CN113969019A - Preparation method of nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material - Google Patents
Preparation method of nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material Download PDFInfo
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- CN113969019A CN113969019A CN202111103455.2A CN202111103455A CN113969019A CN 113969019 A CN113969019 A CN 113969019A CN 202111103455 A CN202111103455 A CN 202111103455A CN 113969019 A CN113969019 A CN 113969019A
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- zirconate titanate
- barium zirconate
- nano barium
- maleic anhydride
- anhydride grafted
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- 229910021523 barium zirconate Inorganic materials 0.000 title claims abstract description 141
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002245 particle Substances 0.000 claims abstract description 70
- 229920001721 polyimide Polymers 0.000 claims abstract description 50
- 239000004743 Polypropylene Substances 0.000 claims abstract description 25
- 229920001155 polypropylene Polymers 0.000 claims abstract description 25
- -1 polypropylene Polymers 0.000 claims abstract description 14
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 238000007873 sieving Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 16
- 238000004146 energy storage Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 239000003990 capacitor Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
- B29C69/001—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore a shaping technique combined with cutting, e.g. in parts or slices combined with rearranging and joining the cut parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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)
- Mechanical Engineering (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention discloses a nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, which comprises the following components in percentage by mass: 5-15 wt% of nano barium zirconate titanate, 42.5-47.5 wt% of maleic anhydride grafted polypropylene and 42.5-47.5 wt% of polypropylene. The disclosure also provides a preparation method of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material and a preparation method of a polyimide composite film containing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material. According to the preparation method, the nano barium zirconate titanate particles are doped, so that the effective dielectric constant of the composite material is greatly improved, and the dielectric loss is kept at an extremely low level.
Description
Technical Field
The disclosure belongs to the field of power capacitors, and particularly relates to a preparation method of a nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material.
Background
As a key energy storage device, the polymer film capacitor with high power density and high withstand voltage is widely applied to the fields of power grid frequency modulation, pulse power systems, new energy power generation and the like. Polypropylene (PP) is a main electrical material for commercial film capacitors at present because of its advantages of high breakdown field strength, low material loss, low cost, excellent mechanical properties, etc. However, the low energy storage density of PP seriously hinders the film capacitor from moving toward large capacityAnd miniaturization. It is well known that for linear electrical materials such as PP, the maximum energy storage density U ismaxCan be visually represented as:
Umax＝1/2ε0εrEb 2
in the formula, epsilon0Is a vacuum dielectric constant of ∈rIs a relative dielectric constant, EbIs the breakdown field strength of the electrical material. The above formula shows that the improvement of the relative dielectric constant and the breakdown field strength of the electric material is the key to improve the energy storage density of the electric material. Research shows that the addition of the nano-filler into the polymer is an effective means for regulating and controlling the energy storage characteristics, so that the nano-composite material is regarded as one of potential ideal capacitor energy storage materials and has wide application prospects. In order to improve the breakdown field strength, a large number of inorganic nanoparticles with good insulation performance and high compressive strength are selected as fillers, and although the breakdown strength of the prepared nanocomposite is improved, the energy density of the nanocomposite is limited to a lower level due to the excessively low dielectric constant (-2.2) of PP from the aspect of engineering application, so that the nanocomposite becomes a great obstacle to the development of high-energy-storage-density capacitors.
Disclosure of Invention
Aiming at the defects in the prior art, the purpose of the disclosure is to provide a preparation method of a nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, so that the composite material has high dielectric constant and can keep low material loss, high breakdown field strength and high charge-discharge efficiency.
In order to achieve the above purpose, the present disclosure provides the following technical solutions:
a nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material comprises the following components in percentage by mass:
5-15 wt% of nano barium zirconate titanate,
42.5 to 47.5 weight percent of maleic anhydride grafted polypropylene,
42.5 to 47.5 weight percent of polypropylene,
the nano barium zirconate titanate comprises the following components in percentage by mass:
69.0 wt% of micron-sized barium carbonate,
22.4 percent by weight of nano-scale titanium dioxide,
nanometer zirconium dioxide 8.6 wt%.
