparing polyaryletherketone containing a rigid cyclic structure, taking 4,4' -difluorobenzophenone, diallyl bisphenol A and the rigid cyclic structure monomer as raw materials, adding a solvent, a water scavenger and a salifying agent, and mixing to obtain a solution; carrying out the following reaction under the protection of nitrogen, carrying out the reaction through a three-stage heating process, carrying out the pre-polymerization salification reaction, heating toluene to reflux for removing water, and finally carrying out the polycondensation reaction at high temperature to obtain a crude product for treatment; pouring the crude product into aqueous solution of hydrochloric acid, crushing, washing with hot water and ethanol respectively, and finally drying to obtain the polyaryletherketone containing the rigid annular structure; 3) Preparing cross-linked polyaryletherketone, stirring the polyaryletherketone containing the rigid ring structure in DMAc solution to obtain stable and uniform mixed solution, coating the mixed solution on a flat glass plate, and drying the solvent at 70 ℃ to form a film; and then placing the film into an oven, and treating at a high temperature of 180-200 ℃ for 6 hours to obtain the polyaryletherketone-based dielectric film with the rigid annular structure.
Preferably, in the step (2), the molar ratio of the diallyl bisphenol a to the rigid cyclic monomer is (9:1) to (7:3).
Preferably, in the step (2), the mass of the rigid cyclic structure monomer in the solvent is 5% to 30%.
Preferably, in the step (3), the solid content of the rigid cyclic structure monomer in the mixed solution is 5 to 30 percent
Preferably, in step (2), the solvent is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone; the water scavenger is toluene; the salifying agent is anhydrous potassium carbonate.
Preferably, the thickness of the high temperature resistant dielectric film is 5 μm to 12 μm; the dielectric constant of the high-temperature resistant dielectric film is 3.0-5.0.
Preferably, the breakdown strength of the high-temperature resistant dielectric film at 150 ℃ is 500 MV/m-750 MV/m, and the energy storage density is 5.0J/cm 3 ～10.0J/cm 3 The energy storage efficiency is not lower than 90%.
The invention also provides a polyaryletherketone-based dielectric film containing a rigid annular structure, such as the polyaryletherketone-based dielectric film containing the rigid annular structure prepared by the preparation method of the polyaryletherketone-based dielectric film containing the rigid annular structure.
The invention also provides application of the polyaryletherketone-based dielectric film containing the rigid annular structure in the fields of capacitors, electric automobile inverters, electric power flexible direct transmission systems, new energy power generation and underground oil and gas exploration.
Compared with the prior art, the technical scheme provided by the invention has at least the following advantages:
the invention provides a polyaryletherketone dielectric film containing a rigid ring structure, a preparation method and application thereof. The introduction of the rigid annular structure is beneficial to improving the heat resistance of the copolymer film, and can effectively reduce the leakage current and improve the breakdown field strength and the energy storage density of the copolymer film. The copolymer film can be conveniently prepared by adopting a solution casting method, and the high-temperature-resistant high-energy-storage dielectric film is obtained after high-temperature annealing treatment. The stable use temperature of the dielectric film prepared by the invention is not lower than 150 ℃, the breakdown strength reaches 500 MV/m-750 MV/m at high temperature, and the energy storage density reaches 5.0J/cm 3 ～10.0J/cm 3 The energy release efficiency is not less than 90%. Meanwhile, after 5000 times of capacitor charge and discharge tests, the release efficiency is not lower than 90%, and the key indexes are superior to those of the existing high-temperature-resistant commercial engineering film, so that the high-temperature-resistant commercial engineering film has the advantages of high temperature resistance, high energy storage, easiness in processing and the like.
Drawings
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings, which are not to be construed as limiting the embodiments unless specifically indicated otherwise.
FIG. 1 is a schematic diagram of the synthetic route of a polyaryletherketone-based dielectric film containing rigid cyclic structures prepared in example 1 of the present invention;
FIG. 2 is a graph showing the dielectric constant and dielectric loss of a polyaryletherketone-based dielectric film containing a rigid ring structure prepared in example 1 according to the present invention as a function of frequency;
FIG. 3 is a Weber distribution diagram of the breakdown strength of a polyaryletherketone-based dielectric film containing rigid cyclic structures prepared in example 1 of the present invention at 150 ℃;
FIG. 4 is a schematic representation of D-E loop at 150℃for a rigid cyclic structure containing polyaryletherketone dielectric film prepared in example 1 of the present invention at 0-650 MV/m;
FIG. 5 is a graph showing the comparison of energy storage density and energy storage efficiency at 150℃for a polyaryletherketone based dielectric film comprising a rigid cyclic structure prepared in example 1 of the present invention.
