CN115232338B - Cross-linked modified P (VMA-MMA) dielectric film and preparation method and application thereof - Google Patents
Cross-linked modified P (VMA-MMA) dielectric film and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CPOQZWDLPWEJET-UHFFFAOYSA-N (4-formyl-2-methoxyphenyl) 2-methylprop-2-enoate Chemical compound COC1=CC(C=O)=CC=C1OC(=O)C(C)=C CPOQZWDLPWEJET-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004146 energy storage Methods 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 230000015556 catabolic process Effects 0.000 claims abstract description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000012141 vanillin Nutrition 0.000 claims abstract description 14
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 7
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 21
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 12
- 230000005684 electric field Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 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 4
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000011104 metalized film Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 17
- 239000003989 dielectric material Substances 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 5
- 229920005610 lignin Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 206010017472 Fumbling Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Organic Insulating Materials (AREA)
Abstract
The invention discloses a crosslinked modified P (VMA-MMA) dielectric film and a preparation method and application thereof, belonging to the technical field of polymer-based dielectric materials. The preparation method adopts the biomass raw material Vanillin (VA) which takes lignin as a source, the Vanillin Methacrylate (VMA) is prepared through esterification reaction, the Vanillin Methacrylate (VMA) and Methyl Methacrylate (MMA) are copolymerized to obtain P (VMA-MMA), and the amino group in the cross-linking agent and the aldehyde group in the P (VMA-MMA) are used for cross-linking, so that the polarization intensity and the dielectric constant can be effectively improved, and the energy storage density of the polymer can be further effectively improved. The preparation method is simple, has good repeatability, can improve the breakdown strength and the energy storage density by controlling the crosslinking degree of P (VMA-MMA), further increases the energy storage efficiency of the polymer, and can be used for improving the breakdown strength and the energy storage density of the film capacitor.
Description
Technical Field
The invention belongs to the technical field of polymer-based dielectric materials, and particularly relates to a crosslinked and modified P (VMA-MMA) dielectric film, and a preparation method and application thereof.
Background
With the rapid development of the electronic and electric industry, the requirements of people on electronic components are increasing. The capacitor is an important microelectronic device and is widely applied to various fields such as vehicles, medical appliances, high-voltage direct-current transmission, military weapons and the like. Currently, miniaturized, lightweight, integrated electronic devices have become an important trend for future development. Dielectric materials are important components in capacitors and play a decisive role in high energy storage and charge-discharge efficiency of the capacitors. Polymer dielectric materials are of great interest because of their good processability, high breakdown field strength and low dielectric loss.
The most studied at present are PVDF-based polymers, P (VDF-HFP) copolymers and BOPP polymers which are the most widely used commercially, but they are all non-renewable, non-biodegradable petroleum derived synthetic polymers. With the increasing exhaustion of non-renewable resources such as petroleum, natural gas, etc., reasonable development and utilization of biomass materials has become a research direction of extensive attention of researchers. At present, the research on biomass dielectric materials is not much, and the acceleration of research and development and the fumbling of some biomass-based dielectric materials are necessary routes for realizing green chemistry.
Vanillin (VA) derived from lignin has wide application as an additive in the food industry and in perfumes, but application research in the field of dielectrics has not been developed, and has potential for application in the field of dielectric materials by functional modification of Vanillin (VA) containing multiple functional groups. Firstly, VA contains-CHO, and the VA is used as a crosslinking point to carry out crosslinking modification, so that the elastic modulus can be improved, the breakdown strength of a dielectric film can be further improved, and the energy storage density can be improved; secondly, the structural advantage of benzene ring and ester group is contained, and delta-pi bonds interact, so that the energy storage density is improved, and the energy loss is reduced. PMMA is a linear polymer with both high breakdown field strength and relatively low dielectric loss, but its increase in energy storage density is limited by relatively low dielectric constant and polarization.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a crosslinked and modified P (VMA-MMA) dielectric film, and a preparation method and application thereof, so as to solve the problem of low energy storage density caused by relatively low dielectric constant and polarization strength of PMMA.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a crosslinked and modified P (VMA-MMA) dielectric film, which comprises the following steps:
1) Preparing VMA from VA, dissolving VMA and MMA in DMF, adding AIBN, reacting under argon atmosphere to obtain mixed solution, purifying the mixed solution, heating and oven drying the solvent to obtain P (VMA-MMA);
2) Dissolving P (VMA-MMA) in DMF, adding an amino-containing cross-linking agent under the condition of ice water bath, uniformly mixing, pouring the mixed solution on the surface of glass to form a film, carrying out a step heating reaction, and carrying out film detachment in deionized water to obtain the cross-linking agent modified P (VMA-MMA) dielectric film.