The present disclosure also provides a preparation method of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, including the following steps:
s100: preparing nano barium zirconate titanate particles;
s200: carrying out surface modification treatment on the nano barium zirconate titanate particles to obtain surface-modified nano barium zirconate titanate particles;
s300: preparing a nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch according to the surface-modified nano barium zirconate titanate particles;
s400: and preparing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material according to the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch.
Preferably, step S100 includes the steps of:
s101: ball-milling micrometer-grade barium carbonate in alcohol or absolute ethyl alcohol for 12-24h, drying, and sieving to obtain nanometer-grade barium carbonate;
s102: mixing nano-scale titanium dioxide, nano-scale zirconium dioxide and nano-scale barium carbonate in alcohol or absolute ethyl alcohol, carrying out ball milling for 4-6h, drying and sieving to obtain first powder;
s103: sintering the first powder at 1100-1300 ℃ for 2-4h to obtain second powder;
s104: and ball-milling the second powder in alcohol or absolute ethyl alcohol for 12-24h, drying and sieving to obtain the nano barium zirconate titanate particles.
Preferably, in step S200, the surface modification treatment of the nano barium zirconate titanate particles includes the following steps:
s201: dispersing nano barium zirconate titanate particles in a hydrogen peroxide solution, carrying out condensation reflux for 4-8h at the temperature of 80-105 ℃, and then carrying out cleaning, drying and sieving to obtain hydroxylated nano barium zirconate titanate particles;
s202: dispersing the hydroxylated nano barium zirconate titanate particles in a toluene or xylene solution, adding a proper amount of silane coupling agent, heating for 12-24h under an inert gas atmosphere at 80-100 ℃, and then cleaning, drying and sieving to obtain surface-modified nano barium zirconate titanate particles.
Preferably, in step S300, the preparing of the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch according to the surface-modified nano barium zirconate titanate particles is performed by the following method: and melting and blending the surface-modified nano barium zirconate titanate particles and maleic anhydride grafted polypropylene at the temperature of 180-200 ℃ for 10-20mins to obtain the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch.
Preferably, in step S400, the preparing of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material according to the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch is performed by the following method: and melting and blending the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch, polypropylene and maleic anhydride grafted polypropylene for 10-20mins at the temperature of 180-200 ℃ to obtain the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material.
The present disclosure also provides a method for preparing a composite film containing a nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, comprising the steps of:
s1000: cutting a plurality of circular holes on the polyimide film A;
s2000: placing a polyimide film B at the bottom of the polyimide film A, placing a proper amount of nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material in a round hole of the polyimide film A, and then placing a polyimide film C above the polyimide film A to package the polyimide film A;
s3000: and carrying out hot-pressing treatment on the packaged polyimide films A-C to obtain the composite film containing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material.
Preferably, the thickness of each of the polyimide film a, the polyimide film B and the polyimide film C is 100 μm.
Preferably, in step S2000, the content of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material placed in the circular hole of the polyimide film a is 0.2 to 0.4 g.
Preferably, in step S3000, the temperature for performing the hot pressing treatment on the packaged polyimide film A-C is 180-.
Compared with the prior art, the beneficial effect that this disclosure brought does:
1. the maleic anhydride and the KH550 which are introduced in the method are combined in a chemical bond mode, so that the dispersibility of the nano barium zirconate titanate particles in the polymer is obviously improved;
2. the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material prepared by the method has the advantages that the high dielectric constant is obtained, the material loss is still maintained at an extremely low level, the breakdown field intensity is high, the energy storage density is higher than that of pure PP, and the high charge-discharge efficiency can be kept.