FIG. 6 is a graph showing the energy storage density and release efficiency of a polyaryletherketone-based dielectric film having a rigid ring structure prepared in example 1 of the present invention after 5000 cycles.
Detailed Description
The existing commercial high-temperature-resistant high-molecular material has the defects that the energy storage performance, particularly the energy release efficiency, is greatly reduced due to the sudden decrease of the resistivity and the increase of the leakage current at high temperature, and the working stability and the service period of the capacitor are greatly reduced.
The inventors have found that Polyaryletherketones (PAEKs) are an important class of high performance aromatic polymers with excellent thermal stability, mechanical properties and chemical resistance. PAEKs can be obtained by polycondensation of a variety of multifunctional monomers by nucleophilic reaction. The molecular structures of the modified polyethylene glycol can be highly adjustable, are easy to functionalize, and can realize wide adjustment of temperature resistance, polarity and flexibility. By a chemical synthesis modification method, a high temperature resistant and charge transport regulating functional group or structure is introduced into a main chain or a side chain of the PAEKs polymer, and the PAEKs polymer with high temperature resistant and high energy storage properties is hopeful to be prepared.
The invention provides a preparation method of a polyaryletherketone-based dielectric film containing a rigid annular structure, which comprises the following steps:
preparation of rigid cyclic monomers including, but not limited to, bis (2-benzimidazolyl) pyridine, bis (4-hydroxyphenyl) adamantane, methacryloxypropyl POSS, norbornene, and the like. The monomers were washed to neutrality in dilute NaOH solution, HCl solution or chloroform solution. Suction filtration and recrystallization. The product was dried in vacuo at 50℃to give a purified monomer containing a rigid cyclic structure.
Diallyl bisphenol A,4 '-difluorobenzophenone and the monomer containing a rigid structure are taken as raw materials, the mol ratio of the diallyl bisphenol A, the 4,4' -difluorobenzophenone and the monomer containing a rigid structure is 9:10:1, DMAc is taken as a solvent, toluene is taken as a water scavenger, anhydrous potassium carbonate is taken as a salifying agent, the raw materials are mixed into a solution, and the following reaction is carried out under the protection of nitrogen.
Wherein the reaction temperature is three-stage, and the prepolymerization is carried out at 130-140 ℃; secondly, heating to 140-150 ℃ to carry out azeotropic dehydration of toluene and simultaneously carrying out salification reaction; finally, the reaction is carried out for 6 hours at 180-200 ℃ to obtain a crude product.
The post-treatment is to pour the crude product into aqueous solution of hydrochloric acid and crush, then wash with hot water and ethanol respectively, and finally dry to obtain the crosslinkable polyaryletherketone containing rigid cyclic structure.
Weighing 0.1-1 g of the prepared novel polyaryletherketone, and stirring in 5-50 mL of DMAc solution for more than 4 hours to obtain a stable and uniform mixed solution.
The mixed solution is coated on a flat glass plate, and the solvent is dried at 70 ℃ to form a film. And then placing the crosslinkable polyaryletherketone film containing the rigid annular structure into an oven, and treating at a high temperature of 180 ℃ for 6 hours to obtain the crosslinked high-temperature-resistant dielectric film. In particular, the introduced rigid structure can improve the temperature resistance of the polyaryletherketone group, and the crosslinked structure can improve the toughness of the film and the compressive strength of the film.
The present invention will be described in detail with reference to the following embodiments.
Example 1 provides a method for preparing a polyaryletherketone-based dielectric film containing a rigid ring structure, which specifically comprises the following steps:
the first step: at N 2 Under the condition that polyphosphoric acid is used as a condensing agent and a solvent, o-phenylenediamine and dipicolinic acid are used as monomers, the molar ratio of the two is 2:1, a mixed solution is prepared, and the mixed solution is reacted for 6 to 8 hours at the temperature of 200 to 210 ℃. The reaction product was washed to neutrality in 15% by mass NaOH solution. Suction filtration and recrystallization from ethanol. The product was dried in vacuo at 50℃to give purified bis (2-benzimidazolyl) pyridine monomer.
And a second step of: into a 250mL three-necked flask equipped with a nitrogen port equipped with a thermometer and a stirring blade and a water-carrying device, diene bisphenol A (6.618 g,0.02 mol), 4' -difluorobenzophenone (5.455 g,0.025 mol), bis (2-benzimidazolyl) pyridine (1.555 g,0.005 mol) and then anhydrous potassium carbonate (7.60 g,0.055 mol) were successively introduced.