Preferably, in step 1), the molar ratio of VMA to MMA is 1: (3-10).
Preferably, in step 1), the reaction is carried out for 12 hours at 80 ℃ under an argon atmosphere; the mixed solution was purified by methanol precipitation.
Preferably, in step 1), the solvent is dried by heating at 80℃for 12 h.
Preferably, in the step 2), the cross-linking agent containing amino is one or more of polyetheramine D400, 4-diaminodiphenyl ether, 4-diaminodiphenyl disulfide, hexamethylenediamine, biphenyldiamine, p-phenylenediamine and polyetheramine T403.
Preferably, in the step 2), the step-heating reaction is sequentially performed at 60 ℃ for 1h, at 80 ℃ for 1h and at 120 ℃ for 1h.
Preferably, in step 2), the molar ratio of amino groups in P (VMA-MMA) to aldehyde groups in the crosslinking agent is (0.8-1): 1.
the invention also discloses the crosslinked and modified P (VMA-MMA) dielectric film prepared by the preparation method, and the thickness of the crosslinked and modified P (VMA-MMA) dielectric film is 5-20 mu m.
Preferably, the crosslinked and modified P (VMA-MMA) dielectric film has an electrical breakdown strength of 620.6-720.2 MV/m and an energy storage density of 5.6-9.1J/cm 3 The energy efficiency is 84-91%.
The invention also discloses application of the crosslinked and modified P (VMA-MMA) dielectric film in preparing a metallized film capacitor.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a crosslinked and modified P (VMA-MMA) dielectric film, which adopts a biomass raw material Vanillin (VA) which takes lignin as a source, obtains Vanillin Methacrylate (VMA) through esterification reaction, obtains P (VMA-MMA) through copolymerization of the Vanillin Methacrylate (VMA) and Methyl Methacrylate (MMA), and utilizes amino in a crosslinking agent and aldehyde group in the P (VMA-MMA) to crosslink, thereby effectively improving the polarization intensity and dielectric constant and further effectively improving the energy storage density of a polymer. The preparation method is simple and has good repeatability, and the breakdown strength and the energy storage density can be improved by controlling the crosslinking degree of P (VMA-MMA), so that the energy storage efficiency of the polymer is improved.
Further, the reaction is carried out under the rare gas argon atmosphere, so that oxygen in the bottle can be removed; the impurities in the solvent can be removed by methanol precipitation and purification to obtain a pure polymer.
Further, the step-wise temperature-rising reaction can better crosslink the amino groups in P (VMA-MMA) with the aldehyde groups in the crosslinking agent.
The invention also discloses a crosslinked and modified P (VMA-MMA) dielectric film, the breakdown strength of the dielectric film is 620.6-720.2 MV/m, and the energy storage density is 5.6-9.1J/cm 3 The energy efficiency is 84-91%, and the method can be used for improving the breakdown strength and the energy storage density of the film capacitor.
Drawings
FIG. 1 is a schematic illustration of VMA preparation of the present invention;
FIG. 2 is a schematic representation of the preparation of P (VMA-MMA) according to the present invention;
FIG. 3 shows the P (VMA-MMA) of the present invention 1 H NMR spectrum schematic;
FIG. 4 is a schematic representation of the preparation of P (VMA-MMA) @ PEA according to the present invention;
FIG. 5 is a schematic representation of FT-IR spectra of P (VMA-MMA) modified with different crosslinking agents according to the invention;
FIG. 6 is a schematic representation of the electric displacement-electric field (D-E) curve of the modified P (VMA-MMA) @ HMD of PMMA and crosslinker of the present invention; wherein, (a) an electric displacement-electric field curve of PMMA, (b) an electric displacement-electric field curve of P (VMA-MMA) @ HMD.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a crosslinked and modified P (VMA-MMA) dielectric film and a preparation method thereof, wherein Vanillin (VA) is used as a raw material to prepare Vanillyl Methacrylate (VMA), then the Vanillyl Methacrylate (VMA) and Methyl Methacrylate (MMA) are polymerized in different proportions to prepare P (VMA-MMA), and the P (VMA-MMA) dielectric film is crosslinked with one or two crosslinking agents of polyetheramine D400 (PEA), 4-diaminodiphenyl ether (ODA), 4-diaminodiphenyl disulfide (BS), hexamethylenediamine (HMD), biphenyldiamine, P-phenylenediamine and polyetheramine T403 to prepare the P (VMA-MMA) dielectric film crosslinked with different crosslinking agents, and dielectric and energy storage properties of the P (VMA-MMA) dielectric film are studied.