Drawings
Fig. 1 is a flowchart of a method for preparing a nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite according to an embodiment of the present disclosure;
fig. 2 is a microscopic morphology characterization SEM image and a particle size distribution diagram of nano barium zirconate titanate particles provided in another embodiment of the present disclosure;
fig. 3(a) to 3(d) are SEM images for characterizing the micro-morphology of a composite material provided by another embodiment of the present disclosure, wherein fig. 3(a) is undoped nano barium zirconate titanate, fig. 3(b) is 5 wt% doped nano barium zirconate titanate, fig. 3(c) is 10 wt% doped nano barium zirconate titanate, and fig. 3(d) is 15 wt% doped nano barium zirconate titanate;
FIG. 4 is a graph of dielectric constant and material loss spectrum of a composite material according to another embodiment of the present disclosure;
FIG. 5 is a Weibull distribution of direct current breakdown of a composite material provided by another embodiment of the present disclosure;
fig. 6(a) to 6(c) illustrate energy storage characteristics of a composite material according to another embodiment of the present disclosure, where fig. 6(a) is a hysteresis loop of the composite material when an electric field strength is 200MV/m, fig. 6(b) is an energy density and a charge/discharge efficiency of the composite material when the electric field strength is 200MV/m, and fig. 6(c) is a maximum energy storage density of the composite material.
Detailed Description
Specific embodiments of the present disclosure will be described in detail below with reference to fig. 1 to 6 (c).
While specific embodiments of the disclosure are shown in the drawings, it should be understood that the disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
It should be noted that certain terms are used throughout the description and claims to refer to particular components. As one skilled in the art will appreciate, various names may be used to refer to a component. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description which follows is a preferred embodiment of the disclosure, but is made for the purpose of illustrating the general principles of the disclosure and not for the purpose of limiting the scope of the disclosure. The scope of the present disclosure is to be determined by the terms of the appended claims.
To facilitate an understanding of the embodiments of the present disclosure, the following detailed description is to be considered in conjunction with the accompanying drawings, and the drawings are not to be construed as limiting the embodiments of the present disclosure.
As shown in fig. 1, the present disclosure provides a nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, which comprises the following components by mass:
5-15 wt% of nano barium zirconate titanate,
42.5 to 47.5 weight percent of maleic anhydride grafted polypropylene,
42.5 to 47.5 weight percent of polypropylene,
the nano barium zirconate titanate comprises the following components in percentage by mass:
69.0 wt% of micron-sized barium carbonate,
22.4 percent by weight of nano-scale titanium dioxide,
nanometer zirconium dioxide 8.6 wt%.
The present disclosure also provides a preparation method of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, including the following steps:
s100: preparing nano barium zirconate titanate particles;
s200: carrying out surface modification treatment on the nano barium zirconate titanate particles to obtain surface-modified nano barium zirconate titanate particles;
s300: preparing a nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch according to the surface-modified nano barium zirconate titanate particles;
s400: and preparing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material according to the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch.
In order to facilitate a more detailed understanding of the above-described methods of preparation provided by the present disclosure, reference is now made to the following examples.
The first embodiment:
a. ball-milling 25g of micron-grade barium carbonate in alcohol for 12 hours, drying and sieving to obtain 25g of nanometer-grade barium carbonate;
b. 5.5875g of nano-scale titanium dioxide, 2.1552g of zirconium dioxide and 17.2573g of nano-scale barium carbonate obtained in the step a are mixed in alcohol, ball-milled for 4 hours, dried and sieved to obtain 25g of first powder;
c. sintering 25g of the first powder for 2 hours at 1100 ℃ to obtain 21.1513g of second powder;
d. ball-milling 20g of the second powder in alcohol for 12h, drying and sieving to obtain 20g of nano barium zirconate titanate particles;
e. dispersing 10g of nano barium zirconate titanate particles in 100mL of hydrogen peroxide solution with the mass fraction of 30 wt%, carrying out washing, drying and sieving after carrying out condensation reflux for 4h at 80 ℃ to obtain 10g of hydroxylated nano barium zirconate titanate particles;
f. dispersing 10g of hydroxylated nano barium zirconate titanate particles in 300mL of toluene solution, adding 5g of silane coupling agent KH550, heating for 12h at 80 ℃ in nitrogen atmosphere, and then cleaning, drying and sieving to obtain 10g of surface-modified nano barium zirconate titanate particles;
g. adding 15g of surface-modified nano barium zirconate titanate particles and 35g of maleic anhydride grafted polypropylene into a torque rheometer, and carrying out melt blending at 180 ℃ for 10mins to obtain 50g of nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch, wherein an antioxidant 1010 with the mass fraction of 0.1 wt% needs to be added in the process;
h. 6.67g of nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch, 19g of polypropylene and 14.33g of maleic anhydride grafted polypropylene are added into a torque rheometer, and are melted and blended for 10mins at the temperature of 180 ℃ to obtain 40g of nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, and in the process, 0.1 wt% of antioxidant 1010 needs to be added.