And a third step of: adding 40-50 mL of sulfolane solvent and 10-20 mL of toluene as a water-carrying agent into the system, introducing nitrogen, and heating until the toluene is refluxed with water under the stirring condition, thereby ensuring that the water in the system is removed.
Fourth step: and (3) sequentially heating the system to 130-140 ℃, 140-150 ℃ and 180-200 ℃ by using a stage heating method to react. After the reaction is completed, discharging the mixture solution into a hydrochloric acid aqueous solution, crushing the mixture solution by a powder machine, and washing the mixture solution for a plurality of times by boiling distilled water and ethanol to remove residual inorganic salts and solvents. Drying in an oven to obtain the polyaryletherketone polymer containing the rigid group.
Fifth step: 200mg of the polyaryletherketone polymer containing a rigid group was placed in a 20mL sample bottle, and 10mLN, N' -dimethylacetamide was added to dissolve the polymer, followed by stirring at room temperature.
Sixth step: the mixed solution obtained above was cast and coated on a glass sheet, and the solvent was dried at 70℃to form a film.
Seventh step: and (3) placing the dielectric film prepared in the sixth step into a drying oven at 180 ℃ for annealing for 6 hours to obtain the crosslinked polyaryletherketone-based dielectric film containing the rigid annular structure.
Eighth step: the dielectric film prepared has the energy storage density of 7.2J/cm under the conditions of the test temperature of 150 ℃, the dielectric constant of 4.3 and the breakdown strength of 600MV/m 3 The energy storage efficiency is 87%.
Example 2 provides a method for preparing a polyaryletherketone-based dielectric film containing a rigid ring structure, which specifically comprises the following steps:
the first step: under the protection of nitrogen, 1, 3-dibromodiamantane and phenol are taken as monomers, aluminum trichloride is taken as a catalyst, and the molar ratio is 5:20:1 are added into a round bottom flask in proportion and react for 12 to 16 hours at 80 ℃. The hydrogen bromide gas produced during the reaction is absorbed with sodium hydroxide solution. After the reaction, washing excessive aluminum trichloride and phenol with hot water, vacuum drying, and Soxhlet extracting with methanol as solvent. And recrystallizing the concentrated solution obtained by Soxhlet extraction to obtain white flaky crystal product bis (4-hydroxyphenyl) adamantane.
And a second step of: into a 250mL three-necked flask equipped with a nitrogen port equipped with a thermometer and a stirrer and equipped with a water-carrying device, diene bisphenol A (4.566 g,0.02 mol), 4' -difluorobenzophenone (5.455 g,0.025 mol), bis (4-hydroxyphenyl) adamantane (1.61 g,0.005 mol) and then anhydrous potassium carbonate (7.60 g,0.055 mol) were successively introduced.
And a third step of: adding 40-50 mL of sulfolane solvent and 20-30 mL of toluene as a water-carrying agent into the system, introducing nitrogen, and heating until the toluene is refluxed with water under the stirring condition, thereby ensuring that the water in the system is removed.
Fourth step: the system is heated to 130-140 deg.c, 150-160 deg.c and 180-200 deg.c successively to react. After the reaction is completed, discharging the mixture solution into a hydrochloric acid aqueous solution, crushing the mixture solution by a powder machine, and washing the mixture solution for a plurality of times by boiling distilled water and ethanol to remove residual inorganic salts and solvents. Drying in an oven to obtain the polyaryletherketone polymer containing the rigid group.
Fifth step: 200mg of the polyaryletherketone polymer containing a rigid group was placed in a 20mL sample bottle, and 10mLN, N' -dimethylacetamide was added to dissolve the polymer, followed by stirring at room temperature.
Sixth step: the mixed solution obtained above was cast and coated on a glass sheet, and the solvent was dried at 70℃to form a film.
Seventh step: and (3) putting the dielectric film prepared in the sixth step into a drying oven with the temperature of 180-200 ℃ for annealing for 6 hours to obtain the crosslinked polyaryletherketone-based dielectric film with the rigid annular structure.