Specifically, the method comprises the following steps:
(1) 1.1g of VMA and (1.5-5) g of MMA were dissolved in DMF, and 0.008g of AIBN was added thereto, followed by reaction at 80℃for 12 hours under an argon atmosphere, purification by precipitation with methanol, and subsequent drying of the solvent to obtain P (VMA-MMA).
(2) Dissolving 0.3g of P (VMA-MMA) in DMF, stirring uniformly at room temperature, adding a certain amount of cross-linking agent (polyetheramine D400 (PEA), 4-diaminodiphenyl ether (ODA), 4-diaminodiphenyl disulfide (BS), hexamethylenediamine (HMD), biphenyldiamine, P-phenylenediamine and polyetheramine T403) into an ice water bath, magnetically stirring uniformly, then thin-coating the obtained mixed solution on the surface of glass washed clean by absolute ethyl alcohol, heating the temperature stepwise (60 ℃, 80 ℃ and 120 ℃ for 1 hour respectively), drying the film, and separating the film in deionized water to obtain the cross-linked modified P (VMA-MMA) dielectric film.
Example 1
(1) 1.1g of VMA and 5g of MMA were dissolved in DMF, and 0.008g of AIBN was added, the vial was sealed and magnetically stirred after 1h of argon introduction, and after 12h the mixed solution was precipitated in methanol, then heated at 80℃for 12h, and the solvent was dried to give P (VMA-MMA).
(2) 0.3g of P (VMA-MMA) was dissolved in DMF and stirred at room temperature before polyetheramine D400 (PEA) (-NH) was added to the ice water bath 2 namely-CHO=0.8:1), namely P (VMA-MMA) @ PEA-80% polymer, after magnetic stirring evenly, immediately coating the obtained mixed solution on the surface of glass washed clean by absolute ethyl alcohol, sequentially raising the temperature stepwise (60 ℃, 80 ℃ and 120 ℃ for 1 hour each), drying the film and separating the film in deionized water to obtain a crosslinked modified P (VMA-MMA) dielectric film, wherein the maximum electric breakdown strength of the crosslinked modified P (VMA-MMA) dielectric film can reach 670.2MV/m, and the energy storage density of the film can reach 7.1J/cm when the electric field strength is 500MV/m 3 The energy efficiency can reach 91 percent.
Example 2
(1) 1.1g of VMA and 5g of MMA were dissolved in DMF, and 0.008g of AIBN was added, the vial was sealed and magnetically stirred after 1h of argon introduction, and after 12h the mixed solution was precipitated in methanol, then heated at 80℃for 12h, and the solvent was dried to give P (VMA-MMA).
(2) Dissolving 0.3g of P (VMA-MMA) in DMF, stirring at room temperature, adding Hexamethylenediamine (HMD) (-NH) into ice water bath 2 namely-CHO=1:1), namely the P (VMA-MMA) @ HMD-100% polymer is obtained, after magnetic stirring is uniform, the obtained mixed solution is immediately coated on the surface of glass washed clean by absolute ethyl alcohol, the temperature is raised (60 ℃, 80 ℃ and 120 ℃ respectively for 1 hour) in sequence in a stepped manner, and then the film is dried and separated from the deionized water, so that the crosslinked modified P (VMA-MMA) dielectric film is obtained. The maximum electric breakdown strength of the film can reach 650.3MV/m, and when the electric field strength is 500MV/m, the energy storage density of the film can reach 8.9J/cm 3 The energy efficiency can reach 84 percent.
Example 3
(1) 1.1g of VMA and 5g of MMA were dissolved in DMF, and 0.008g of AIBN was added, the vial was sealed and magnetically stirred after 1h of argon introduction, and after 12h the mixed solution was precipitated in methanol, then heated at 80℃for 12h, and the solvent was dried to give P (VMA-MMA).