Second embodiment:
a. ball-milling 25g of micron-grade barium carbonate in absolute ethyl alcohol for 18 hours, drying and sieving to obtain 25g of nanometer-grade barium carbonate;
b. 5.5875g of nano-scale titanium dioxide, 2.1552g of zirconium dioxide and 17.2573g of nano-scale barium carbonate obtained in the step a are mixed in absolute ethyl alcohol, and are dried and sieved after being ball-milled for 5 hours, so that 25g of first powder is obtained;
c. sintering 25g of the first powder for 3 hours at 1200 ℃ to obtain 21.1513g of second powder;
d. ball-milling 20g of the second powder in absolute ethyl alcohol for 18h, drying and sieving to obtain 20g of nano barium zirconate titanate particles;
e. dispersing 10g of nano barium zirconate titanate particles in 100mL of hydrogen peroxide solution with the mass fraction of 30 wt%, carrying out condensation reflux for 6h at 80 ℃, and then carrying out cleaning, drying and sieving to obtain 10g of hydroxylated nano barium zirconate titanate particles;
f. dispersing 10g of hydroxylated nano barium zirconate titanate particles in 300mL of xylene solution, adding 5g of silane coupling agent KH550, heating for 18h at 90 ℃ under argon atmosphere, and then cleaning, drying and sieving to obtain 10g of surface-modified nano barium zirconate titanate particles;
g. adding 15g of surface-modified nano barium zirconate titanate particles and 35g of maleic anhydride grafted polypropylene into a torque rheometer, and carrying out melt blending at 190 ℃ for 15mins to obtain 50g of nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch, wherein an antioxidant 1010 with the mass fraction of 0.1 wt% needs to be added in the process;
h. adding 13.33g of nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch, 18g of polypropylene and 8.67g of maleic anhydride grafted polypropylene into a torque rheometer, and carrying out melt blending at 190 ℃ for 15mins to obtain 40g of nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, wherein antioxidant 1010 with the mass fraction of 0.1 wt% needs to be added in the process.
The third embodiment:
a. ball-milling 25g of micron-grade barium carbonate in alcohol for 24 hours, drying and sieving to obtain 25g of nanometer-grade barium carbonate;
b. 5.5875g of nano-scale titanium dioxide, 2.1552g of zirconium dioxide and 17.2573g of nano-scale barium carbonate obtained in the step a are mixed in alcohol, ball-milled for 6 hours, dried and sieved to obtain 25g of first powder;
c. sintering 25g of the first powder for 4 hours at 1300 ℃ to obtain 21.1513g of second powder;
d. ball-milling 20g of the second powder in alcohol for 24h, drying and sieving to obtain 20g of nano barium zirconate titanate particles;
e. dispersing 10g of nano barium zirconate titanate particles in 100mL of hydrogen peroxide solution with the mass fraction of 30 wt%, carrying out condensation reflux for 8h at 105 ℃, and then carrying out cleaning, drying and sieving to obtain 10g of hydroxylated nano barium zirconate titanate particles;
f. dispersing 10g of hydroxylated nano barium zirconate titanate particles in 300mL of toluene solution, adding 5g of silane coupling agent KH550, heating for 24h under a helium atmosphere at 100 ℃, and then cleaning, drying and sieving to obtain 10g of surface-modified nano barium zirconate titanate particles;
g. adding 15g of surface-modified nano barium zirconate titanate particles and 35g of maleic anhydride grafted polypropylene into a torque rheometer, and carrying out melt blending at the temperature of 200 ℃ for 20mins to obtain 50g of nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch, wherein an antioxidant 1010 with the mass fraction of 0.1 wt% needs to be added in the process;
h. adding 20g of nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch, 17g of polypropylene and 3g of maleic anhydride grafted polypropylene into a torque rheometer, and carrying out melt blending at the temperature of 200 ℃ for 20mins to obtain 40g of nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, wherein an antioxidant 1010 with the mass fraction of 0.1 wt% needs to be added in the process.