Example 3 provides a method for preparing a polyaryletherketone-based dielectric film containing a rigid ring structure, which specifically comprises the following steps:
the first step: 40-50 mL of absolute ethanol and 0.1mol of p-benzoquinone are added into a conical flask, and placed into an ice-water bath. After ten minutes, 0.11 to 0.13mol of cyclopentadiene was added and stirred for fifteen minutes. The solution was allowed to stand at room temperature for 1h, from cloudy to clear and orange-yellow with a large amount of pale yellow precipitate. Ethanol was distilled off under reduced pressure at low temperature to give a pale yellow solid. Recrystallizing with petroleum ether to obtain pale yellow needle-like crystals. To the product was added 100mL of ethyl acetate and 20g of basic alumina, and stirred for 12h in a water bath at 25 ℃. Basic alumina was removed by filtration and ethyl acetate was removed by rotary evaporation to give a red viscous liquid. Chloroform was added to the solution for washing until a white solid of norbornene-containing hydroquinone monomer was obtained.
And a second step of: into a 250mL three-necked flask equipped with a nitrogen port equipped with a thermometer, a stirring blade and a water-carrying device were successively introduced diene bisphenol A (4.56 g,0.02 mol), 4' -difluorobenzophenone (5.455 g,0.025 mol), norbornene-containing hydroquinone monomer (1.555 g,0.005 mol), and then anhydrous potassium carbonate (7.60 g,0.055 mol).
And a third step of: adding 40-50 mL of solvent DMAc and 10-20 mL of water-carrying agent toluene into the system, introducing nitrogen, and heating until the toluene carries water to reflux under the stirring condition, thereby ensuring that the water in the system is removed.
Fourth step: and (3) sequentially heating the system to 130-140 ℃, 140-160 ℃ and 180-200 ℃ by using a stage heating method to react. After the reaction is completed, discharging the mixture solution into a hydrochloric acid aqueous solution, crushing the mixture solution by a powder machine, and washing the mixture solution for a plurality of times by boiling distilled water and ethanol to remove residual inorganic salts and solvents. Drying in an oven to obtain the polyaryletherketone polymer containing the rigid group.
Fifth step: 200mg of the polyaryletherketone polymer containing a rigid group was placed in a 20mL sample bottle, and 10mLN, N' -dimethylacetamide was added to dissolve the polymer, followed by stirring at room temperature.
Sixth step: the mixed solution obtained above was cast and coated on a glass sheet, and the solvent was dried at 70℃to form a film.
Seventh step: and (3) placing the dielectric film prepared in the sixth step into a drying oven at 180 ℃ for annealing for 6 hours to obtain the crosslinked polyaryletherketone-based dielectric film containing the rigid annular structure.
Example 4 provides a method for preparing a polyaryletherketone-based dielectric film containing a rigid ring structure, which specifically comprises the following steps:
the first step: diene bisphenol A (4.566 g,0.02 mol), 4' -difluorobenzophenone (5.455 g,0.025 mol) and then anhydrous potassium carbonate (7.60 g,0.055 mol) were successively introduced into a 250mL three-necked flask equipped with a thermometer and a stirrer.
And a second step of: adding 40-50 mL of sulfolane solvent and 10-20 mL of toluene as a water-carrying agent into the system, introducing nitrogen, and heating until the toluene is refluxed with water under the stirring condition, thereby ensuring that the water in the system is removed.
And a third step of: and (3) sequentially heating the system to 130-140 ℃, 140-150 ℃ and 180-200 ℃ by using a stage heating method to react. After the reaction is completed, discharging the mixture solution into a hydrochloric acid aqueous solution, crushing the mixture solution by a powder machine, and washing the mixture solution for a plurality of times by boiling distilled water and ethanol to remove residual inorganic salts and solvents. Drying in an oven to obtain the poly (arylene ether ketone) polymer with double bonds.
Fourth step: 200mg of the polyaryletherketone polymer containing a rigid group was placed in a 20mL sample bottle, and 10mLN, N' -dimethylacetamide was added to dissolve the polymer, followed by stirring at room temperature.
Fifth step: and (3) adding 0.05mol of methacryloxypropyl POSS into the solution obtained in the fourth step, adding a small amount of benzoyl peroxide, and reacting for 10-12 hours to finish the reaction.
Sixth step: the mixed solution obtained above was cast and coated on a glass sheet, and the solvent was dried at 70℃to form a film.
Seventh step: and (3) placing the dielectric film prepared in the sixth step into a drying oven at 180 ℃ for annealing for 6 hours to obtain the crosslinked polyaryletherketone-based dielectric film containing the rigid annular structure.