(2) 0.3g of P (VMA-MMA) was dissolved in DMF and stirred at room temperature before 4, 4-diaminodiphenyl disulfide (BS) (-NH) was added to an ice water bath 2 namely-CHO=1:1), namely P (VMA-MMA) @ BS-100% polymer, after magnetic stirring is uniform, the obtained mixed solution is coated on the surface of glass washed clean by absolute ethyl alcohol, the temperature is raised (60 ℃, 80 ℃ and 120 ℃ for 1 hour respectively) in sequence, and then the film is dried and separated in deionized water, so that the crosslinked modified P (VMA-MMA) dielectric film is obtained. The maximum electric breakdown strength of the film can reach 659.9MV/m, and when the electric field strength is 550MV/m, the energy storage density of the film can reach 9.1J/cm 3 The energy efficiency can reach 86 percent.
Example 4
(1) 1.1g of VMA and 5g of MMA were dissolved in DMF, and 0.008g of AIBN was added, the vial was sealed and magnetically stirred after 1h of argon introduction, and after 12h the mixed solution was precipitated in methanol, then heated at 80℃for 12h, and the solvent was dried to give P (VMA-MMA).
(2) 0.3g of P (VMA-MMA) was dissolved in DMF and stirred at room temperature and then stirred in ice waterAdding 4, 4-diaminodiphenyl ether (ODA) (-NH) into bath 2 namely-CHO=1:1), namely the P (VMA-MMA) @ ODA-100% polymer is obtained, after magnetic stirring is uniform, the obtained mixed solution is immediately coated on the surface of glass washed clean by absolute ethyl alcohol, the temperature is sequentially increased stepwise (60 ℃, 80 ℃ and 120 ℃ for 1 hour each), and then the film is dried and separated from the deionized water, so that the crosslinked modified P (VMA-MMA) dielectric film is obtained. The maximum electric breakdown strength of the film can reach 663.4MV/m, and when the electric field strength is 500MV/m, the energy storage density of the film can reach 6.3J/cm 3 The energy efficiency can reach 87%.
Comparative example 1
(1) 1.1g of VMA and 1.5g of MMA were dissolved in DMF, and 0.008g of AIBN was added, the vial was sealed and magnetically stirred after 1h of argon was introduced, and after 12h the mixed solution was precipitated in methanol, then heated at 80℃for 12h, and the solvent was dried to give P (VMA-MMA).
(2) 0.3g of P (VMA-MMA) was dissolved in DMF and stirred at room temperature before polyetheramine D400 (PEA) (-NH) was added to the ice water bath 2 namely-CHO=0.8:1), namely P (VMA-MMA) @ PEA-80% polymer is obtained, after magnetic stirring is uniform, the obtained mixed solution is immediately coated on the surface of glass washed clean by absolute ethyl alcohol, the temperature is sequentially increased stepwise (1 hour each at 60 ℃, 80 ℃ and 120 ℃), and then the film is dried and separated from the deionized water, so that the crosslinked modified P (VMA-MMA) dielectric film is obtained. The maximum electric breakdown strength of the film can reach 620.6MV/m, and when the electric field strength is 500MV/m, the energy storage density of the film can reach 6.8J/cm 3 The energy efficiency can reach 88 percent.
Comparative example 2
(1) 1.1g of VMA and 2.5g of MMA were dissolved in DMF, and 0.008g of AIBN was added, the vial was sealed and magnetically stirred after 1h of argon was introduced, and after 12h the mixed solution was precipitated in methanol, then heated at 80℃for 12h, and the solvent was dried to give P (VMA-MMA).
(2) 0.3g of P (VMA-MMA) was dissolved in DMF and stirred at room temperature before polyetheramine D400 (PEA) (-NH) was added to the ice water bath 2 namely-CHO=0.8:1), namely the P (VMA-MMA) @ PEA-80% polymer is obtained, and magnetic stirring is carried outAfter homogenizing, the obtained mixed solution is coated on the surface of glass washed by absolute ethyl alcohol, the temperature is raised (60 ℃, 80 ℃ and 120 ℃ for 1 hour respectively) in sequence in a stepped way, and then the film is dried and separated in deionized water, so that the crosslinked modified P (VMA-MMA) dielectric film is obtained. The maximum electric breakdown strength of the film can reach 720.2MV/m, and when the electric field strength is 500MV/m, the energy storage density of the film can reach 5.6J/cm 3 The energy efficiency can reach 84 percent.