In the above embodiments, it should be noted that, in the step a, the setting of the ball milling time is only an exemplary description, and in order to ensure that the particle size of the particles reaches the nanometer level, a skilled person may select the time according to the actual situation; in the step c, the temperature and the time required for sintering the first powder are the best data obtained by the test of the disclosure, and in the temperature and time range, the barium zirconate titanate ceramic can be generated, if the sintering temperature is lower than 1100 ℃ and the sintering time is lower than 2 hours, lattice structure impurity phases can be caused, and the ceramic powder with a single perovskite structure cannot be synthesized; if the sintering temperature is higher than 1300 ℃ and the sintering time is higher than 4 hours, the crystal grains are excessively grown and the grain size is excessively large. In the step d, the setting of the ball milling time of the second powder is only an exemplary illustration, and in order to ensure that the particle size of the particles reaches the nanometer level, a technician can select the time according to the actual situation; in the step e, the temperature and the time for condensing and refluxing the second powder are the best data obtained by the experiment of the disclosure, and if the temperature is lower than 80 ℃, the temperature required by the hydroxylation reaction cannot be provided; if the temperature is higher than 105 ℃, there is a safety hazard to cause explosion of the reaction apparatus. In addition, if the reaction time is less than 4 hours, the reaction tends to proceed incompletely, and it is considered that the reaction is completed when the reactants are consumed after 4 to 8 hours. In step f, if the temperature is lower than 80 ℃, the temperature required by the hydroxylation reaction cannot be provided; if the temperature is higher than 100 ℃, there is a safety hazard to cause explosion of the reaction apparatus. In addition, if the reaction time is less than 12 hours, the reaction is easy to be incomplete, and it is considered that the surface active sites of the hydroxylated nano barium zirconate titanate particles are completely reacted after 12 to 24 hours. In the step g, if the melting temperature is lower than 180 ℃, the maleic anhydride grafted polypropylene cannot be fully melted and has poor fluidity; if the melting temperature is higher than 200 ℃, the maleic anhydride grafted polypropylene may be oxidized. In addition, if the melting time is less than 10min, the uniform dispersion of the nano barium zirconate titanate particles in the maleic anhydride grafted polypropylene cannot be ensured; if the melting time is more than 20min, oxidation of the maleic anhydride grafted polypropylene may also occur. In the step h, if the melting temperature is lower than 180 ℃, polypropylene and maleic anhydride grafted polypropylene cannot be fully melted and have poor fluidity; if the melting temperature is higher than 200 ℃, the polypropylene and the maleic anhydride grafted polypropylene may be oxidized. In addition, if the melting time is less than 10min, the uniform dispersion of the nano barium zirconate titanate particles in the polypropylene and the maleic anhydride grafted polypropylene cannot be ensured; if the melting time is more than 20min, oxidation of the polypropylene and the maleic anhydride grafted polypropylene may also occur.
In addition, in the step g and the step h, if the content of the added antioxidant is less than 0.1 wt%, the antioxidant cannot play a role in inhibiting the oxidation of the polymer; if the content of the antioxidant is more than 0.1 wt%, the properties of the composite material may be changed, and the breakdown property may be reduced due to the introduction of too many small molecules.