FIG. 1 is a synthetic route to polyaryletherketone polymer polymers, monomers being diene bisphenol A, 4' -difluorobenzophenone, and bis (2-benzimidazolyl) pyridine, including but not limited to monomers of this route. FIG. 2 shows that such polymers can have dielectric constants of 4.0-4.5 and dielectric losses of 0.004-0.01. As can be seen from the analysis of FIGS. 3 to 6, the maximum polarization value of example 1 was 2.94. Mu.c/m at a test temperature of 150℃and a breakdown strength of 650MV/m 2 . The high-temperature-resistant dielectric film prepared by the invention is beneficial to the improvement of discharge energy storage density. As can be seen from the analysis of FIG. 5, the high temperature resistant dielectric film prepared in example 1 of the present invention has an energy storage density of 5.3 to 8.7J/cm at a test temperature of 150℃and a breakdown strength of 500 to 650MV/m 3 The releasable efficiency of the stored energy is 82% -91%. In addition, as seen from FIG. 6, the high temperature resistant dielectric film prepared by the present invention can be recycled more than 5000 times at 150 ℃ and 250MV/m, and the efficiency is still as high as more than 95%. The novel polyaryletherketone-based material has more excellent high-temperature application, and effectively solves the problems that the temperature rise can cause the internal conductivity of a dielectric material to increase exponentially, and the energy storage density and the charge-discharge efficiency are reduced.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of implementing the present application and that various changes in form and details may be made therein without departing from the spirit and scope of the present application. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention shall be defined by the appended claims.
Claims (6)
1. The preparation method of the polyaryletherketone-based dielectric film containing the rigid annular structure is characterized in that firstly, a rigid annular structure monomer is prepared; then the rigid ring structure monomer is used as a raw material to prepare polyaryletherketone containing a rigid ring structure; finally, polyaryletherketone containing a rigid annular structure is used as a raw material to prepare a polyaryletherketone dielectric film containing the rigid annular structure;
the method comprises the following specific steps:
1) Preparing a rigid cyclic structure monomer, wherein the rigid cyclic structure monomer is one or more of bis (2-benzimidazolyl) pyridine, bis (4-hydroxyphenyl) adamantane and methacryloxypropyl POSS;
2) Preparing polyaryletherketone containing a rigid cyclic structure, taking 4,4' -difluorobenzophenone, diallyl bisphenol A and the rigid cyclic structure monomer as raw materials, adding a solvent, a water scavenger and a salifying agent, and mixing to obtain a solution; carrying out the following reaction under the protection of nitrogen, carrying out the reaction through a three-stage heating process, carrying out the pre-polymerization salification reaction, heating toluene to reflux for removing water, and finally carrying out the polycondensation reaction at high temperature to obtain a crude product for treatment; pouring the crude product into aqueous solution of hydrochloric acid, crushing, washing with hot water and ethanol respectively, and finally drying to obtain the polyaryletherketone containing the rigid annular structure;
3) Preparing cross-linked polyaryletherketone, stirring the polyaryletherketone containing the rigid cyclic structure in DMAc solution to obtain stable and uniform mixed solution, coating the mixed solution on a flat glass plate, and drying the solvent at 70 ℃ to form a film; then placing the film into an oven, and treating 6h at a high temperature of 180-200 ℃ to obtain a polyaryletherketone-based dielectric film with a rigid annular structure;
in the step 2), the molar ratio of the diallyl bisphenol A to the rigid cyclic structure monomer is (9:1) - (7:3).
2. The method for producing a polyaryletherketone-based dielectric film according to claim 1, wherein in the step 2), the solvent is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone; the water scavenger is toluene; the salifying agent is anhydrous potassium carbonate.
3. The method for preparing the polyaryletherketone-based dielectric film with the rigid annular structure according to claim 1, wherein the thickness of the polyaryletherketone-based dielectric film is 5-12 [ mu ] m; the dielectric constant of the polyaryletherketone-based dielectric film is 3.0-5.0.
4. The method for preparing a polyaryletherketone-based dielectric film containing a rigid ring structure according to claim 1, wherein the polyaryletherketone-based dielectric film has a breakdown strength of 500MV/m to 750MV/m at 150 ℃ and an energy storage density of 5.0J/cm 3 ~10.0 J/cm 3 The energy storage efficiency is not lower than 90%.
5. A polyaryletherketone-based dielectric film having a rigid ring structure, wherein the polyaryletherketone-based dielectric film having a rigid ring structure is prepared by the method for preparing a polyaryletherketone-based dielectric film having a rigid ring structure according to any one of claims 1 to 4.
6. The use of the polyaryletherketone-based dielectric film comprising a rigid ring structure according to claim 5 in the fields of capacitors, electric vehicle inverters, electric flexible direct transmission systems, new energy power generation and downhole oil and gas exploration.
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