The invention is described in further detail below with reference to the attached drawing figures:
FIG. 3 shows the P (VMA-MMA) of the present invention 1 H NMR spectrum is schematically shown by 1 H NMR determines the chemical structure of P (VMA-MMA), as shown in the figure, the nuclear magnetic peaks at δ=0.7-2.5 ppm, δ=3.5-4.1 ppm represent hydrogen atoms on methyl and methylene groups and on VMA and mmamethoxy groups of the main and side chains of the copolymer, respectively, the nuclear magnetic peaks at δ=7.26-7.5 ppm correspond to hydrogen atoms on benzene rings, and the nuclear magnetic peaks at δ=9.8-9.9 ppm are hydrogen atoms on aldehyde groups in VMA.
FIG. 5 is a schematic view of FT-IR spectrum of P (VMA-MMA) modified with different crosslinking agents according to the invention, from which it can be seen that 3200-3400cm -1 the-NH stretching vibration absorption peak at the position disappears, which indicates that the aldehyde group completely consumes the amino group in the reaction, and the crosslinking modification is successful.
FIG. 6 is a schematic diagram showing the electric displacement-electric field (D-E) profile of the modified PMMA and crosslinking agent P (VMA-MMA) @ HMD of the present invention, from which it can be seen that the external electric field strength is applied starting at 100MV/m and gradually increasing in magnitude every 50MV/m until the film breaks down. In the first quadrant, the highest point on the electric hysteresis loop gradually rises along with the increase of the electric field intensity, and the area enclosed by the electric hysteresis loop and the coordinate axis is also larger and larger, which shows that the energy loss is also more serious along with the increase of the electric field intensity, and the polarization intensity of the polymer film is increased. For a P (VMA-MMA) @ HMD dielectric film, the energy storage density was 8.9J/cm at an electric field strength of 500MV/m 3 。
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (6)
1. A method for preparing a crosslinked modified P (VMA-MMA) dielectric film, comprising the steps of:
1) Preparing vanillin methacrylate VMA from vanillin VA, dissolving VMA and methyl methacrylate MMA in DMF, adding AIBN, reacting under argon atmosphere to obtain mixed solution, purifying the mixed solution, heating and drying the solvent to obtain P (VMA-MMA);
2) Dissolving P (VMA-MMA) in DMF, adding an amino-containing cross-linking agent under the condition of ice water bath, uniformly mixing, pouring the mixed solution on the surface of glass to form a film, carrying out a step heating reaction, and carrying out film detachment in deionized water to obtain a cross-linking agent modified P (VMA-MMA) dielectric film;
in step 1), the molar ratio of VMA to MMA is 1: (3-10);
in the step 2), the cross-linking agent containing amino is one or more of polyetheramine D400, 4-diaminodiphenyl ether, 4-diaminodiphenyl disulfide, hexamethylenediamine, biphenyldiamine, p-phenylenediamine and polyetheramine T403;
in the step 2), the step heating reaction is sequentially carried out at 60 ℃ for 1h, at 80 ℃ for 1h and at 120 ℃ for 1h;
in the step 2), the molar ratio of the amino group in P (VMA-MMA) to the aldehyde group in the crosslinking agent is (0.8-1): 1.
2. the method for producing a crosslinked modified P (VMA-MMA) dielectric film according to claim 1, wherein in step 1), 12h is reacted at 80 ℃ under an argon atmosphere; the mixed solution was purified by methanol precipitation.
3. The method for producing a crosslinked modified P (VMA-MMA) dielectric film according to claim 1, wherein in step 1), the solvent is dried by heating 12h at 80 ℃.
4. The crosslinked and modified P (VMA-MMA) dielectric film according to any one of claims 1 to 3, wherein the crosslinked and modified P (VMA-MMA) dielectric film has a thickness of 5 to 20. Mu.m.
5. The crosslinked and modified P (VMA-MMA) dielectric film according to claim 4, wherein the crosslinked and modified P (VMA-MMA) dielectric film has an electric breakdown strength of 620.6 to 720.2MV/m and an energy storage density of 5.6 to 9.1J/cm at an electric field strength of 500MV/m 3 The energy efficiency is 84-91%.
6. Use of the cross-linked modified P (VMA-MMA) dielectric film of any of claims 4 or 5 for the preparation of metallized film capacitors.
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