The present disclosure also provides a method for preparing a composite film containing a nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, comprising the steps of:
s1000: cutting a plurality of circular holes on the polyimide film A;
s2000: placing a polyimide film B at the bottom of the polyimide film A, placing a proper amount of nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material in a round hole of the polyimide film A, and then placing a polyimide film C above the polyimide film A to package the polyimide film A;
s3000: and carrying out hot-pressing treatment on the packaged polyimide films A-C to obtain the composite film containing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material.
The following describes the preparation method of the composite film in detail with reference to specific examples:
the first embodiment:
a. cutting a plurality of circular holes with the diameter of 5cm on the polyimide film A with the thickness of 100 mu m by using a circular cutter with the diameter of 50 mm;
b. placing a polyimide film B with the thickness of 100 mu m at the bottom of the polyimide film A, placing 0.2g of nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material in a round hole of the polyimide film A, and then placing a polyimide film C with the thickness of 100 mu m above the polyimide film A to package the polyimide film A;
c. and placing the packaged polyimide films A-C in two square iron plates, and carrying out hot-pressing treatment on the polyimide films by using a flat vulcanizing instrument to obtain the composite film containing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material, wherein the temperature of the flat vulcanizing instrument is set to 180 ℃, the pressure is set to 15MPa, the treatment time is set to 10mins, the exhaust frequency is set to 15 times, and the exhaust time is set to 10s each time.
Second embodiment:
unlike the first embodiment, the amount of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material placed in the round hole in the present embodiment was 0.3g, and the parameters of the vulcanizing press were adjusted as follows: the temperature was set at 190 ℃, the treatment time was set at 15mins, the number of exhausts was set at 10, and the time per exhaust was set at 15 s.
The third embodiment:
unlike the first embodiment, in this embodiment, the amount of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material placed in the circular hole is 0.4g, and the parameters of the flat vulcanization instrument are adjusted as follows: the temperature was set at 200 ℃, the pressure at 20MPa, the treatment time at 20mins and the exhaust time at 20s each.
In the above examples, it should be noted that, if the hot pressing temperature is lower than 180 ℃, the polymer in the polyimide film cannot be melted sufficiently, and the flowability is poor; if the hot pressing temperature is higher than 200 c, the polymer in the polyimide film may be oxidized. If the pressure is less than 15MPa, the surface smoothness of the polyimide film is difficult to ensure; if the pressure is more than 20MPa, the crystallization state of the polymer in the polyimide film is affected; if the hot pressing time is less than 10min, the polymer in the polyimide film cannot be ensured to be fully melted; if the hot pressing time is more than 20min, the oxidation of the polymer in the polyimide film may also occur.
The technical effects of the solution of the present disclosure will be described below with reference to fig. 3(a) to 6 (c).
Fig. 3(a) is a microscopic morphology characterization SEM image of polypropylene-maleic anhydride grafted polypropylene composite material not doped with nano barium zirconate titanate, fig. 3(b) to 3(d) are microscopic morphology characterization SEM images of polypropylene-maleic anhydride grafted polypropylene composite material doped with nano barium zirconate titanate with different percentage contents, and it can be seen from fig. 3(b) to 3(d) that nano barium zirconate titanate particles are uniformly dispersed without obvious agglomeration at doping amount of 5-15 wt%, which indicates that the nano particles have good compatibility with polymer matrix.
Fig. 4 is a graph of the dielectric constant and the material loss spectrum of the composite material, as shown in fig. 4, the dielectric constant of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material shows a monotonous rising trend along with the increase of the content of the nano barium zirconate titanate particles, and when the content of the nano barium zirconate titanate particles is 15 wt%, the dielectric constant of the composite material is increased to 3.18(0.1Hz), which is increased by 40.7% compared with pure PP (2.25). Notably, at 10-1105In the range of Hz, the dielectric constant of the composite material has good frequency stability. The nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material is prepared at 102-103The weak loss peak in the Hz range is introduced by the turning polarization of the MAH polar groups. At 10-1-102In the low frequency range of Hz, the material loss increases slightly due to the small amount of relaxation loss introduced by impurity ions. In general, compared with pure PP, the introduction of the high dielectric constant nano barium zirconate titanate particles does not cause obvious increase of material loss along with zirconiumThe change trend of the doped content of the barium titanate is not obvious and still keeps 10-2Order of magnitude and good frequency stability. As a potential ideal capacitor material, the low material loss obtained by the composite material has important significance in the field of engineering application.
FIG. 5 shows the Weibull distribution diagram of the DC breakdown of the composite material, as shown in FIG. 4, the introduction of nano barium zirconate titanate particles can cause the breakdown field strength to be reduced slightly. When the content of the nano barium zirconate titanate particles is respectively 5 wt%, 10 wt% and 15 wt%, the breakdown field strength of the composite material is reduced by 22.52 MV/m, 46.62 MV/m and 64.43MV/m compared with that of pure PP, and although the breakdown field strength of the composite material is slightly reduced, all samples maintain high breakdown field strength of more than 350 Mv/m. The composite material still has enough margin and higher voltage withstanding level when used as a power capacitor material.
Fig. 6(a) to 6(c) show energy storage characteristics of the composite material, where fig. 6(a) shows a hysteresis loop of the composite material when the electric field strength is 200MV/m, fig. 6(b) shows energy density and charge/discharge efficiency of the composite material when the electric field strength is 200MV/m, and fig. 6(c) shows a maximum energy storage density of the composite material. As shown in fig. 6(a), the nano barium zirconate titanate particles significantly improve the saturation potential shift vector of the composite material; meanwhile, the more the content of the nano barium zirconate titanate particles in the composite material is, the larger the corresponding saturated potential shift vector is; the D-E loop of the PP is linear, and the D-E loop of the composite material is characterized by a nonlinear dielectric medium due to the nano barium zirconate titanate particles, so that little energy loss exists. But the nonlinear degree of the composite dielectric hysteresis loop is extremely low, and the residual polarization intensity in the D-E loop of the composite material is almost zero in overall view. As shown in fig. 6(b), at the same electric field intensity, the discharge energy density of the composite material shows a monotone increasing trend as the content of the nano barium zirconate titanate particles increases. In particular, when the nano barium zirconate titanate particle filling content is 15 wt%, the high polarization strength generated by the composite material enables the discharge energy density to be as high as 0.554J/cm3 compared with pure PP (0.398J/cm)3) The increase is 39.3%. Although the charge-discharge efficiency of the composite material is reduced, the minimum value is reduced to 93.44 percent, and the composite material still has the advantages of low charge-discharge efficiency and low costThe high level of more than 90 percent is maintained. The composite material has ultrahigh charge-discharge efficiency, and is expected to avoid the problem that the energy storage characteristic of the thin film capacitor is reduced due to overlarge energy dissipation under the high field condition. The maximum energy storage density calculation result of the composite material is shown in fig. 6(c), although the breakdown field strength of the composite material is slightly reduced, the dielectric constant of the composite material is remarkably improved due to the introduction of the nano barium zirconate titanate particles, and the energy storage density of the composite material is improved under the balance regulation of the dielectric constant and the breakdown field strength. When the nano barium zirconate titanate particle filling content is 5 wt%, the maximum energy storage density of the composite material is 1.972J/cm3 compared with pure PP (1.756J/cm)3) The improvement is 12.3%.
The foregoing description has been presented for purposes of illustration and description. Furthermore, the description is not intended to limit embodiments of the application to the form disclosed herein. While a number of example aspects and embodiments have been discussed above, those of skill in the art will recognize certain variations, modifications, alterations, additions and sub-combinations thereof.
Claims (10)
1. A nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material comprises the following components in percentage by mass:
5-15 wt% of nano barium zirconate titanate,
42.5 to 47.5 weight percent of maleic anhydride grafted polypropylene,
42.5 to 47.5 weight percent of polypropylene,
the nano barium zirconate titanate comprises the following components in percentage by mass:
69.0 wt% of micron-sized barium carbonate,
22.4 percent by weight of nano-scale titanium dioxide,
nanometer zirconium dioxide 8.6 wt%.
2. A preparation method of a nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material preferably comprises the following steps:
s100: preparing nano barium zirconate titanate particles;
s200: carrying out surface modification treatment on the nano barium zirconate titanate particles to obtain surface-modified nano barium zirconate titanate particles;
s300: preparing a nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch according to the surface-modified nano barium zirconate titanate particles;
s400: and preparing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material according to the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch.
3. The method of claim 2, wherein step S100 comprises the steps of:
s101: ball-milling micrometer-grade barium carbonate in alcohol or absolute ethyl alcohol for 12-24h, drying, and sieving to obtain nanometer-grade barium carbonate;
s102: mixing nano-scale titanium dioxide, nano-scale zirconium dioxide and nano-scale barium carbonate in alcohol or absolute ethyl alcohol, carrying out ball milling for 4-6h, drying and sieving to obtain first powder;
s103: sintering the first powder at 1100-1300 ℃ for 2-4h to obtain second powder;
s104: and ball-milling the second powder in alcohol or absolute ethyl alcohol for 12-24h, drying and sieving to obtain the nano barium zirconate titanate particles.
4. The method according to claim 2, wherein the step S200 of performing surface modification treatment on the nano barium zirconate titanate particles comprises the following steps:
s201: dispersing nano barium zirconate titanate particles in a hydrogen peroxide solution, carrying out condensation reflux for 4-8h at the temperature of 80-105 ℃, and then carrying out cleaning, drying and sieving to obtain hydroxylated nano barium zirconate titanate particles;
s202: dispersing the hydroxylated nano barium zirconate titanate particles in a toluene or xylene solution, adding a proper amount of silane coupling agent, heating for 12-24h under an inert gas atmosphere at 80-100 ℃, and then cleaning, drying and sieving to obtain surface-modified nano barium zirconate titanate particles.
5. The method of claim 2, wherein the preparing of the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch from the surface-modified nano barium zirconate titanate particles in step S300 is performed by: and melting and blending the surface-modified nano barium zirconate titanate particles and maleic anhydride grafted polypropylene at the temperature of 180-200 ℃ for 10-20mins to obtain the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch.
6. The method of claim 2, wherein the preparing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material according to the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch in the step S400 is performed by the following method: and melting and blending the nano barium zirconate titanate-maleic anhydride grafted polypropylene master batch, polypropylene and maleic anhydride grafted polypropylene for 10-20mins at the temperature of 180-200 ℃ to obtain the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material.
7. A method for preparing a composite film containing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material of claim 1, comprising the following steps:
s1000: cutting a plurality of circular holes on the polyimide film A;
s2000: placing a polyimide film B at the bottom of the polyimide film A, placing a proper amount of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material in a round hole of the polyimide film A, and then placing a polyimide film C above the polyimide film A to package the polyimide film A;
s3000: and carrying out hot-pressing treatment on the packaged polyimide films A-C to obtain the composite film containing the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material.
8. The method of claim 7, wherein the thickness of each of the polyimide film A, the polyimide film B, and the polyimide film C is 100 μm.
9. The method of claim 7, wherein in the step S2000, the content of the nano barium zirconate titanate-polypropylene-maleic anhydride grafted polypropylene composite material placed in the round holes of the polyimide film A is 0.2-0.4 g.
10. The method as claimed in claim 7, wherein the step S3000 comprises performing the thermocompression treatment on the packaged polyimide films a-C at a temperature of 180-200 ℃, a pressure of 15-20MPa, and a time of 10-20 mins.
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